JP2017008024A - Patches - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide patches excellent in re-applicable property.SOLUTION: In patches equipped with a support and an adhesive layer, the adhesive layer is formed from an adhesive composition containing (A) polyacrylic acid and/or a salt thereof, (B) polyalkylene oxide-based water-absorbing resin, and (C) one or more organic acids selected from tartaric acid, malic acid, lactic acid, and citric acid, wherein the average molecular weight of component (A) is 3 million or more, the compounding mass ratio of component (A) and component (C) meets the relationship of formula [acrylate unit of component (A)-carboxyl group of component (C)]/[acrylate unit of component (A) + acrylic acid unit of component (A)]≤0.22, and the adhesive composition has a pH of 4-5.5, and a moisture content of 80 mass% or more.SELECTED DRAWING: None

Description

  The present invention relates to a patch having a cooling effect that is used by being affixed to a portion of the body such as the forehead to be cooled, and particularly relates to a patch excellent in re-sticking property.

  Conventionally, a gel-like pressure-sensitive adhesive having a cooling effect on one side of a support such as a non-woven fabric as a patch having a cooling effect for heat countermeasures or for obtaining a cooling sensation or lowering body temperature during heat generation Many patches with a layer formed are on the market. With these patches, in order to be able to use them more effectively and comfortably, try to improve the cooling effect, its durability and adhesiveness (hardness to peel), and reduce stickiness and irritation during use. Many attempts have been made to improve the feeling of use.

  For example, Japanese Patent Application Laid-Open No. 2010-284519 (Patent Document 1) discloses an invention relating to a cooling sheet used by being attached to clothing. In this invention, by reviewing the structure of the sheet, it can be used without being directly attached to the skin, a sufficient refreshing feeling and cooling effect can be obtained, and the pain caused by the refreshing feeling can be suppressed. Further, in Japanese Patent Application Laid-Open No. 2004-33279 (Patent Document 2), the water-containing pressure-sensitive adhesive layer is infiltrated between the fibers of the fiber sheet layer having a low basis weight so that both layers are firmly bonded and highly transparent. A technique for obtaining an agent has been proposed. The patch obtained by this technique is not conspicuous even when it is applied, has a high cooling effect, and is not sticky to the surface of the support. In addition, JP-A No. 2002-136578 (Patent Document 3) discloses an adhesive for external use with an increased cooling effect by using a highly water-absorbing polymer compound having a specific water-absorbing ability as a dispersion aid to improve the water content. Agent compositions have been proposed.

  As described above, many improvements have been made with respect to the cooling effect and feeling of use of the patch. However, when the patch is put on the body once, it has an adhesive strength when peeled off. In many cases, sufficient adhesive strength cannot be obtained when reattaching and using. For example, if the hair is caught on the body, the hair is uncomfortable, or the hair cannot be applied to the target part, it is assumed that it is peeled off and then attached again. In particular, under the forehead or armpit where the patch of the present invention is affixed, there are many opportunities to re-apply because it cannot be applied while visually observing. In such a case, the peeled patch is affixed to the same location again. Even so, the adhesive strength was remarkably reduced, so it often peeled off immediately. Therefore, there is still room for improvement with respect to the adhesive strength (re-adhesive strength) when the adhesive is reapplied.

  Other prior art documents related to the present invention include JP-A-2005-94595 (Patent Document 4) and JP-A-2004-131383 (Patent Document 5).

JP 2010-284519 A JP 2004-33279 A JP 2002-136578 A JP 2005-94595 A JP 2004-131383 A

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a patch having high re-adhesive strength and excellent restickability.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have determined that the adhesive layer comprises (A) polyacrylic acid and / or a salt thereof in a patch comprising a support and an adhesive layer. B) a polyalkylene oxide water-absorbent resin, and (C) a pressure-sensitive adhesive composition containing one or more organic acids selected from tartaric acid, malic acid, lactic acid, and citric acid. By adjusting the average molecular weight, the blending mass ratio of the component (A) and the component (C), the pH of the pressure-sensitive adhesive composition, and the water content to a specific range, It has been found that the adhesive strength is improved, and the present invention has been made.

That is, the present invention provides the following patch.
[1] In a patch comprising a support and an adhesive layer, the adhesive layer comprises:
(A) polyacrylic acid and / or a salt thereof,
(B) a polyalkylene oxide water-absorbing resin,
(C) formed of a pressure-sensitive adhesive composition containing one or more organic acids selected from tartaric acid, malic acid, lactic acid, and citric acid, and the average molecular weight of component (A) is 3 million or more, (A) The blending mass ratio of the component and the component (C) is the following formula: [(A) component acrylate unit- (C) component carboxyl group] /
[Acrylate unit of component (A) + Acrylic acid unit of component (A)] ≦ 0.22
And the adhesive composition has a pH of 4 to 5.5 and a water content of 80% by mass or more.
[2] The patch according to [1], further comprising (D) a polyvalent metal salt.
[3] The patch according to [1] or [2], further comprising (E) glycerin in the pressure-sensitive adhesive composition in an amount of 1% by mass to less than 5% by mass.
[4] The patch according to any one of [1] to [3], wherein the content of the component (A) is 1 to 15% by mass in the pressure-sensitive adhesive composition.
[5] The patch according to any one of [1] to [4], wherein the content of the component (B) is 0.01 to 5% by mass in the pressure-sensitive adhesive composition.
[6] The patch according to any one of [1] to [5], further comprising (F) sodium carboxymethylcellulose in an amount of 1 to 10% by mass in the pressure-sensitive adhesive composition.
[7] The patch according to any one of [1] to [6], wherein the content of the component (C) is 0.1 to 5% by mass in the pressure-sensitive adhesive composition.

  ADVANTAGE OF THE INVENTION According to this invention, the patch which has the re-adhesive force and has the cooling effect excellent in re-sticking property can be provided.

The patch of the present invention is formed by forming a gel-like pressure-sensitive adhesive layer (hereinafter sometimes referred to as “plaster”) having a cooling effect on the surface of a support such as a nonwoven fabric. The agent layer is formed of a pressure-sensitive adhesive composition containing the following components.
Hereinafter, the pressure-sensitive adhesive composition will be described in detail.

(A) Polyacrylic acid and / or salt thereof (A) As component (A), polyacrylic acid salt such as polyacrylic acid or sodium polyacrylate, partially neutralized product obtained by neutralizing part of polyacrylic acid with salt (Polyacrylic acid partial neutralized product), carboxyvinyl polymer partially cross-linked with polyacrylic acid, and the like. These can be used individually by 1 type or in combination of 2 or more types. In the present invention, polyacrylic acid salt and polyacrylic acid may be used in combination, or a polyacrylic acid partial neutralized product may be used alone, or a polyacrylic acid partial neutralized product and polyacrylic acid or polyacrylic acid. An acrylate, a carboxyvinyl polymer partially cross-linked with polyacrylic acid, or the like may be used in combination. Examples of the counter ion of the polyacrylate and the partially neutralized polyacrylic acid include sodium, potassium, and amines. The average molecular weight of the component (A) needs to be 3 million or more, and is preferably 3.5 million or more from the viewpoint of the development of adhesive strength and the shape retention of the gel. On the other hand, the upper limit of the average molecular weight is not particularly limited, but is 7.5 million or less, preferably 4.5 million or less. When the molecular weight of the component (A) is less than 3 million, the re-adhesive force is inferior. Here, said average molecular weight means the mass average molecular weight measured by gel permeation chromatography (GPC).

The partially neutralized polyacrylic acid usually contains a metal ion such as sodium ion, and a part of the carboxyl group in the molecule is neutralized by the metal ion. The degree of neutralization of the component (A) is not particularly limited, but it is preferable to select a component that is somewhat low from the relationship that satisfies the blending mass ratio with the component (C) described later. The degree of neutralization is not particularly limited, but specifically, 30 to 70 mol% is preferable, and 30 to 60 mol% is more preferable. If the degree of neutralization of component (A) is too high, it is necessary to increase the amount of component (C) in order to satisfy the relational expression described below. In addition, the said neutralization degree is a value calculated | required by the following formula.
Degree of neutralization (mol%) = 100 × “number of moles of neutralized carboxyl groups in the molecule” /
"Total number of moles of carboxyl groups in the molecule (including neutralized and unneutralized)"

  In addition, in this invention, when using 2 or more types of (A) component, said average molecular weight and neutralization degree say the average value as the whole (A) component.

  (A) Content of a component does not have a restriction | limiting in particular, Although it can select suitably according to the objective, 1-15 mass% is preferable in a composition, and 3-10 mass% is more preferable. (A) Adhesive force (re-adhesive force) improves by making content of a component more than a minimum, and the viscosity at the time of manufacture does not become high too much, and productivity is ensured.

(B) Polyalkylene oxide water-absorbing resin (B) Polyalkylene oxide water-absorbing resin is a nonionic water-absorbing resin having a three-dimensional network structure due to partial modification of polyoxyethylene. Cork (manufactured by Sumitomo Seika Co., Ltd.) can be mentioned. The content of component (B) is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferably 0.01 to 5% by mass and more preferably 0.1 to 3% by mass in the composition. When the content of the component (B) is 0.01% by mass or more, sufficient shape retention of the gel can be obtained. On the other hand, when the content of the component (B) is 5% by mass or less, the water content is high and the adhesive strength is improved.

(C) Organic acid As the organic acid (C), citric acid, tartaric acid, malic acid, and lactic acid can be used, and tartaric acid can be particularly preferably used in the present invention. (C) 0.01-5 mass% is preferable in a composition, and, as for content of a component, 0.1-2 mass% is more preferable. The said (C) component may be used individually by 1 type, and may use 2 or more types together.

Moreover, in this invention, the compounding mass ratio of (A) component and (C) component is following formula [Acrylate unit of (A) component-carboxyl group of (C) component] /
[Acrylate unit of component (A) + Acrylic acid unit of component (A)] ≦ 0.22
It needs to be formulated to satisfy the relationship
0.1 ≦ [(A) component acrylate unit− (C) component carboxyl group] /
[Acrylate unit of component (A) + Acrylic acid unit of component (A)] ≦ 0.22
It is preferable to satisfy the relationship
0.1 ≦ [(A) component acrylate unit− (C) component carboxyl group] /
[Acrylate unit of component (A) + Acrylic acid unit of component (A)] ≦ 0.17
It is more preferable to satisfy this relationship. When the value obtained from the above formula exceeds 0.22, not only a sufficient adhesive strength cannot be obtained, but also the re-adhesive strength decreases.

Here, the calculation method of the value of the above formula will be described by taking Example 1 described later as an example. In the following calculation, the molecular weight of acrylic acid was 72, the molecular weight of sodium was 23, and the molecular weight of tartaric acid was 150 (valence: 2).
The conditions of Example 1 are as follows.
Compounding amount of component (A) and component (C) (when the total amount of the composition is 100 g)
(A) Polyacrylic acid partial neutralized product (neutralization degree: 40 mol%) 4.8 g
(C) Tartaric acid (valence: 2) 1 g

(1) Acrylate unit and acrylic acid unit of component (A) In the 4.8 g of the above polyacrylic acid partial neutralized product, X is the total number of acrylate units and acrylic acid units, and the number of acrylate units is If Y,
72X + 23Y = 4.8
Y = 0.4X
The following equation holds. Here, when X and Y are obtained by solving the above equation,
X = 0.0591 (I)
Y = 0.0236 (II)
Is obtained.
(2) Carboxyl group of component (C) From the above conditions 1 × 2/150 = 0.0133 (III)
(3) Calculation of value From (I) to (III) above,
[(II)-(III)] / (I)
= (0.0236-0.0133) /0.0591=0.17

Therefore, it can be confirmed that the blending mass ratio of the component (A) and the component (C) in Example 1 satisfies the above formula.

  The pH (25 ° C.) of the pressure-sensitive adhesive composition is 4 to 5.5, preferably 4.1 to 5.0. By satisfying the above relational expression and setting the pH of the pressure-sensitive adhesive composition within the above range, the desired excellent reattachability can be obtained. If the pH of the composition is too low, skin irritation may occur. On the other hand, when the pH of the composition is too high, the adhesive strength (re-adhesive strength) decreases. In the present invention, the pH is measured with a pH meter (Toa Denpa Kogyo Co., Ltd., model: HM-30V).

(D) Polyvalent metal salt In the pressure-sensitive adhesive composition of the present invention, the component (A) is preferably a crosslinked product of (D) a polyvalent metal salt. (D) As polyvalent metal salt, the kind in particular is not restrict | limited, What is used for the adhesive layer (plaster) can be used. Specific examples include alums such as potassium alum, ammonium alum, iron alum, aluminum hydroxide, aluminum sulfate, aluminum chloride, aluminum acetate, aluminum oxide, aluminum silicate, aluminum metasilicate, calcium hydroxide, calcium carbonate, Calcium sulfate, calcium nitrate, calcium chloride, calcium acetate, calcium oxide, calcium phosphate, magnesium hydroxide, magnesium carbonate, magnesium sulfate, magnesium acetate, magnesium silicate, magnesium oxide, magnesium hydroxide alumina, magnesium magnesium metasilicate, silicic acid Examples include magnesium aluminate, synthetic hydrotalcite, and dihydroxyaluminum aminoacetate. These can be used individually by 1 type or in combination of 2 or more types.

  In the present invention, those that act gradually rather than those that act immediately are preferable from the viewpoint that the pressure-sensitive adhesive composition is uniformly applied to at least one surface of the support in the spreading step. As such a polyvalent metal salt, for example, magnesium aluminate silicate, magnesium aluminate hydroxide, magnesium aluminate metasilicate, synthetic hydrotalcite, dihydroxyaluminum aminoacetate and the like are preferable. Synthetic hydrotalcite, dihydroxyaluminumamino Acetate is most preferred.

  The blending amount of component (D) is not particularly limited, and is appropriately selected depending on the type of polyvalent metal salt, (A) polyacrylic acid and / or its salt, and the type of water-soluble polymer compound other than polyacrylic acid. However, 0.005 to 3% by mass is preferable in the composition, and 0.03 to 1% by mass is more preferable. When the blending amount of the component (D) is 0.005% by mass or more, sufficient gel shape retention can be obtained, and by setting it to 3% by mass or less, the adjustment of the curing rate at the time of manufacture can be easily performed. can do.

(E) Glycerin The pressure-sensitive adhesive composition of the present invention preferably contains (E) glycerin. By containing (E) component, since the softness | flexibility of an adhesive layer is maintained even after water evaporates during use, the adhesiveness in use (during sticking) can be maintained more. The content of the component (E) is preferably 1% by mass or more and less than 5% by mass, and more preferably 2% by mass or more and less than 4% by mass.

(F) Sodium carboxymethylcellulose (F) As carboxymethylcellulose sodium, a 1% aqueous solution having a viscosity of 10 to 3000 mPa · s at 25 ° C. and a degree of etherification of 0.5 or more can be suitably used. By setting the viscosity to 10 mPa · s or more, the gel retainability can be obtained, so that the pressure-sensitive adhesive composition does not protrude from the side of the support and the back spot is less likely to occur. On the other hand, by setting the viscosity to 3000 mPa · s or less, the viscosity does not become too high, and the workability of kneading and spreading is improved. Specific examples of the component (F) include CMC Daicel 1380 (Daicel Finechem Co., Ltd.), CMC Daicel 1390 (same as above), etc., which may be used alone or in combination of two or more. May be. The content of the component (F) is not particularly limited, and is appropriately selected depending on the type of (D) polyvalent metal salt, (A) polyacrylic acid and / or its salt, and other water-soluble polymer compound. Although 1-10 mass% is preferable in a composition, 3-8 mass% is more preferable. When the content is 1% by mass or more, the shape retention necessary for the patch is obtained, and when the content is 10% by mass or less, the adhesiveness can be improved. The viscosity is a value measured by a BH viscometer (rotor: No. 2, rotation speed: 20 rpm) manufactured by Tokyo Keiki Co., Ltd.

(G) Other components The other components are not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose. For example, the water-soluble polymer compound (component (A) and (Excluding component (F)), curing modifier, mineral powder, fragrance, pigment, preservative, polyhydric alcohol (excluding component (E)), emulsifier (surfactant), cooling agent, and stabilizer Etc. can be blended. There is no restriction | limiting in particular in content of each said component, According to the objective, it can select suitably.

  Examples of the water-soluble polymer compound (excluding the components (A) and (F)) include, for example, gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxypropyl cellulose, hydroxyethyl cellulose, methyl cellulose, sodium alginate, xanthan gum, arabic gum, tragacanth gum, karaya gum And maleic anhydride copolymer. Among these, polyvinyl alcohol is preferable. These may be used individually by 1 type and may use 2 or more types together. The content of the water-soluble polymer compound is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of sufficiently obtaining the shape retention of the gel, 1 to 15% by mass in the composition is preferable, 5-10 mass% is more preferable. In addition, the water solubility in this invention means melt | dissolving in water by the density | concentration of 1 mass% or more.

  The type of the curing regulator for adjusting the curing by the (D) polyvalent metal salt is not particularly limited, and those conventionally used for adhesive layers (plasters) of patches can be used. it can. Specific examples include disodium edetate (EDTA-2Na). These can be used individually by 1 type or in combination of 2 or more types. Although the compounding quantity of a hardening regulator can be selected suitably, 0.001-5 mass% is suitable in a composition normally. By setting the blending amount within the above range, the curing rate is appropriately delayed, and the effect rate at the time of production can be easily adjusted.

  There is no restriction | limiting in particular as mineral powder, According to the objective, it can select suitably. Specific examples of the mineral powder include kaolin, bentonite, montmorillonite, zinc oxide, titanium oxide, and anhydrous silicic acid. These may be used individually by 1 type and may use 2 or more types together. Although the compounding quantity of mineral powder can be suitably selected according to the objective, 1-5 mass% is preferable in a composition from the point which acquires the shape-retaining property of gel enough. If the blending amount of the mineral powder is too large, the plaster hardness may become so hard that it cannot be spread.

  The type of the fragrance is not particularly limited, and for example, what is usually used as a fragrance for the patch can be appropriately selected according to the purpose. Specific examples of flavors include anise, angelica, benzoin, immortelle, chamomile, garlic, cardamom, galvanum, caraway, carrot seed, guaiac wood, clarisage, grapefruit, cypress, sandalwood, cedarwood, juniper, star anise, sage , Geranium, celery, thyme, tarragon, turpentine, spruce, frankincense, violet, pine, parsley, birch, patchouli, rose, hyssop, fennel, black pepper, bodaiju flower, myrrh, yarrow, lemon, lemongrass, rosemary, laurel , Shimotsukegiku, Peach, Cornflower, Eucalyptus, Yuzu, Lavender and other herbal oils or extracts, other lower alcohols, aldehydes and the like. These may be used individually by 1 type and may use 2 or more types together. There is no restriction | limiting in particular in the compounding quantity of a fragrance | flavor, Although it can select suitably according to the objective, About 0.0001-1 mass% is suitable in a composition. If the blending amount is too small, the effect of blending cannot be obtained sufficiently, and if it is too large, there is a risk of causing skin irritation.

  There is no restriction | limiting in particular as a pigment | dye, The thing conventionally used for the adhesive layer (plaster) can be suitably selected according to the objective. Specific examples of the dye include Red No. 2, Red No. 3, Red No. 102, Red No. 104, Red No. 105, Red No. 106, Red No. 201, Red No. 202, Red No. 203, Red No. 204 and Red No. 205. Red 206, Red 207, Red 208, Red 213, Red 214, Red 215, Red 218, Red 219, Red 220, Red 221, Red 223, Red 225, Red 226, Red 227, Red 228, Red 230 (1), Red 230 (2), Red 231, Red 232, Red 401, Red 404, Red 405, Red 501 Red 502, Red 503, Red 504, Red 505, Red 506, Yellow 4, Yellow 5, Yellow 201, Yellow 202 (1), Yellow 202 (2), Yellow No. 203 Yellow 204, Yellow 205, Yellow 401, Yellow 402, Yellow 403 (1), Yellow 404, Yellow 405, Yellow 406, Yellow 407, Green 3, Green 201, Green 202 No., Green No. 204, Green No. 205, Green No. 401, Green No. 402, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 202, Blue No. 203, Blue No. 204, Blue No. 205, Blue No. 401, Blue 403, Blue 404, Orange 201, Orange 203, Orange 204, Orange 205, Orange 206, Orange 207, Orange 401, Orange 402, Orange 403, Brown 201, Purple 201 No., purple No. 401, black No. 401 and the like. These may be used individually by 1 type and may use 2 or more types together. There is no restriction | limiting in particular in the compounding quantity of a pigment | dye, Although it can select suitably according to the objective, 0.00005-0.1 mass% is preferable in a composition, and 0.0001-0.01 mass% is more preferable. . If the blending amount is too small, the effect of blending may not be sufficiently obtained, and if it is too large, the color tone may be too strong. In addition, when blending a dye, after the dye is dissolved in water, fats and oils, alcohol, etc., so that the density of the dye and spots do not occur when the pressure-sensitive adhesive composition is spread on the surface of the support, It is preferable to knead.

  The preservative is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methyl paraoxybenzoate (methyl paraben) and propyl paraoxybenzoate (propyl paraben). These may be used individually by 1 type and may use 2 or more types together.

  Furthermore, in the present invention, in addition to the above components, the polyhydric alcohol (humectant) such as sorbitol, propylene glycol, polyethylene glycol, polysorbate 80 (polyoxyethylene sorbitan fatty acid ester), polyoxyethylene is added within the range not impairing the effects of the invention. Surfactants (emulsifiers) such as hardened castor oil and polyoxyethylene fatty acid esters, cooling agents such as peppermint oil and l-menthol, sodium metaphosphate (stabilizer), and the like can be appropriately blended.

  The water content of the pressure-sensitive adhesive composition obtained by blending each of the above components is 80% by mass or more, preferably 80 to 90% by mass in the composition. If the water content is too low, a sufficient cooling effect cannot be obtained. If the water content is too high, the pressure-sensitive adhesive composition may protrude from the side of the support or cause a back spot.

A well-known thing can be used as a support body, For example, paper, a woven fabric, a nonwoven fabric, a knitted fabric, a plastic film etc. can be mentioned. The amount of spread when the pressure-sensitive adhesive composition is spread on the support is not particularly limited, but for example, 1 to 100 g is preferable and 140 to 50 g is more preferable per 140 cm ^{2 of the} support. In addition, after spreading the pressure-sensitive adhesive composition on the support, when the product is manufactured, the spread surface is covered with a plastic film (facing) such as polyethylene or polyethylene terephthalate, if necessary, and cut into an appropriate size. Can be used.

  According to the present invention, the adhesive strength (initial adhesive strength) when the patch obtained above is first applied is preferably 0.4 to 1.0 N, more preferably 0.5 to 1.0 N. is there. Further, the adhesive strength (re-adhesive strength) when the peeled patch is applied again is preferably 0.3 to 1.0 N, more preferably 0.3 to 0.8 N. The re-adhesive strength retention rate (adhesive strength retention rate) relative to the initial adhesive strength is preferably 60% or higher, more preferably 70% or higher, relative to the initial adhesive strength.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Examples 1 to 16, Comparative Examples 1 to 6]
Each component was mixed with the composition shown in Tables 1 to 4 using a Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd., model: FM 20C / I) to obtain an adhesive composition. Subsequently, the pressure-sensitive adhesive composition obtained above was applied to a non-woven fabric having a width of 30 cm (polyester non-woven fabric manufactured by Kurashiki Fiber Processing Co., Ltd .: non-woven fabric basis weight 90 g / m ² ). TC-340) is uniformly spread to form a pressure-sensitive adhesive layer, and the surface of the pressure-sensitive adhesive layer is further covered with a plastic film (facing, polyester film manufactured by Unitika Ltd .: thickness 25 μm) An agent was obtained. The spread amount of the pressure-sensitive adhesive composition was 28.5 g with respect to the support 140 cm ² . The obtained patch was placed in an inner bag (paper 64 g / m ² / PE 15 μm / AL 7 μm / EMAA 20 μm) and sealed by heat sealing in order to prevent drying.
About the obtained patch, the following items were evaluated. The results are also shown in the table.

[Adhesiveness]
About the patch produced above, while measuring initial adhesive force and re-adhesive force by the following method, adhesive force retention was calculated and adhesiveness was evaluated. The re-adhesive strength means the adhesive strength when the adhesive patch adhered to the adherend surface is peeled off and then adhered to the same portion again.
For the measurement of adhesive strength, a texture analyzer (model: TA-XT2i) manufactured by Eihiro Seiki Co., Ltd. was used. A patch cut to 12 cm × 5 cm was used. A glass probe having a diameter of 10 mmφ was pressed perpendicularly to the adhesive surface at a speed of 2 mm / min, held at a stress of 1 N for 5 seconds, and then the maximum stress when pulled up perpendicularly to the adhesive surface at a speed of 2 mm / min was defined as the initial adhesive force. . The same operation was repeated again, and the maximum stress during the second pulling was defined as the re-adhesive force.
From the measured initial adhesive strength and re-adhesive strength, the adhesive strength retention was determined by the following formula and evaluated according to the following criteria.
Adhesive strength retention (%) = re-adhesive strength / initial adhesive strength × 100
<Criteria>
◎: 70% or more ○: 60% or more and less than 70% △: 50% or more and less than 60% ×: less than 50%

[Sensory evaluation of adhesive strength]
Thirty healthy males and females were evaluated by a sensory test as panelists. The plastic film of the patch cut to 5 cm × 12 cm was peeled off and attached to the forehead part of the panel. After 8 hours, the number of people who had no peeling or turning was measured and evaluated according to the following criteria. The number of persons who had no peeling or turning was determined to be acceptable if the number was 15 or more (that is, “◎” or “○” evaluation).
<Criteria>
◎: 20 or more ○: 15 or more and 19 or less △: 10 or more and 14 or less ×: 9 or less

The raw materials used in the above examples are shown below. Unless otherwise specified, the amount of each component in the table is a pure conversion amount.
Polyacrylic acid partially neutralized product: manufactured by Toa Gosei Co., Ltd., “Aronbis AH-106X”, mass average molecular weight: 4.5 million, degree of neutralization: 40 mol%
Polyacrylic acid 1: manufactured by Toa Gosei Co., Ltd., “Jurimer SH8α”, mass average molecular weight: 1 million, degree of neutralization: 0 mol%
Polyacrylic acid 2: manufactured by Toagosei Co., Ltd., “Jurimer AC-10Hα”, mass average molecular weight: 150,000, degree of neutralization: 0 mol%
Polyalkylene oxide water-absorbing resin: "Aqua Coke TWB-P" manufactured by Sumitomo Seika Co., Ltd.
N-vinylacetamide crosslinked product: “NA-010” manufactured by Showa Denko KK
Acrylamide cross-linked: “Diacetone Acrylamide” manufactured by Nippon Kasei Co., Ltd.
Glycerin: Sakamoto Pharmaceutical Co., Ltd., “Japanese Pharmacopoeia Concentrated Glycerin”
Carboxymethylcellulose: “CMC1380”, manufactured by Daicel Finechem Co., Ltd.
Dihydroxyaluminum aminoacetate: Glycinal, manufactured by Kyowa Chemical Industry Co., Ltd.
Synthetic hydrotalcite: “Alkamak SH” manufactured by Kyowa Chemical Industry Co., Ltd.
Magnesium aluminate metasilicate: "Neoaluminum S" manufactured by Tomita Pharmaceutical Co., Ltd.
Alumina magnesium hydroxide: Kyowa Chemical Industry Co., Ltd., “SANALMIN”
Sodium metaphosphate: Taihei Chemical Co., Ltd., “Sodium Metaphosphate”
Edetate disodium: manufactured by Chubu Kirest Co., Ltd., “Sodium edetate”
Methyl paraoxybenzoate: “Methyl paraoxybenzoate” manufactured by Ueno Pharmaceutical Co., Ltd.
Propyl paraoxybenzoate: "Propyl paraoxybenzoate" manufactured by Ueno Pharmaceutical Co., Ltd.
Polysorbate 80: manufactured by Nikko Chemicals Co., Ltd., “TO-10MV”, polyoxyethylene (20) sorbitan monooleate tartaric acid: manufactured by Iwata Chemical Industry Co., Ltd., “tartaric acid”
Citric acid: "Citric acid" manufactured by Iwata Chemical Industry Co., Ltd.
Malic acid: “Malic acid” manufactured by Kyowa Hakko Kogyo Co., Ltd.
Lactic acid: “Lactic acid” manufactured by Pure Chemical Co., Ltd.
Sodium hydroxide: Pure Chemical Co., “Sodium hydroxide”
l-Menthol: “L-Menthol” manufactured by Takasago International Corporation
Pepper oil: Made from Takasago International Corporation
Lavender oil: “Lavender oil” manufactured by Takasago International Corporation
Eucalyptus oil: Made by Takasago International Corporation, “eucalyptus oil”
Rosemary extract: “Rosemary extract BG-J” manufactured by Maruzen Pharmaceutical Co., Ltd.
Clarisage extract: “Salvia extract BG-J” manufactured by Maruzen Pharmaceutical Co., Ltd.
Time extract: Maruzen Pharmaceutical Co., Ltd., “Tachija Sou extract BG”
Green LK: manufactured by Sakai Kasei Co., Ltd., “Green LK”
Purified water: Kyoei Pharmaceutical Co., Ltd., “Purified water (distilled)”

Claims (7)

In a patch comprising a support and an adhesive layer, the adhesive layer is
(A) polyacrylic acid and / or a salt thereof,
(B) a polyalkylene oxide water-absorbing resin,
(C) formed of a pressure-sensitive adhesive composition containing one or more organic acids selected from tartaric acid, malic acid, lactic acid, and citric acid, and the average molecular weight of component (A) is 3 million or more, (A) The blending mass ratio of the component and the component (C) is the following formula: [(A) component acrylate unit- (C) component carboxyl group] /
[Acrylate unit of component (A) + Acrylic acid unit of component (A)] ≦ 0.22
And the adhesive composition has a pH of 4 to 5.5 and a water content of 80% by mass or more.   The patch according to claim 1, further comprising (D) a polyvalent metal salt.   Furthermore, (E) The patch of Claim 1 or 2 which contains 1 mass% or more and less than 5 mass% of glycerol in an adhesive composition.   The patch according to any one of claims 1 to 3, wherein the content of the component (A) is 1 to 15% by mass in the pressure-sensitive adhesive composition.   (B) Content of a component is 0.01-5 mass% in an adhesive composition, The patch of any one of Claims 1-4.   Furthermore, the patch of any one of Claims 1-5 which contains 1-10 mass% of (F) sodium carboxymethylcellulose in an adhesive composition.   (C) Content of component is 0.1-5 mass% in an adhesive composition, The patch of any one of Claims 1-6.