KR102636944B1 - Patch and its manufacturing method - Google Patents

Abstract

A patch having an adhesive layer and a support,
The adhesive layer,
(A) at least one selected from polyacrylic acid and its salts,
(B) a cellulose derivative containing sodium carboxymethylcellulose having a 1% by mass aqueous solution viscosity of 2,000 mPa·s or less at 25°C and sodium carboxymethylcellulose having a 1% by mass aqueous solution viscosity of 2,500mPa·s or more at 25°C,
(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 having a high-hydrometry adhesive layer and a method for producing the same.

A patch with a high moisture content adhesive layer has excellent cooling effect sustainability. Sodium carboxymethyl cellulose (hereinafter sometimes referred to as CMCNa) may be used in the high water content adhesive layer. In a general pressure-sensitive adhesive layer manufacturing process, CMCNa is dispersed in a polyhydric alcohol as a dispersant to uniformly disperse and dissolve in the adhesive layer (Patent Document 1: Japanese Patent Application Laid-Open No. 2014-028767). However, when dispersing in polyhydric alcohol, if the CMCNa concentration in the dispersion was high, there was a problem that it could not be uniformly dispersed in the adhesive layer and insoluble aggregates were formed. In addition, when stirring for a long period of time to eliminate insoluble aggregates, the temperature of the adhesive layer rises, which causes manufacturing problems such as accelerated 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 water content adhesive layer with a water content of 70% by mass or more, there is an upper limit to the amount of polyhydric alcohol mixed, so the above-described problem of CMCNa becoming high in concentration in the polyhydric alcohol and forming insoluble aggregates could not be solved (Patent Document 2 : Japanese Patent Publication No. 2002-136587).

Meanwhile, a method of uniformly dispersing a polyhydric alcohol and a highly absorbent polymer compound in the adhesive layer is known (Patent Document 3: Japanese Patent Laid-Open No. 2001-122772), but the highly absorbent polymer is expensive and the polyhydric alcohol, which is a plasticizer, is known. Because this is small, the solid becomes hard when dried, so there is a problem that pain may be felt when peeling off the patch.

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

The present invention was made in consideration of the above circumstances, and provides a patch that suppresses the generation of insoluble aggregates in the adhesive layer and suppresses peeling, curling, and backside staining (seepage of the adhesive layer onto the backside of the support). The purpose is to provide

As a result of intensive studies to achieve the above object, the present inventors have found a patch comprising an adhesive layer and a support having a water content of 70% by mass or more, a specific amount of (A) at least one selected from polyacrylic acid and its salts, a specific It was discovered that the above-mentioned problem could be solved by using a patch containing (B) a cellulose derivative essentially containing sodium carboxymethyl cellulose, (C) a polyhydric alcohol, and (D) a polyvalent metal salt, and the present invention was achieved. will be.

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

1. A patch comprising an adhesive layer with a moisture content of 70% by mass or more and a support,

The adhesive layer,

(A) at least one selected from polyacrylic acid and its salts,

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

(C) polyhydric alcohol, and

(D) A patch containing a polyvalent metal salt.

2. In 1,

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

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

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

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

3. In 1 or 2,

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

4. In any one of 1 to 3,

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

5. In any one of 1 to 4,

(E) A patch further containing one or more types selected from active ingredients, refreshing agents, and warming agents.

6. A method for producing the patch according to any one of 1 to 5, comprising:

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

7. In 6,

Method for producing a patch in which component (A) and component (B) are powder.

According to the present invention, it is possible to provide a patch and a method for producing the same that suppress the generation of insoluble aggregates in the adhesive layer and suppress peeling, curling, and staining on the back surface of the patch.

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

(i) Adhesive layer

[(A) Ingredient]

(A) Component is one or more types selected from polyacrylic acid and its salts, and mainly acts as an adhesive. Component (A) includes polyacrylic acid, a neutralized product in which all of polyacrylic acid is neutralized (polyacrylic acid salt) or part of the polyacrylic acid is neutralized (partially neutralized polyacrylic acid), crosslinked polyacrylic acid, and salts thereof. Counter ions of polyacrylate or partially neutralized polyacrylic acid include those neutralized with monovalent metal salts such as sodium and potassium, amine salts such as monoethanolamine, diethanolamine and triethanolamine, and ammonium salts. These can be used individually or in an appropriate combination of two or more types. In addition, (A) component is preferably powder.

(A) The mass average molecular weight of component is not particularly limited, but is preferably 4 million to 5 million. Additionally, 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, rotation 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 method of measuring the mass average molecular weight is gel permeation chromatography (GPC), and the degree of neutralization is a value obtained by the following formula.

Degree of neutralization (mol%) = 100

(A) The content of component is preferably 2.4 to 10.0 mass%, more preferably 3 to 9 mass%, and still more preferably 5 to 8.4 mass% in the adhesive layer. By setting it to 2.4% by mass or more, the adhesive strength is further improved, peeling and curling of the patch can be further suppressed, and insoluble aggregates are less likely to form. On the other hand, by setting it to 10.0% by mass or less, the equations (I) and (II) described later] and a moisture content of 70% by mass or more can be satisfied.

[(B) Ingredient]

Component (B) is sodium carboxymethyl cellulose having a 1 mass% aqueous solution viscosity of 2,000 mPa·s or less at 25°C, preferably 1,000 to 2,000 mPa·s, and a 1 mass% aqueous solution viscosity of 2,500 mPa·s at 25°C. Above, it is a cellulose derivative containing sodium carboxymethyl cellulose, preferably 2,500 to 4,500 mPa·s, and mainly acts as a shape-retaining agent. The blending mass ratio expressed as sodium carboxymethyl cellulose with a 1 mass% aqueous solution viscosity of 2,000 mPa·s or less at 25°C/sodium carboxymethyl cellulose with a 1 mass% aqueous solution viscosity of 2,500 mPa·s or more at 25°C is 1/3 to 3. /1 is preferred.

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

Component (B) contains two types of sodium carboxymethyl cellulose with different viscosities as essential ingredients, but other cellulose derivatives of component (B) include carboxymethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, and hydroxypropyl methyl. Water-soluble cellulose ethers such as cellulose, hydroxypropyl hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxymethyl cellulose, methyl cellulose, and croscarmellose sodium, cationized cellulose, and salts thereof. Cellulose derivatives used in combination with sodium carboxymethyl cellulose include carboxymethyl cellulose, hydroxypropyl cellulose, and croscarmellose sodium. From the viewpoint of manufacturability and gel retention properties, the ratio of sodium carboxymethyl cellulose in component (B) is preferably 70 to 100% by mass. The amount of sodium carboxymethyl cellulose in the adhesive layer is preferably 2 to 5% by mass. Moreover, (B) component is preferably powder.

(B) The content of component is preferably 1.5 to 5.4 mass%, more preferably 2 to 5 mass%, and even more preferably 3 to 4 mass% in the adhesive layer. By setting the component (B) to 1.5% by mass or more, backside staining is further suppressed. By setting it to 5.4% by mass or less, the equations (I) and (II) described later and the moisture content of 70% by mass or more can be satisfied.

[(C)Component]

Component (C) is a polyhydric alcohol, and mainly acts as a dispersing agent for the components (A) and (B). Polyhydric alcohols include ethylene glycol, 1,3-butanediol, propylene glycol, isoprene glycol, amylene glycol, glycerin, diglycerol, triglycerol, polyglycerin, diethylene glycol, dipropylene glycol, polyethylene glycol, and diethylene glycol monoalkyl ether. These can be mentioned, and one type can be used alone or in an appropriate combination of two or more types. Among them, it is preferable to use glycerin.

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

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

Formula (II): [Content of component (C)]/{1.5 It is specified, and 1 to 3 is preferable. The above equation specifies the amounts of component (A) and component (B) that can be uniformly dispersed in component (C) and uniformly dissolved in the adhesive layer, respectively, (A) This means that 1.5 times the amount of component (C) is needed for component (C) and 2 times the amount of component (C) for component (B). By setting this ratio to 1 or more, components (A) and (B) are uniformly dissolved in the adhesive layer, making it more difficult for insoluble aggregates to form. On the other hand, by setting it to 3 or less, the above-mentioned equation (I) and the moisture content of 70% by mass or more can be satisfied.

[(D) Ingredient]

(D) Component is a polyvalent metal salt and acts as a crosslinking agent. Polyvalent metal salts include alums such as potassium alum, ammonium alum, and iron alum, aluminum hydroxide, aluminum sulfate, aluminum chloride, aluminum acetate, aluminum oxide, aluminum silicate, aluminum metasilicate, calcium hydroxide, calcium carbonate, calcium phosphate, calcium nitrate, and calcium chloride. , calcium acetate, calcium oxide, calcium phosphate, magnesium hydroxide, magnesium carbonate, magnesium sulfate, magnesium acetate, magnesium silicate, magnesium oxide, magnesium alumina hydroxide, magnesium aluminometasilicate, magnesium aluminosilicate, synthetic hydrotalcite, and di. Hydroxyaluminum aminoacetate, etc. can be mentioned. These can be used individually or in an appropriate combination of two or more types. Among them, in the spreading process of the adhesive layer, the adhesive composition that becomes the adhesive layer is uniformly applied to at least one surface of the support, so it acts slowly rather than immediately (it is less water soluble than water soluble and gradually dissolves in the adhesive layer). It is desirable to do so. Preferred such components include, for example, magnesium alumina hydroxide, magnesium aluminometasilicate, magnesium aluminum silicate, synthetic hydrotalcite, and dihydroxyaluminum aminoacetate.

(D) The content of component is preferably 0.01 to 2% by mass, more preferably 0.03 to 1% by mass, and still more preferably 0.05 to 0.5% by mass in the adhesive layer. By setting it to 0.01% by mass or more, the retention properties of the adhesive layer can be more sufficiently obtained, and backside unevenness is further suppressed. On the other hand, by setting it to 2% by mass or less, peeling and curling of the patch is further suppressed, adjustment of the crosslinking speed during production becomes easy, and uneven application of the adhesive composition that becomes the adhesive layer is suppressed.

[(E) Ingredient]

The pressure-sensitive adhesive layer of the present invention may contain (E) one or more types selected from active ingredients, refreshing agents, and imparting warmth. Active ingredients include steroid anti-inflammatory agents, non-steroid anti-inflammatory agents, herbal medicine, and essential oil ingredients.

Steroid-based anti-inflammatory agents include, for example, amcinoids, prednisolone valerate, diflucortholone valerate, betamethasone valerate, betamethasone acetate, dexamethasone acetate, betamethasone dipropionate, dexamethasone, triamcinolone acetonide, rylcinonide, hydrocortisone, and blood. Flumethasone, fluocinonide, fluocinolone acetonide, fluorometholone, fludroxycortide, prednisolone, clobetasol propionate, beclomethasone propionate, betamethasone, methylprednisolone, methylprednisolone acetate, hydrocortisone butyrate. etc. can be mentioned. When mixing these steroid-based anti-inflammatory agents, the content is preferably 0.05 to 5% by mass in the adhesive layer.

Non-steroidal anti-inflammatory drugs include, for example, loxoprofen, diclofenac, felbinac, indomethacin, glycol salicylate, salicylic acid, acetylsalicylic acid (aspirin), acetaminophen, aminopyrine, antipyrine, oxyphenbutazone, sulphyrin, and ibuprofen. , sulindac, naproxen, ketoprofen, etofenamate, salicylamide, triethanolamine salicylate, flufenamic acid, meclofenamic acid, colchicine, bupexamac, fenbufen, diflunisal, alclofenac, phenyl Butazone, mefenamic acid, fenoprofen, bendazac, piroxicam, flurbiprofen, zaltoprofen, etodolac, pranoprofen, mepirizole, suprofen, glycyrrhetinic acid, glycyrrhizic acid and Their salts and derivatives, etc. can be mentioned. When mixing a non-steroidal anti-inflammatory agent, the content is preferably 0.05 to 5% by mass in the adhesive layer.

Herbal medicine and essential oil ingredients include, for example, herbal medicine powders such as barley, extracts of herbal medicines such as yellow and white, Chinese chives, herbal medicine, licorice, goldenrod, gardenia, angelica root, elderberry, columbine, coix rice, etc., peppermint oil, white peppermint oil, cinnamon oil, etc. Essential oils, etc. can be mentioned. When mixing herbal medicine or essential oil components, the content is preferably 0.05 to 5% by mass in the adhesive layer.

Freshening agents include, for example, limonene, terpinolene, methane, terpene hydrocarbon compounds such as p-methane such as terpinene and monocyclic monoterpene hydrocarbon compounds derived therefrom, l-menthol, isopuregol, 1 Menthol-related compounds such as ,3-methoxypropane-1,2-diol, camphor, thymol, etc. are suitably used. When mixing a refreshing agent, the content is preferably 0.05 to 5% by mass in the adhesive layer.

The warmth imparting agent may be any substance that causes a feeling of warmth when applied to the skin. Examples of such substances include capsaicin analogues such as capsicoside, capsaicin, capsaicinoid, dihydroxycapsaicin, and capsanthin, and red pepper extract. , substances that provide warmth derived from peppers such as red pepper tincture and red pepper powder, benzyl nicotinic acid, β-butoxyethyl nicotinic acid, N-acylwanilamide, nonylwanylamide, vanillyl butyl ether, tocopherol acetate, acetyleugenol, herbal medicine. Extracts, charcoal bark extract, arnica tincture, ginger extract, cinnamon oil, etc. When mixing a warmth imparting agent, the content is preferably 0.05 to 5% by mass in the adhesive layer.

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

The content when mixing (E) component is good as an effective amount, but 0.05-5 mass % is preferable in an adhesive layer, and 0.2-2 mass % is more preferable. By setting it to 0.05% by mass or more, sufficient medicinal effect, refreshing sensation, and warm sensation can be obtained. Even if it is mixed in excess of 5% by mass, higher medicinal efficacy, cooling sensation, or warm sensation cannot be obtained, and skin irritation may occur.

[Random Component]

In the adhesive layer of the present invention, the following components generally used in water-containing adhesives can be used in appropriate amounts individually or in appropriate combinations of two or more types, as long as the effects of the present invention are not impaired. In addition, the following components are examples, and depending on the component, they may be described overlappingly.

(1) Hardening modifier

Sodium edetate, sodium edetate hydrate, sodium metaphosphate, citric acid, etc. can be used. When mixing the curing regulator, the content is preferably 0.01 to 3% by mass in the adhesive layer.

(2) Organic acids

Tartaric acid, malic acid, lactic acid, etc. can be mentioned. When mixing an organic acid, the content is preferably 0.1 to 3% by mass in the adhesive layer.

(3) Preservatives

Examples include methyl paraoxybenzoate (methylparaben) and propyl paraoxybenzoate (propylparaben). When mixing a preservative, the content is preferably 0.01 to 2% by mass in the 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, polyoxyethylene glycol fatty acid ester, Examples include ethylene glycol ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene phytosterol, sorbitan fatty acid ester, and glycerin fatty acid ester. When mixing the surfactant, the content is preferably 0.2 to 5.0% by mass in the adhesive layer.

(5) Spices

Fennel oil, fragrant oil, clove oil, thyme oil, turpentine oil, henopody oil, yamazin oil, eucileptops oil, lavender oil. Examples include peppermint oil, lemon oil, orange oil, turmeric oil, bergamot oil, rose oil, citronella oil, lemongrass oil, camphor oil, geranium oil, rosemary oil, and sage oil. In addition, plant extracts include, for example, aloe, anise, angelica, benzoin, emotel, chamomile, chamomile, garlic, cardamom, galbanum, caraway, carrot seed, coriander tree, grapefruit, cypress, sandalwood, and cedarwood. , juniper, star anise, sage, geranium, celery, thyme, tarragon, turpentine, frankincense, violet, pine, parsley, birch, patchouli, rose, hyssop, fennel, black pepper, barley, myrrh, yarrow, lemon, Lemongrass, rosemary, laurel, spirea chrysanthemum, spirea grass, cornflower, almond, thistle, arnica, cypress, fennel, goldenrod, erica, cedar, mustard, persimmon, persimmon, chrysanthemum, umbrella grass, marigold, celandine , watercress, azalea, gentiana, cherry, psyllium, birch, cedar, chinensis, camphor, gerbil, gentian, plum, pear, eucalyptus, jujube, dandelion, syringa, chervil, gerbil, asparagus root. , winter bean sprouts, wild roses, wild carrots, achemilla, ash trees, sagebrush, daisy, borage, mugwort, marjoram, melissa, peach, peach, mistletoe, eucalyptus, lavender, forsythia, horseradish, etc. Extracts can be given. Among these, extracts from chamomile, sage, parsley, rosemary, chrysanthemum, chives, cornflower, anise, laurel, angelica, fennel, peppermint, lemon balm, lavender, thyme, etc. are particularly suitable. Specific components of such extracts include, for example, cineole, borneol, camphor, linanol, berbenol, flavonoids, choline, amino acids, tannins, plant acids, fatty acids, cyanogenic glycosides, salvin, condensed tannins, Phenolic acid, carnosic acid, triterpenic acid, thujone, salbene, pinene, apiol, apiolin, myristic acid, coumarin, chamazulene, farnesene, bisabolol, geraniol, eugenol, terpene, pheland Examples include ren, anethole, menthone, citral, citronellal, and eugenol acetate. When mixing fragrance, the content is preferably 0.01 to 1% by mass in the 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 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 Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 205, Orange No. 206, Orange No. 207, Orange No. 401, Orange No. 402, Orange No. 403, Brown No. 201, Purple No. 201, Purple No. 401, Black No. 401 etc. can be mentioned. The content of the dye is not particularly limited and can be appropriately selected depending on the purpose, but the content when mixing the dye is preferably 0.00005 to 0.1% by mass, more preferably 0.0001 to 0.01% by mass of the adhesive layer. If the content is too small, there is a risk that the effect of mixing may not be sufficiently obtained, and if the content is too high, there is a risk that the color tone may become too strong. In addition, when mixing a pigment, it is preferable to dissolve the pigment in water, oil, alcohol, etc. and then knead it with other ingredients so that the pigment does not darken or have spots when spreading the adhesive composition on the surface of the support.

The water content of the adhesive layer is 70% by mass or more, and is preferably 70 to 82% by mass. Sufficient cooling effect is obtained by setting the moisture content to 70% by mass or more, and staining of the back surface is suppressed by setting it to 82% by mass or less.

The pH of the 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 (e.g., HM-30V, flat type pH electrode GST-5313F, manufactured by DKK-TOA CORPORATION) into contact with the adhesive composition after spreading on the support under conditions of 25°C.

(ii) Manufacturing method of adhesive layer

The method for producing the adhesive layer is not particularly limited, but in order to make it more difficult to form insoluble aggregates of components (A) and (B), for example, (A) at least one selected from polyacrylic acid and its salts, It is preferable to include a step of dispersing (B) the cellulose derivative in (C) polyhydric alcohol.

More specifically, (C) one or more types selected from polyacrylic acid and its salts in powder form (A) and (B) a cellulose derivative are added to polyhydric alcohol, and the components (A) and (B) are dispersed and stirred. Thus, prepare preliminary dispersion 1. Separately, it includes a process of dispersing component (D) into component (C) to produce preliminary dispersion 2. Component (E) may be dispersed in a preliminary dispersion, but it is preferable to include a step of mixing it with an emulsifier along with a fragrance or preservative. It is preferable to include the step of adding preliminary dispersion 1 to a preliminary mixture of water and other optional components and stirring, then adding and stirring preliminary dispersion 2. Optional components may be added as a pre-dissolution or pre-dispersion, respectively.

(iii) support

As the support, a known support can be used, and examples include paper, woven fabric, non-woven fabric, and knitted fabric. Among them, knitted fabric with a basis weight of 90 to 140 g/m2 or nonwoven fabric with a basis weight of 70 to 140 g/m2 is preferable. The amount of roll applied when spreading the pressure-sensitive adhesive composition that becomes the pressure-sensitive adhesive layer onto the support is not particularly limited, but is preferably 800 to 1,200 g per 1 m2 of the support.

As for knitted fabric, the material (type) of the fiber is not particularly limited, and examples include polyester, nylon, polyolefin (PE, PP, etc.), vinylon, polyvinylidene chloride, polyvinyl chloride, acrylic resin, and polyurethane. There are tributaries. In addition, their degree of polymerization is not particularly limited, and those having a degree of polymerization commonly used as materials for knitted fabrics can be used.

The knitting method of the knitted fabric is not particularly limited, and examples include warp knitting (tricat knitting, denbit coat knitting, satin knitting, atlas knitting, flat knitting, rim knitting, pearl knitting), circular knitting (double-sided terry knitting, Single-sided knitting, circular rib knitting), horizontal knitting, circular knitting knitted with multifilament yarns, multi-step double-sided knitting, knit miss knitting, cross inlay knitting, inlay knitting, etc. are employed. Preferably, tricot knitting, double-sided knitting, single-sided knitting, circular rib knitting, circular knitting made of multifilament yarns, and multi-stage double-sided knitting are employed. The fiber used in knitted fabric can generally be 10 to 80 denier when single yarn is used. When using multifilament, fibers of 40 to 100 denier can generally be used.

The basis weight of the knitted fabric is preferably 90 to 140 g/m2, and the lower limit is more preferably 95 g/m2 or more, and even more preferably 100 g/m2 or more. If the basis weight is less than 90 g/㎡, the degree of twist becomes weak, and there is a risk of clumping and sagging in the adhesive layer during rolling. 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/m2, the adhesive layer becomes hard, and there is a risk that the usability, such as conformability to the skin, may deteriorate.

As a nonwoven fabric, the material of the fiber is not particularly limited, and examples include polyester resins such as polyamide, polyethylene, and polyethylene terephthalate, polyolefin resins such as polypropylene, polyester ether, polyurethane resin, acrylic resin, and polyvinyl. Alcohol, polystyrene-based resin, etc. can be mentioned.

The manufacturing method is not particularly limited, and nonwoven fabrics using manufacturing methods such as spunlace, spunbond, thermal bond, chemical bond, and needle punch are selected.

The basis weight of the nonwoven fabric is preferably 70 to 140 g/m2, and the lower limit is preferably 75 g/m2 or more, and more preferably 80 g/m2 or more. If the basis weight is less than 70g/㎡, the degree of twist becomes weak, and there is a risk of clumping and sagging in the adhesive layer during rolling. 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/m2, the adhesive layer becomes hard, and there is a risk that the usability, such as conformability to the skin, may deteriorate.

(iv) Patch and method of manufacturing the same

The patch of the present invention includes an adhesive layer with a moisture content of 70% by mass or more and a support. For example, an adhesive layer is formed on one side of the support. After spreading the adhesive composition that becomes the adhesive layer on the support, if necessary, use a plastic film (release liner) such as polyethylene, polypropylene, or polyethylene terephthalate to cover the surface of the adhesive layer, and cut it to the desired size. there is. Alternatively, after spreading the adhesive composition that becomes the adhesive layer on the release liner, it can be bonded to a support, cut to a desired size, and used.

It is preferable that the adhesive strength according to the volatic value of the adhesive layer is 10 to 32, and more preferably 16 to 30. By setting it above the lower limit, the adhesive strength is improved and peeling and curling of the patch can be further suppressed. On the other hand, by setting it below the upper limit, skin irritation and pain when peeling off decrease. In addition, the method of measuring adhesive force by bolt tack is measured according to the method described in JIS Z 0237. Specifically, the ball rolling device used in JIS Z 0237 is used, the inclination angle is 30°, the length of the running path is 100 mm, and the measuring surface is 50 mm. Balls made of the material specified in JIS G 4805 are used, and the sizes of the balls are 31 types ranging from 1/16 to 1 of the “nominal ball dimension” of JIS B 1501, and are 32 times the “nominal ball dimension” of JIS B 1501. The numerical value is used as the ball number as an indicator of adhesive strength. Attach the test piece with the adhesive side up at a predetermined position on the inclined plate of the ball rolling device, and set balls of each size in the gate. Open the gate slowly, roll the balls, find the largest ball that is completely still (not moving for more than 5 seconds) within the measurement surface, and use that ball number as the ball tack value.

The method of using the patch of the present invention is not particularly limited, and for example, the patch is used by attaching it to a human's shoulder, waist, calf, thigh, or sole.

Example

Hereinafter, the present invention will be described in detail by way of Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, in the examples below, unless otherwise specified, “%” in the composition indicates mass% and ratio indicates mass ratio.

[Examples, comparative examples]

<Manufacturing method>

Sodium edetate hydrate was added to purified water with stirring to obtain (preliminary lysate 1). Sodium metaphosphate or citric acid was added to purified water while stirring to obtain (preliminary lysate 2). Tartaric acid, malic acid, or lactic acid was added to purified water while stirring to obtain (preliminary lysate 3). Component (E), l-menthol, preservative, and fragrance were added to the emulsifier and stirred to obtain (preliminary mixture 1). Powdered component (A) and component (B) were added to a portion of component (C), stirred, and uniformly dispersed and dissolved to obtain (preliminary dispersion 1). Component (D) was added to part of component (C) and stirred to obtain (preliminary dispersion 2). Pigment was added to the remaining component (C) and stirred to obtain (preliminary dispersion 3).

Preliminary dissolution 2 and preliminary dispersion 3 were added to preliminary dissolution 1 and stirred with a Henschel mixer to obtain (dough 1).

Preliminary dispersion 1 was stirred into dough 1 and kneaded in a Henschel mixer to obtain (dough 2).

Preliminary dispersion 2 was added to dough 2 and stirred with a Henschel mixer to obtain dough 3.

Preliminary dissolution 3 and preliminary dissolution 1 were added to dough 3 and stirred with a Henschel mixer to obtain an adhesive composition.

The adhesive composition was spread uniformly on the release liner so that the adhesive layer per patch (14 cm x 10 cm) was about 12 g. After that, a polyester knitted fabric ("Basic weight 105 ± 10 g/m2, thickness 0.70 mm, thickness 75 denier" (manufactured by Teijin Frontier Co., Ltd.)) is applied to the surface of the adhesive layer, and the desired size ( It was cut into pieces (14cm x 10cm) and a patch was prepared. The following evaluation was performed on the obtained patch. In addition, the adhesive strength of the patches obtained in the examples was 10 to 32 according to the bolt-tack value.

[Evaluation of the incidence of insoluble aggregates]

The rate of occurrence of insoluble aggregates was evaluated based on the rate at which insoluble aggregates with a diameter of 2 mm or more occurred during sampling (100 sheets of 12 g/14 cm x 10 cm formulation) in the leading edge of the adhesive composition obtained by kneading. Based on the evaluation criteria below, “◎” or “○” was considered passing.

<Judgment criteria>

◎: 2% or less

○: More than 2% but less than 5%

×: greater than 5%

[Peeling and drying after 8 hours]

A patch cut to 10 cm x 14 cm was applied to the calves of nine healthy adults, and the condition after 8 hours was evaluated based on the ratings below. The results are expressed according to the following evaluation criteria based on the total score of 9 people. A score of 27 or higher was considered passing.

<Rating>

5: No peeling or curling of the patch

4: Peeling and curling around the patch (less than 1/4 of the total)

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

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

1: More than 1/2 of the patch is curled or peeled off.

<Evaluation criteria for peeling and curling after 8 hours>

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

○: The total score of 9 evaluation results is 27 or more but less than 36.

×: Total score of 9 evaluation results is less than 27 points

[Backside stain]

After manufacturing the patch, 20 sheets were stacked on top of each other, and after standing for a full day, the patch at the bottom was evaluated by visual and sensory evaluation according to the following evaluation criteria.

◎: No stains on the back side are observed.

○: There is some staining on the back, but it is at the limit level for use.

×: You can confirm that it is moist.

[pH]

Measurement was performed under conditions of 25°C using HM-30V manufactured by DKK-TOA CORPORATION as a pH meter and a flat type pH electrode GST-5313F by bringing it into direct contact with the adhesive composition.

For the adhesive composition of Example 16, a patch was also prepared in the same manner using a nonwoven fabric with a basis weight of 90 g/m2. As a result of evaluating the obtained patch for back staining in the same manner as in the above Example, back staining was not confirmed.

In Comparative Example 1, since there were too many insoluble aggregates and an adhesive layer could not be produced, evaluation of “peeling/curling after 8 hours” and “back surface staining” was not performed.

The raw materials used in the above examples are shown below. In addition, unless otherwise specified, the amount of each component in the table is the pure amount converted.

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

Sodium carboxymethyl cellulose: “Daicel CMC1390”: (manufactured by DAICEL FINECHEM LTD.), 1% aqueous solution viscosity 2,500 to 4,500 mPa·s at 25°C (BL viscometer: rotor No. 4, 25°C, rotation speed 60 rpm), Etherification degree 1.0~1.5, white powder

Carboxymethyl cellulose: “NS-300”: (Gotoku Chemical Company Ltd.)

・Hydroxypropyl cellulose: “HPC-H”: (Nippon Soda Co., Ltd.)

· Croscarmellose sodium: “KICCOLATE ND-2HS”: (Nichirin Chemical Industries, Ltd.)

Glycerin: Concentrated glycerin “Pharmacy Concentrated Glycerin” (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)

・Propylene glycol: “Propylene glycol” (manufactured by Mitsui Takeda Chemical Co., Ltd.)

·Dihydroxyaluminum aminoacetate: “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” (made 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)

· Loxoprofen sodium: “Japanese Pharmacopoeia Loxoprofen Sodium Hydrate” (manufactured by Daiwa Pharmaceutical Co., Ltd.)

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

・Felbinac: “Felbinac” (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.)

· Propyl paraoxybenzoic acid: “Metkins-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 oil: “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 “basis weight 105 ± 10 g/m2, thickness 0.70 mm, thickness 75 denier (manufactured by Teijin Frontier Co., Ltd.)

· Release liner: Polypropylene film “CPP30μ, thickness 0.12mm” (manufactured by OG CORPORATION)

(Note): Items in 「」 are product names.

Claims (7)

A patch comprising an adhesive layer having a moisture content of 70% by mass or more and a support,
The adhesive layer,
(A) at least one selected from polyacrylic acid and its salts,
(B) a cellulose derivative containing sodium carboxymethylcellulose having a 1% by mass aqueous solution viscosity of 2,000 mPa·s or less at 25°C and sodium carboxymethylcellulose having a 1% by mass aqueous solution viscosity of 2,500mPa·s or more at 25°C,
(C) polyhydric alcohol, and
(D) contains a polyvalent metal salt,
Formula (I): [content of (A) component]/[content of (B) component] (mass ratio) is 1.0 to 6.67, and
Formula (II): A patch where [content of (C) component]/{1.5×[content of (A) component]+2×[content of (B) component]} (mass ratio) is 1 to 3. According to claim 1,
(E) A patch further containing one or more types selected from active ingredients, refreshing agents, and warming agents. The method of claim 1 or 2,
(A) The content of component is 2.4 to 10.0% by mass in the adhesive layer,
(B) A patch in which the content of component is 1.5 to 5.4% by mass in the adhesive layer. The method of claim 1 or 2,
(C) A patch in which the content of component is 11 to 25.2% by mass in the adhesive layer. The method of claim 1 or 2,
(D) A patch in which the content of component is 0.01 to 2% by mass in the adhesive layer. A method for producing the patch according to claim 1 or 2, comprising:
A method for producing a patch comprising the step of dispersing (A) at least one selected from polyacrylic acid and its salts, and (B) a cellulose derivative in (C) a polyhydric alcohol. According to claim 6,
Method for producing a patch in which component (A) and component (B) are powder.