KR20200103618A - Patch and its manufacturing method - Google Patents

Abstract

As a patch provided with an adhesive layer and a support,
The pressure-sensitive adhesive layer,
(A) one or more selected from polyacrylic acid and salts thereof,
(B) a cellulose derivative comprising sodium carboxymethylcellulose having a viscosity of 1 mass% aqueous solution at 25°C of 2,000 mPa·s or less and sodium carboxymethyl cellulose having a viscosity of 1 mass% aqueous solution at 25°C of 2,500 mPa·s or more,
(C) polyhydric alcohol, and
(D) A patch containing a polyvalent metal salt.

Description

Patch and its manufacturing method

The present invention relates to a patch provided with a high water content pressure-sensitive adhesive layer and a method for producing the same.

The patch having a high water content pressure-sensitive adhesive layer is excellent in persistence of the cooling effect. In some cases, sodium carboxymethylcellulose (hereinafter, sometimes referred to as CMCNa) is used for the pressure-sensitive adhesive layer having a high water content. In a general pressure-sensitive adhesive layer manufacturing process, CMCNa is uniformly dispersed and dissolved in the pressure-sensitive adhesive layer by dispersing CMCNa in polyhydric alcohol as a dispersant (Patent Document 1: Japanese Patent Laid-Open No. 2014-028767). However, upon dispersion in a polyhydric alcohol, if the CMCNa concentration in the dispersion is high, there is a problem that it cannot be uniformly dispersed in the adhesive layer, and insoluble aggregates are generated. In addition, when stirring for a long time in order to eliminate the insoluble aggregates, the temperature of the pressure-sensitive adhesive layer rises, resulting in a problem in production such as rapid curing and inability to spread.

On the other hand, when the moisture content is less than 70% by mass, the dispersion efficiency of CMCNa can be improved by using a large amount of polyhydric alcohol. However, in the case of a high moisture pressure-sensitive adhesive layer having a water content of 70% by mass or more, since there is an upper limit on the blending amount of polyhydric alcohol, the above problem that CMCNa becomes a high concentration in the polyhydric alcohol, resulting in insoluble aggregates could not be solved (Patent Document 2 : Japanese Patent Publication No. 2002-136587).

On the other hand, a method of uniformly dispersing a polyhydric alcohol and a superabsorbent polymer compound in the pressure-sensitive adhesive layer is known (Patent Document 3: Japanese Patent Laid-Open No. 2001-122772), but the superabsorbent polymer is expensive, and polyhydric alcohol, which is a plasticizer. Because of this small amount, there has been a problem in that the solid becomes hard during drying, and pain may be felt in the back when peeling off the patch.

Japanese Patent Publication No. 2014-028767 Japanese Patent Publication No. 2002-136587 Japanese Patent Laid-Open No. 2001-122772

The present invention has been made in view of the above circumstances, and suppresses the occurrence of insoluble aggregates in the pressure-sensitive adhesive layer, and suppresses peeling, curling, and unevenness on the back surface of the patch (seepage to the back surface of the support of the adhesive layer). It aims to provide.

The inventors of the present invention have studied intensively in order to achieve the above object, as a result of an adhesive layer having a water content of 70% by mass or more, and a patch having a support, a specific amount of at least one selected from (A) polyacrylic acid and its salt, specific Amount of (B) carboxymethylcellulose sodium as essential cellulose derivative, (C) polyhydric alcohol, and (D) a patch containing a polyvalent metal salt found that the above problems could be solved, and thus achieved the present invention. will be.

Accordingly, the present invention provides a patch and a method for producing the patch.

1. As a patch provided with an adhesive layer and a support having a water content of 70% by mass or more,

The pressure-sensitive adhesive layer,

(A) one or more selected from polyacrylic acid and salts thereof,

(B) a cellulose derivative comprising sodium carboxymethylcellulose having a viscosity of 1 mass% aqueous solution at 25°C of 2,000 mPa·s or less and sodium carboxymethyl cellulose having a viscosity of 1 mass% aqueous solution at 25°C of 2,500 mPa·s or more,

(C) polyhydric alcohol, and

(D) A patch containing a polyvalent metal salt.

2. In 1,

The content of the component (A) is 2.4 to 10.0% by mass in the pressure-sensitive adhesive layer,

The content of the component (B) is 1.5 to 5.4 mass% in the pressure-sensitive adhesive layer,

Formula (I): [content of (A) component]/[content of (B) component] (mass ratio) is 1.0 to 6.67, and,

Formula (II): [content of (C) component]/{1.5 x [content of (A) component] + 2 x [content of (B) component]} (mass ratio) of 1 to 3 patch.

3. In 1 or 2,

(C) A patch in which the content of the component is 11 to 25.2% by mass in the pressure-sensitive adhesive layer.

4. In any one of 1 to 3,

(D) A patch in which the content of the component is 0.01 to 2% by mass in the pressure-sensitive adhesive layer.

5. In any one of 1 to 4,

(E) A patch further containing at least one selected from an active ingredient, a refreshing agent, and a warmth imparting agent.

6. As a method for producing a patch according to any one of 1 to 5,

(A) At least one selected from polyacrylic acid and salts thereof, and (B) a method for producing a patch comprising a step of dispersing a cellulose derivative in (C) a polyhydric alcohol.

7. In 6,

(A) component and (B) component are the manufacturing method of the patch which is powder.

(Effects of the Invention)

ADVANTAGE OF THE INVENTION According to this invention, while suppressing the generation|occurrence|production of an insoluble aggregate in an adhesive layer, peeling, curling, and the back surface unevenness of a patch were suppressed, a patch and its manufacturing method can be provided.

Hereinafter, (i) a pressure-sensitive adhesive layer, (ii) a method of manufacturing the pressure-sensitive adhesive layer, (iii) a support, (iv) a patch, and a manufacturing method thereof will be described in detail.

(i) adhesive layer

[(A) component]

The component (A) is one or more selected from polyacrylic acid and salts thereof, and mainly acts as an adhesive. Examples of the component (A) include polyacrylic acid, a neutralized product in which all of the polyacrylic acid is neutralized (polyacrylic acid salt) or partially neutralized (partially neutralized polyacrylic acid), a crosslinked polyacrylic acid, and a salt thereof. Examples of the counter ion of the polyacrylic acid salt or the partially neutralized polyacrylic acid include monovalent metal salts such as sodium and potassium, amine salts such as monoethanolamine, diethanolamine, and triethanolamine, and those neutralized with an ammonium salt. These can be used alone or in combination of two or more as appropriate. In addition, powder is preferable as for (A) component.

Although there is no restriction|limiting in particular as a mass average molecular weight of (A) component, 4 million-5 million are preferable. Further, the degree of neutralization of the partially neutralized polyacrylic acid is preferably 10 to 50 mol%, more preferably 20 to 40 mol%, and even more preferably 40 mol%. In addition, the 0.2 mass% aqueous solution viscosity (B type viscometer: rotor No. 2, rotational speed 30 rpm, 20°C) is preferably 100 to 10,000 mPa·s, more preferably 100 to 5,000 mPa·s, and 100 to 1,000 mPa -S is more preferable. In addition, the measurement method of the mass average molecular weight is gel permeation chromatography (GPC), and the neutralization degree is a value calculated|required by the following formula.

Degree of neutralization (mol%) = 100 × "the number of moles of neutralized carboxyl groups in the molecule" / "the total number of moles of carboxyl groups in the molecule"

The content of the component (A) is preferably 2.4 to 10.0% by mass, more preferably 3 to 9% by mass, and still more preferably 5 to 8.4% by mass in the pressure-sensitive adhesive layer. By setting it as 2.4 mass% or more, adhesive force is improved more, peeling and curling of a patch can be suppressed more, and insoluble aggregates become more difficult to produce. On the other hand, by setting it as 10.0 mass% or less, formula (I) and (II) mentioned later and a water content of 70 mass% or more can be satisfied.

[(B) component]

Component (B) has a viscosity of 1% by mass aqueous solution at 25°C of 2,000 mPa·s or less, preferably 1,000 to 2,000 mPa·s of sodium carboxymethylcellulose, and a viscosity of 1% by mass aqueous solution at 25°C of 2,500 mPa·s. As described above, it is a cellulose derivative containing sodium carboxymethylcellulose, preferably 2,500 to 4,500 mPa·s, and mainly acts as an imparting shape. The blending mass ratio represented by sodium carboxymethylcellulose having a viscosity of 1 mass% aqueous solution at 25°C of 2,000 mPa·s or less/sodium carboxymethyl cellulose having a viscosity of 1 mass% aqueous solution at 25°C of 2,500 mPa·s or more is 1/3 to 3 /1 is preferred.

In addition, the measuring method of the viscosity of (B) component uses a BL viscometer. A 1 mass% aqueous solution viscosity at 25°C of less than 1,000 mPa·s is measured at a rotation speed of 60 rpm using rotor Nos. 1-3, and a 1 mass% aqueous solution viscosity at 25° C. of 1,000 to 2,000 mPa·s is a rotor No. 3 or No. 4 is used to measure at a rotation speed of 60 rpm, and a viscosity of 2,500 to 4,500 mPa·s in a 1% by mass aqueous solution at 25°C is measured at a rotation speed of 60 rpm using a rotor No. 4.

Component (B) contains two kinds of sodium carboxymethylcellulose having different viscosities as essential components, but the cellulose derivatives of component (B) include carboxymethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, and hydroxypropylmethyl. And water-soluble cellulose ethers such as cellulose, hydroxypropylhydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxymethylcellulose, methylcellulose, and croscarmellose sodium, cationized cellulose, and salts thereof. As a cellulose derivative used in combination with sodium carboxymethylcellulose, carboxymethylcellulose, hydroxypropylcellulose, and croscarmellose sodium are preferable. From the viewpoint of manufacturability and gel retention, the ratio of sodium carboxymethylcellulose in the component (B) is preferably 70 to 100% by mass. The amount of sodium carboxymethylcellulose in the pressure-sensitive adhesive layer is preferably 2 to 5% by mass. In addition, as for the component (B), powder is preferable.

The content of the component (B) is preferably 1.5 to 5.4 mass%, more preferably 2 to 5 mass%, and still more preferably 3 to 4 mass% in the pressure-sensitive adhesive layer. By making the component (B) 1.5% by mass or more, unevenness on the back surface is more suppressed. By setting it as 5.4 mass% or less, formulas (I) and (II) mentioned later and a water content of 70 mass% or more can be satisfied.

[(C) ingredient]

The component (C) is a polyhydric alcohol, and mainly acts as a dispersant for the component (A) and component (B). Polyhydric alcohols include ethylene glycol, 1,3-butanediol, propylene glycol, isoprene glycol, amylene glycol, glycerin, diglycerin, triglycerin, polyglycerin, diethylene glycol, dipropylene glycol, polyethylene glycol, diethylene glycol monoalkyl ether And the like, and can be used alone or in combination of two or more as appropriate. Among them, it is preferable to use glycerin.

The content of the component (C) is preferably 11 to 25.2% by mass, more preferably 15 to 20% by mass, and still more preferably 16 to 20% by mass in the pressure-sensitive adhesive layer. By setting the content of the component (C) to 11% by mass or more, the flexibility of the pressure-sensitive adhesive layer in use can be maintained, and the components (A) and (B) are uniformly dissolved in the pressure-sensitive adhesive layer, making it more difficult to form insoluble aggregates. By setting it as 25.2 mass% or less, formulas (I) and (II) mentioned later and a water content of 70 mass% or more can be satisfied.

Formula (I): [content of the component (A)]/[content of the component (B)] (mass ratio) defines the content of the component (A) relative to the component (B), and is preferably 1 to 6.67, 1 to 4.5 are more preferable, and 1.25 to 2.8 are still more preferable. By setting this ratio to 1 or more, the components (A) and (B) are uniformly dissolved in the pressure-sensitive adhesive layer, and insoluble aggregates are more difficult to form. Further, by setting it as 1 or more, peeling and curling of the patch is more easily suppressed. On the other hand, by setting it as 6.67 or less, Formula (II) mentioned later and a moisture content 70 mass% or more can be satisfied.

Formula (II): [content of (C) component]/{1.5 x [content of (A) component] + 2 x [content of (B) component]} (mass ratio) indicates the required amount of polyhydric alcohol acting as a dispersant It is defined, and 1-3 are preferable. The above formula defines the amount of (A) component and (B) component uniformly dispersed in (C) component and uniformly soluble in the pressure-sensitive adhesive layer as each of (A) component and (B) component, and (A) It means that 1.5 times the amount of component (C) and 2 times the amount of component (C) with respect to the component are required. By setting this ratio to 1 or more, the components (A) and (B) are uniformly dissolved in the pressure-sensitive adhesive layer, and insoluble aggregates are more difficult to form. On the other hand, by setting it as 3 or less, above-mentioned Formula (I) and water content 70 mass% or more can be satisfied.

[(D) ingredient]

(D) Component is a polyvalent metal salt, and acts as a crosslinking agent. Examples of polyvalent metal salts include alum 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 phosphate, calcium nitrate, calcium chloride. , Calcium acetate, calcium oxide, calcium phosphate, magnesium hydroxide, magnesium carbonate, magnesium sulfate, magnesium acetate, magnesium silicate, magnesium oxide, alumina magnesium hydroxide, magnesium metasilicate, magnesium aluminate, magnesium aluminate, synthetic hydrotalcite, and di And hydroxyaluminum aminoacetate. These can be used alone or in combination of two or more as appropriate. Among them, the pressure-sensitive adhesive composition used as the pressure-sensitive adhesive layer is uniformly applied to at least one surface of the support in the process of leading the pressure-sensitive adhesive layer, so that it acts more slowly than the immediate effect (it is less water soluble than water-soluble, and gradually dissolves in the pressure-sensitive adhesive layer. To do) is preferable. As such a component, for example, magnesium alumina hydroxide, magnesium alumina metasilicate, magnesium aluminate silicate, synthetic hydrotalcite, and dihydroxyaluminum aminoacetate are preferable.

The content of the component (D) is preferably 0.01 to 2 mass% in the pressure-sensitive adhesive layer, more preferably 0.03 to 1 mass%, and even more preferably 0.05 to 0.5 mass%. By setting it as 0.01 mass% or more, the shape retention of a pressure-sensitive adhesive layer can be obtained more sufficiently, and unevenness on the back surface is more suppressed. On the other hand, when the amount is 2% by mass or less, peeling and curling of the patch is more suppressed, the crosslinking rate is easily adjusted during production, and uneven coating of the pressure-sensitive adhesive composition serving as the pressure-sensitive adhesive layer is suppressed.

[(E) component]

The pressure-sensitive adhesive layer of the present invention may contain one or more selected from (E) an active ingredient, a refreshing agent, and imparting warmth. As an active ingredient, steroid type anti-inflammatory agent, non-steroid type anti-inflammatory agent, herbal medicine and essential oil ingredient are mentioned.

As a steroid-based anti-inflammatory agent, for example, anti-inflammatory drugs are hypokinoids, prednisolone valerate, diflucoltolone valerate, betamethasone valerate, betamethasone acetate, dexamethasone acetate, betamethasone dipropionate, dexamethasone, triamcinolone acetonide, rilcinonide, hydrocoorthione. Flumethasone divergent, fluorosinonide, fluocinolone acetonide, fluorometholone, fludroxycortide, prednisolone, clobetasol propionate, beclomethasone propionate, betamethasone, methylprednisolone, methylprednisolone acetate, butyric acid hydrocolate And the like. The content in the case of blending these steroid-based anti-inflammatory agents is preferably 0.05 to 5% by mass in the pressure-sensitive adhesive layer.

Non-steroidal anti-inflammatory agents include, for example, loxoprofen, diclofenac, felbinac, indomethacin, salicylic acid glycol, salicylic acid, acetylsalicylic acid (aspirin), acetaminophen, aminopyrine, antipyrine, oxyfenbutazone, sulpyrine, ibuprofen. , Sulindac, naproxen, ketoprofen, etofenamate, salicylamide, triethanolamine salicylate, flufenamic acid, meclofenamic acid, colchicine, bupexamak, fenbufen, diflunisal, alclofenac, phenyl Butazone, mefenamic acid, fenoprofen, bendazac, piroxicam, flurbiprofen, zaltoprofen, etodolac, pranoprofen, mepyrazole, suprofen, glycyrrhetinic acid, glycyrrhizic acid and And their salts and derivatives. The content of the non-steroidal anti-inflammatory agent is preferably 0.05 to 5% by mass in the pressure-sensitive adhesive layer.

As a herbal medicine/essential oil component, for example, herbal medicine powder such as barley, Hwangbaek, Japanese pepper tree, sugar medicine, licorice, golden, gardenia, angelica, elderberry, yangmaepi, extracts of herbal medicines such as barley, mentha oil, mint white oil, cinnamon oil, etc. And essential oils. In the case of blending the herbal medicine or essential oil component, the content is preferably 0.05 to 5% by mass in the pressure-sensitive adhesive layer.

Examples of the refreshing agent include p-methane such as limonene, terpinolene, methane, and terpinene, and terpene-based hydrocarbon compounds such as monocyclic monoterpene-based hydrocarbon compounds derived therefrom, l-menthol, isopuregol, 1 Menthol related (類緣) compounds such as ,3-methoxypropane-1,2-diol, camphor, thymol, and the like are suitably used. The content in the case of blending a refreshing agent is preferably 0.05 to 5% by mass in the pressure-sensitive adhesive layer.

As the warmth imparting agent, any material that makes the feeling of warmth when applied to the skin may be used.For example, capsaicin analogues such as capsicoside, capsaicin, capsaicinoid, dihydroxycapsaicin, and capxanthin, pepper extract , Red pepper tink, red pepper powder, etc., benzyl nicotinate, β-butoxyethyl nicotinic acid, N-acylwanilamide, nonylic acid vanilamide, vanillyl butyl ether, tocopherol acetate, acetyleugenol, jointed herb Extract, charcoal extract, arnica tincture, ginger extract, cinnamon oil, and the like. The content in the case of blending the warmth imparting agent is preferably 0.05 to 5% by mass in the pressure-sensitive adhesive layer.

Among these (E) components, in the present invention, loxopropene sodium, diclofenac sodium, felbinac, indomethacin, salicylic acid glycol, l-menthol, red pepper extract, and white peppermint are preferred.

The content in the case of blending the component (E) is good in an effective amount, but 0.05 to 5 mass% in the pressure-sensitive adhesive layer is preferred, and 0.2 to 2 mass% is more preferred. By setting it as 0.05 mass% or more, sufficient medicinal effect, a feeling of refreshment, and a feeling of warmth are obtained. Even if it is blended in excess of 5% by mass, a higher medicinal effect, refreshing sensation, and warm sensation cannot be obtained, and skin irritation may occur.

[Optional ingredient]

In the pressure-sensitive adhesive layer of the present invention, an appropriate amount of the following components generally used for a water-containing pressure-sensitive adhesive may be used alone or in an appropriate combination of two or more, within a range not impairing the effects of the present invention. In addition, the following components are examples, and depending on the components, they may be repeatedly described.

(1) hardening modifier

Sodium edetate, sodium edetate hydrate, sodium metaphosphate, citric acid, and the like can be used. The content in the case of blending the curing modifier is preferably 0.01 to 3% by mass in the pressure-sensitive adhesive layer.

(2) organic acid

Tartaric acid, malic acid, and lactic acid. The content in the case of blending an organic acid is preferably 0.1 to 3% by mass in the pressure-sensitive adhesive layer.

(3) preservative

Methyl paraoxybenzoate (methylparaben), propyl paraoxybenzoate (propylparaben), and the like. The content in the case of blending a preservative is preferably 0.01 to 2% by mass in the pressure-sensitive adhesive layer.

(4) emulsifier (surfactant)

Polyoxyethylene sorbitan fatty acid ester such as polyoxyethylene hydrogenated castor oil, polyoxyethylene (20) sorbitan monooleate (polysorbate 80), polyoxyethylene glycerin fatty acid ester, polyoxyethylene glycol fatty acid ester, polyoxy Ethylene glycol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene phytosterol, sorbitan fatty acid ester, glycerin fatty acid ester, and the like. The content in the case of blending a surfactant is preferably 0.2 to 5.0% by mass in the pressure-sensitive adhesive layer.

(5) fragrance

Fennel oil, big oil, clove oil, thyme oil, turpentine oil, henopodilla oil, yamajin oil, oil lip tops oil, lavender oil. Peppermint oil, lemon oil, orange oil, lantern oil, bergamot oil, rose oil, citronella oil, lemongrass oil, camphor oil, geranium oil, rosemary oil, sage oil, and the like. In addition, as a plant extract, for example, aloe, anise, angelica, benzoin, imoteel, chamomile, chamomile, garlic, cardamom, galvanum, caraway, carrot seed, rapeseed, grapefruit, cypress, sandalwood, cedarwood , Juniper, star anise, sage, geranium, celery, thyme, tarragon, turpentine, frankincense, violet, pine, parsley, birch, patchouli, rose, hyssop, fennel, black pepper, bodhi, myrrh, yarrow, lemon, Lemongrass, rosemary, laurel tree, spirea chrysanthemum, spirea, cornflower, almond, thistle, arnica, cypress, fennel, marigold, Erica, locust, mustard, gorilla root, persimmon tree, chrysanthemum grass, umbrella grass, marigold, celandine , Watercress, rhododendron, gentiana, cherry, tea plantation, birch, cedar, boredom, camphor, jujube, large leaf gentian, plum, pear, golden tree, jujube, texas, dandelion, jimo, chervil, jeeryeong, asparagus root , Winter sweets, brier flowers, wild carrots, akemila, ash tree, purple purple sprouts, baby swimming, bokryeong, borage, mugwort, marjoram, melissa, neck barrel, peach, mistletoe, eucalyptus, lavender, forsythia, mustard radish, etc. And extracts of. Among these, extracts from chamomile, sage, parsley, rosemary, spirea chrysanthemum, spirea grass, cornflower, anise, laurel, angelica, fennel, peppermint, lemon balm, lavender, thyme, and the like are particularly suitable. Specific components of such an extract include, for example, cineol, borneol, and other camphor (camper), linanol, berbenol, flavonoids, choline, amino acids, tannins, vegetable acids, fatty acids, cyanoglycosides, salbins, condensed tannins, Phenolic acid, carnosic acid, triterpenic acid, tuyon, salben, pinene, apiol, apiolin, myristic acid, coumarin, camazulene, farnesene, bisabolol, geraniol, oigenol, terpene, phelland Ren, anetol, menthone, citral, citronellal, and eugenol acetate. The content in the case of blending the fragrance is preferably 0.01 to 1% by mass in the pressure-sensitive adhesive layer.

(6) pigment

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, Red No. 205, Red No. 206, Red No. 207 Red No.208, Red No.213, Red No.214, Red No.215, Red No.218, Red No.219, Red No.220, Red No.221, Red No.223, Red No.225, Red No.226, Red No.227, Red No.228, Red No.230 (1), Red No.230 (2), Red No.231, Red No.232, Red No.401, Red No.404, Red No.405, Red No.501, Red No.502, Red No.503, Red No.504, Red No.505, Red No.506, Yellow No.4, Yellow No.5, Yellow No.201, Yellow No.202 (1), Yellow No.202 (2), Yellow No.203, Yellow No.204, Yellow No.205, Yellow No.401, Yellow No.402, Yellow No.403 (1), Yellow No.404, Yellow No.405, Yellow No.406, Yellow No.407, Green No.3, Green No.201, Green No.202, 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 No.403, Blue No.404, Orange 201, Orange 203, Orange 204, Orange 205, Orange 206, Orange 207, Orange 401, Orange 402, Orange 403, Brown 201, Purple 201, Purple 401, Black 401 And the like. The content of the dye is not particularly limited and can be appropriately selected depending on the purpose, but the content in the case of blending the dye is preferably 0.00005 to 0.1% by mass, and more preferably 0.0001 to 0.01% by mass in the pressure-sensitive adhesive layer. If the content is too small, there is a fear that the effect due to the blending may not be sufficiently obtained, and if it is too large, the color tone may become too strong. In addition, in the case of blending a dye, it is preferable to dissolve the dye with water, fat or oil, alcohol, etc., and then knead it with other ingredients so that when the pressure-sensitive adhesive composition is spread on the surface of the support, so as not to cause shades or spots of the dye.

The water content of the pressure-sensitive adhesive layer is 70% by mass or more in the pressure-sensitive adhesive layer, and preferably 70 to 82% by mass. When the water content is 70% by mass or more, a sufficient cooling effect is obtained, and when the content is 82% by mass or less, unevenness on the back side is suppressed.

The pH of the pressure-sensitive adhesive layer is preferably 3.5 to 6, more preferably 4 to 5, and even more preferably 4.2 to 4.7. The pH is measured by bringing a pH meter (for example, HM-30V manufactured by DKK-TOA CORPORATION, flat pH electrode GST-5313F) into contact with the pressure-sensitive adhesive composition after spreading to the support under the conditions of 25°C.

(ii) Method for producing an adhesive layer

Although it does not specifically limit as a manufacturing method of an adhesive layer, From the point which makes insoluble aggregate of (A) and (B) component more difficult to generate|occur|produce, For example, (A) one or more types selected from polyacrylic acid and its salt, and, It is preferable to include the step of dispersing (B) a cellulose derivative in (C) polyhydric alcohol.

More specifically, (C) at least one selected from powdery (A) polyacrylic acid and salts thereof, and (B) a cellulose derivative are added to a polyhydric alcohol, and the components (A) and (B) are dispersed and stirred. To prepare pre-dispersion 1. Separately, a step of dispersing the component (D) in the component (C) to prepare a pre-dispersion 2 is included. The component (E) may be dispersed in a pre-dispersion, but it is preferable to include a step of mixing the emulsifier together with a fragrance or preservative. It is preferable to include a step of adding and stirring the pre-dispersion 2 after adding and stirring the pre-dispersion 1 to the pre-mixture in which water and other optional components are mixed. Optional components may be added as a pre-dissolved product and a pre-dispersion, respectively.

(iii) support

Known things can be used as the support, and examples thereof include paper, woven fabric, nonwoven fabric, and knitted fabric. Among them, a knitted fabric having a basis weight of 90 to 140 g/m2 or a nonwoven fabric having a basis weight of 70 to 140 g/m2 is preferable. The amount of leading edge when leading the pressure-sensitive adhesive composition serving as the pressure-sensitive adhesive layer to the support is not particularly limited, but is preferably 800 to 1,200 g per 1 m 2 of the support.

The material (type) of the fiber is not particularly limited as the knitted fabric, and for example, polyester, nylon, polyolefin (PE, PP, etc.), vinylon, polyvinylidene chloride, polyvinyl chloride, acrylic resin, polyurethane, etc. Tributaries are mentioned. In addition, the degree of polymerization of these is not particularly limited, and those of the degree of polymerization that are usually used as a material for a knitted fabric can be used.

The knitting method of the knitted fabric is not particularly limited, and for example, warp knitting (tricoat knitting, denvitricoat knitting, satin knitting, atlas knitting, flat knitting, rim knitting, pearl knitting), circular knitting (double-sided meriyasu knitting, Single-sided yarn knitting, circular rib yarn knitting), horizontal knitting, circular knitting knitted by multifilament yarn, double-sided yarn knitting in multiple stages, knit miss knitting, cross inlay knitting, inlay knitting, etc. are employed. Preferably, tricot knitting, double-sided yarn knitting, single-sided yarn knitting, circular rib yarn knitting, circular knitting knitted by multifilament yarn, and multiple stages of double-sided yarn knitting are preferably employed. In the case of using single yarn, the fiber used for the knitted fabric can be generally 10 to 80 denier. When multifilament is used, fibers of 40 to 100 denier can be used in general.

The basis weight of the knitted fabric is preferably 90 to 140 g/m 2, the lower limit is more preferably 95 g/m 2 or more, and even more preferably 100 g/m 2 or more. If the basis weight is less than 90g/m2, the degree of twisting is weakened, and there is a concern that agglomeration and sagging may occur in the pressure-sensitive adhesive layer during leading edge. The upper limit is preferably 130 g/m 2 or less, and more preferably 120 g/m 2 or less. If the basis weight exceeds 140 g/m 2, there is a fear that the pressure-sensitive adhesive layer becomes hard and the feeling of use, such as conformability to the skin, is deteriorated.

As a nonwoven fabric, the material of the fiber is not particularly limited, and for example, polyester resins such as polyamide, polyethylene, polyethylene terephthalate, polyolefin resins such as polypropylene, polyester ether, polyurethane resin, acrylic resin, polyvinyl Alcohol, polystyrene resin, etc. are mentioned.

The manufacturing method is not particularly limited, and a nonwoven fabric by a manufacturing method such as spunlace, spunbond, thermal bond, chemical bond, and needle punch is selected.

The basis weight of the nonwoven fabric is preferably 70 to 140 g/m 2, the lower limit is preferably 75 g/m 2 or more, and more preferably 80 g/m 2 or more. If the basis weight is less than 70g/m2, the degree of twisting is weakened, and there is a concern that agglomeration and sagging may occur in the pressure-sensitive adhesive layer during leading edge. The upper limit is preferably 130 g/m 2 or less, and more preferably 120 g/m 2 or less. If the basis weight exceeds 140 g/m 2, there is a fear that the pressure-sensitive adhesive layer becomes hard and the feeling of use, such as conformability to the skin, is deteriorated.

(iv) patch and its manufacturing method

The patch of the present invention comprises an adhesive layer and a support having a water content of 70% by mass or more. For example, an adhesive layer is formed on one side of the support. After spreading the pressure-sensitive adhesive composition that becomes the pressure-sensitive adhesive layer on the support, if necessary, the surface of the pressure-sensitive adhesive layer is covered with a plastic film (release liner) such as polyethylene, polypropylene, and polyethylene terephthalate, and cut to the desired size. have. Alternatively, after spreading the pressure-sensitive adhesive composition serving as the pressure-sensitive adhesive layer on the release liner, this may be bonded to a support, and cut to a desired size.

It is preferable that it is 10-32, and, as for the adhesive force by the vortex value of an adhesive layer, 16-30 are more preferable. By setting it as more than the lower limit, adhesive force is improved and peeling and curling of a patch can be suppressed more. On the other hand, by making it below the upper limit, skin irritation and pain at the time of peeling are reduced. In addition, the measuring method of the adhesive force by a vortex is measured according to the method described in JIS Z 0237. Specifically, a ball rolling device used in JIS Z 0237 is used, the inclination angle is 30°, the length of the runway is 100 mm, and the surface to be measured is 50 mm. Balls made of the material specified in JIS G 4805 are used, and the size of the balls is 31 types in total from 1/16 to 1 of the "Nominal Dimensions of Balls" of JIS B 1501, which is 32 times the "nominal dimensions of balls". Use the numerical value as the ball number as an index of adhesion. A test piece is attached to a predetermined position on the inclined plate of the ball rolling device with the adhesive surface facing up, and balls of each size are set on the gate. Open the gate slowly, roll the ball, find the largest ball that stops completely within the measuring surface (does not move for more than 5 seconds), and uses the ball number as the voltaic value.

The method of using the patch of the present invention is not particularly limited, and for example, the patch is applied to the shoulder, waist, calf, thigh or sole of a human being used.

Example

Hereinafter, examples and comparative examples are shown to specifically describe the present invention, but the present invention is not limited to the following examples. In addition, in the following examples, when there is no particular indication, "%" of a composition represents mass %, and a ratio represents a mass ratio.

[Examples, Comparative Examples]

<Production method>

Sodium edetate hydrate was added to purified water while stirring to obtain (pre-dissolved product 1). Sodium metaphosphate or citric acid was added to purified water while stirring to obtain (pre-lysate 2). Tartaric acid, malic acid, or lactic acid was added to purified water while stirring to obtain (pre-dissolved product 3). (Preliminary mixture 1) was obtained by adding and stirring (E) component, 1-menthol, preservative, and fragrance to an emulsifier. Powdered (A) component and (B) component were added to some (C) components and stirred, and these were uniformly dispersed and dissolved to obtain (pre-dispersion 1). (D) component was added and stirred to some (C) component, and (pre-dispersion 2) was obtained. A dye was added to the remaining (C) component and stirred to obtain (pre-dispersion 3).

Pre-lysate 2 and pre-dispersion 3 were added to the pre-lysed product 1, and stirred with a Henschel mixer to obtain (kneaded product 1).

To the dough 1, the pre-dispersion 1 was stirred into a Henschel mixer and kneaded to obtain (kneaded product 2).

The pre-dispersion 2 was added to the dough 2 and stirred with a Henschel mixer to obtain (dough 3).

The pre-dissolved product 3 and the pre-dissolved product 1 were added to the dough 3 and stirred with a Henschel mixer to obtain a pressure-sensitive adhesive composition.

The pressure-sensitive adhesive composition was spread uniformly on the release liner so that the pressure-sensitive adhesive layer per sheet (14 cm x 10 cm) was about 12 g. Thereafter, a polyester knitted fabric ("base weight 105±10g/m2, thickness 0.70mm, thickness 75 denier" (manufactured by Teijin Frontier Co., Ltd.)) was affixed to the surface of the pressure-sensitive adhesive layer, and the desired size (manufactured by Teijin Frontier Co., Ltd.) was pasted. 14 cm x 10 cm) to prepare a patch. The following evaluation was performed about the obtained patch. In addition, the adhesive strength by the vortex value of the patch obtained in Examples was 10 to 32.

[Evaluation of insoluble aggregate incidence rate]

In the sampling during the leading edge of the pressure-sensitive adhesive composition obtained by kneading (100 sheets of 12 g/14 cm x 10 cm formulations were taken) as the insoluble aggregate incidence rate, evaluation was performed at the rate of occurrence of insoluble aggregates having a diameter of 2 mm or more. "◎" or "○" was taken as the pass in the following evaluation criteria.

<Judgment Criteria>

◎: 2% or less

○: more than 2% and less than 5%

×: more than 5%

[Peeling and curling after 8 hours]

A patch cut into 10 cm x 14 cm was applied to the calf of 9 healthy adults, and the condition after 8 hours was evaluated based on the following rating. The results are shown in the following evaluation criteria from the total score of nine people. 27 points or more were taken as pass.

<rating>

5: No peeling or curling of the patch

4: There is peeling and curling around the patch (less than 1/4 of the whole)

3: Peeling and curling around the patch (more than 1/4 to less than 1/3 of the whole)

2: Peeling and curling around the patch (more than 1/3 of the whole but less than 1/2)

1: There is curling more than 1/2 of the circumference of the patch, or peeling off

<Evaluation criteria for peeling and curling after 8 hours>

◎: The total score of the evaluation results of 9 persons is 36 points or more

○: The total score of the evaluation results of 9 persons is 27 points or more and less than 36 points

×: The total score of the evaluation results of 9 persons is less than 27 points

[Back stain]

Twenty sheets of the patch were stacked after production, and after standing for one day, the bottom patch was evaluated by visual and sensory evaluation according to the following evaluation criteria.

◎: No stains on the back side

○: There is some dirt on the back side, but it is a limit level that can be used.

×: It can be confirmed that it is moist and wet.

[pH]

Measurement was carried out by directly contacting the pressure-sensitive adhesive composition using HM-30V manufactured by DKK-TOA CORPORATION and flat pH electrode GST-5313F as a pH meter under the conditions of 25°C.

For the pressure-sensitive adhesive composition of Example 16, a patch was also prepared using a nonwoven fabric having a basis weight of 90 g/m 2 in the same manner. As a result of evaluating the back side unevenness of the obtained patch in the same manner as in the above example, no back side unevenness was observed.

In Comparative Example 1, since there were too many insoluble aggregates and the pressure-sensitive adhesive layer could not be produced, evaluation of "peeling and curling after 8 hours" and [backside unevenness] were not performed.

The raw materials used in the above examples are shown below. In addition, unless otherwise specified, the amounts of each component in the table are in terms of net content.

Partially neutralized polyacrylic acid: "ARONVIS AH-106X" (manufactured by Toagosei Co., Ltd.), mass average molecular weight: 4.5 million (gel permeation chromatography), degree of neutralization 40 mol%, white powder

Sodium carboxymethylcellulose: “Daicel CMC1380” (manufactured by DAICEL FINECHEM LTD.), 1% aqueous solution viscosity at 25°C 1,000 to 2,000 mPa·s (BL viscometer: Rotor No.3 or No.4, 25°C·Rotation speed) 60rpm), etherification degree 1.0~1.5, white powder

Sodium carboxymethylcellulose: "Daicel CMC1390": (manufactured by DAICEL FINECHEM LTD.), viscosity of 1% aqueous solution at 25°C 2,500 to 4,500 mPa·s (BL viscometer: Rotor No.4, 25°C, rotation speed 60 rpm), Etherization degree 1.0~1.5, white powder

Carboxymethylcellulose: "NS-300": (Gotoku Chemical Company Ltd.)

Hydroxypropyl cellulose: "HPC-H": (Nippon Soda Co., Ltd.)

・Crosscarmellose sodium: 「KICCOLATE ND-2HS」: (Nichirin Chemical Industries, Ltd.)

Glycerin: Strong glycerin "Pharmacy Defense Strong Glycerin" (manufactured by Sakamoto Yakuhin kogyo Co., Ltd.)

Propylene glycol: "Propylene glycol" (made by Mitsui Takeda Chemical Co., Ltd.)

Dihydroxyaluminum amino acetate: 「GLYCINAL」 (Showa Kagaku Kogyo Co., Ltd,)

Synthetic hydrotalcite: "ALCAMAC SH" (manufactured by Kyowa Chemical Industry Co., Ltd.)

・Sodium edetate hydrate: "Sodium edetate" (manufactured by Chelest Corporation)

Sodium metaphosphate: “Sodium metaphosphate” (manufactured by Taihei Chemical Industrial Co., Ltd.)

Citric acid: "Citric acid" (manufactured by Iwata Chemical Co., Ltd.)

Tartaric acid: "tartaric acid" (manufactured by Iwata Chemical Co., Ltd.)

・Malic acid: 「Malic acid」 (manufactured by Kyowa Hakko Kogyo Kabushiki Kaisha)

-Lactic acid: "lactic acid" (manufactured by Junsei Chemical Co., Ltd.)

-L-menthol: "Menthol JP" (manufactured by Takasago International Corporation)

・Sodium loxoprofen: "Japanese Pharmacopoeia Loxoprofen sodium hydrate" (manufactured by Daiwa Pharmaceutical Co., Ltd.)

Diclofenac sodium: 「Japanese Pharmacopoeia Diclofenac Sodium」 (manufactured by Daiwa Pharmaceutical Co., Ltd.)

Felvinac: 「Felvinac」 (manufactured by HANSEO CHEMICAL)

Indomethacin: 「Indomethacin」 (manufactured by KONGO CHEMICAL CO., LTD.)

・Salicylic acid glycol: 「Saliment」 (API Corporation)

Polyoxyethylene (20) sorbitan oleic acid ester: "NIKKOL TO-10MV" (manufactured by Nikko Chemicals Co., Ltd.)

Methyl paraoxybenzoate: "Methyl paraoxybenzoate" (manufactured by Ueno Fine Chemicals Industry, Ltd.)

-Paraoxybenzoic acid propyl: "Mechkins-P" (manufactured by Ueno Fine Chemicals Industry, Ltd.)

Orange oil: 「ORANGE」 (manufactured by Takasago International Corporation)

Lemon oil: "LEMON" (manufactured by Takasago International Corporation)

Lavender oil: 「LAVENDER EC-3439」 (manufactured by Takasago International Corporation)

Rosemary oil: 「ROSEMARY B LT-8240」 (manufactured by Takasago International Corporation)

Sage Yu: ``SAGE M_0020336'' (manufactured by V. Mane Fils Japan, Ltd.)

Red No. 404: 「RED 4」 (manufactured by Kishi Kasei Co., Ltd.)

· Support: Polyester knitted fabric “Basic weight 105±10g/m², thickness 0.70mm, thickness 75 denier (manufactured by Teijin Frontier Co., Ltd.)

Peeling liner: Polypropylene film "CPP30μ, thickness 0.12mm" (manufactured by OG CORPORATION)

(Note): ``'' is the product name

Claims (7)

As a patch provided with a pressure-sensitive adhesive layer and a support having a water content of 70% by mass or more,
The pressure-sensitive adhesive layer,
(A) one or more selected from polyacrylic acid and salts thereof,
(B) a cellulose derivative comprising sodium carboxymethylcellulose having a viscosity of 1 mass% aqueous solution at 25°C of 2,000 mPa·s or less and sodium carboxymethyl cellulose having a viscosity of 1 mass% aqueous solution at 25°C of 2,500 mPa·s or more,
(C) polyhydric alcohol, and
(D) A patch containing a polyvalent metal salt. The method of claim 1,
The content of the component (A) is 2.4 to 10.0 mass% in the pressure-sensitive adhesive layer,
The content of the component (B) is 1.5 to 5.4 mass% in the pressure-sensitive adhesive layer,
Formula (I): [content of (A) component]/[content of (B) component] (mass ratio) is 1.0 to 6.67, and
Formula (II): [content of (C) component]/{1.5 x [content of (A) component] + 2 x [content of (B) component]} (mass ratio) of 1 to 3 patch. The method according to claim 1 or 2,
(C) A patch in which the content of the component is 11 to 25.2% by mass in the pressure-sensitive adhesive layer. The method according to any one of claims 1 to 3,
(D) A patch in which the content of the component is 0.01 to 2% by mass in the pressure-sensitive adhesive layer. The method according to any one of claims 1 to 4,
(E) A patch further containing at least one selected from an active ingredient, a refreshing agent, and a warmth imparting agent. As a manufacturing method of the patch according to any one of claims 1 to 5,
(A) at least one selected from polyacrylic acid and its salt, and (B) a method for producing a patch comprising a step of dispersing a cellulose derivative in (C) a polyhydric alcohol. The method of claim 6,
(A) component and (B) component are the manufacturing method of the patch which is powder.