JPH0794382B2 - Patch agent - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a poultice, and more specifically, it has a strong adhesive force and can be easily applied to a joint without fixing with a bandage, an adhesive tape or the like. At the same time, it relates to an extremely stable poultice.

[Technical background of the invention]

A poultice applied to the skin of an affected area for the purpose of anti-inflammatory or analgesia generally contains a medicinal component such as methyl salicylate, ethylene glycol salicylate, camphor and menthol in a base having a complicated composition. There is. Alternatively, in recent years, a plaster consisting of the above-mentioned medicinal ingredients and a base is applied to a non-woven fabric or a woven fabric, a peelable protective film is attached to the plaster surface, and the protective film is peeled off at the time of use and attached to the skin. Many types of poultices have been put to practical use.

Regarding such a poultice, in terms of quality, the active ingredient is stable, there are no side effects, it has appropriate viscoelasticity and adhesiveness, it has appropriate water retention,
Although it is required to have properties such as no loss of sweat, good shape retention, and no change over time, in recent years it has become more adhesive and stretchable and can be bandaged on elbows or knees. There has been a strong demand for a poultice that can be reliably applied without using adhesive tape or the like. Conventionally,
As a poultice having this strong adhesive strength, a gel made of sodium polyacrylate, gelatin, etc. is kneaded with an adhesive such as polyacrylic acid, acrylic ester, etc., and acid PH is added to stabilize medicinal components such as methyl salicylate. Although a weakly acidic poultice prepared by adjusting the above is known, sodium polyacrylate, gelatin and the like have a disadvantage that the viscosity is drastically lowered by the addition of an acid and the workability during production is deteriorated. In order to compensate for this, it has been attempted to add another water-soluble polymer or a large amount of powder such as kaolin to adjust the viscoelasticity of the plaster during production, but the formulation is complicated. In addition to increasing the amount of kaolin, the adhesive strength becomes weaker, and it becomes necessary to further increase the adhesive strength to compensate for this adhesive strength, which makes the formulation extremely complicated, resulting in complicated processes, and There was a situation that the manufacturing cost also increased.

[Object of the Invention] The present invention has been made based on the above circumstances, and an object of the present invention is to combine the above-mentioned various characteristics required for a poultice, and further to have a stronger adhesive property in a joint part. It is to provide a poultice that can be used without any discomfort without using bandages or adhesive tape.

[Details of Invention]

α ・ β-Unsaturated carboxylic acid or its derivative and α ・ β-
The polycarboxylic acid cross-linked copolymer obtained by cross-linking the alkali metal salt of unsaturated carboxylic acid with a polyfunctional cross-linking agent is rich in water retention and tackiness. It is possible to obtain an adhesive poultice. However, in a poultice that basically contains a considerable amount of water and various components and is applied to the affected skin,
By simply adding the cross-linked copolymer, the poultice for plastering a patch may cause a phenomenon such as troche during perspiration or so-called sagging with time, and the above-mentioned various properties required for the poultice are sufficiently satisfied. I can't get the drug.

The present inventor has made earnest studies to obtain a poultice that satisfies the above-mentioned various characteristics and has a strong adhesive force. As a result, it is possible to crosslink aluminum with an α / β-unsaturated carboxylic acid having strong adhesive force or a derivative thereof. In the presence of an oxy acid, a polycarboxylic acid-based cross-linking copolymer having a PH of 8 or less obtained by polymerizing an alkali metal salt of α / β-unsaturated carboxylic acid in the presence of a polyfunctional crosslinking agent A plaster containing a cross-linked product obtained by cross-linking aluminum has good shape retention, sagging,
It does not cause troche at all, has a strong adhesive force, and since the polycarboxylic acid-based cross-linked copolymer aqueous solution itself is weakly acidic, a small amount of acid needs to be added, resulting in almost no decrease in viscosity. The present invention has been completed by finding that a poultice having the above-mentioned various properties can be obtained with an extremely simple manufacturing formulation.

That is, the poultice of the present invention has the general formula (In the formula, R represents H, COOH or COOX, and R ₁ is H, C
Indicates H ₃ , CH ₂ COOH or CH ₂ COOX ₁ . Also, X and X ₁
Indicates an alkali metal. ) Α-β-unsaturated carboxylic acid represented by (In the formula, R ₂ represents H, COOH or COOX ₃ , and R ₃ represents H, C
Indicates H ₃ , CH ₂ COOH or CH ₂ COOX ₄ . Also, X ₂ X ₃ and X
₄ indicates an alkali metal. ) A polycarboxylic acid-based cross-linking copolymer having a PH of 8 or less, which is obtained by polymerizing a mixed monomer consisting of an α / β-unsaturated carboxylic acid alkali metal salt in the presence of a polyfunctional crosslinking agent. 1 to 10% by weight (total weight ratio of the base material) and 0.01 to 1% by weight (total weight ratio of the base material) of the sparingly soluble aluminum compound are crosslinked in the presence of an oxy acid to form a crosslinked product. 4.8
It is characterized by being set to ~ 6.0.

In the present invention, examples of the α / β-unsaturated carboxylic acid represented by the general formula (A) or its derivative used for obtaining the polycarboxylic acid-based crosslinked copolymer include acrylic acid, methacrylic acid, fumaric acid, Examples thereof include maleic acid and itaconic acid. Further, as the alkali metal salt of α / β-unsaturated carboxylic acid represented by the general formula (B),
For example, sodium acrylate, potassium acrylate,
Examples thereof include lithium acrylate, sodium methacrylate, potassium methacrylate, lithium methacrylate and the like. In that case, especially when acrylic acid is used as the .alpha..beta.-unsaturated carboxylic acid or its derivative and sodium acrylate is used as the alkali metal salt of the .alpha..beta.-unsaturated carboxylic acid, it is suitable to obtain the desired poultice. .

α ・ β-Unsaturated carboxylic acid or its derivative and α ・ β-
The mixing ratio of the unsaturated carboxylic acid with the alkali metal salt is such that the PH of the crosslinked copolymer obtained by polymerizing these mixed monomers in the presence of a polyfunctional crosslinking agent is 8 or less. It is not particularly limited. Further, the adhesive strength changes depending on this mixing ratio, and becomes stronger as the amount of α / β-unsaturated carboxylic acid increases, but in order to realize the above-mentioned various properties required for poultices as a whole, α / β-unsaturated When acrylic acid is used as the carboxylic acid or its derivative and sodium acrylate is used as the alkali metal salt of α / β-unsaturated carboxylic acid, acrylic acid: sodium acrylate = 50: 50
Is particularly preferable.

Examples of the polyfunctional crosslinking agent include divinyl ether, divinyl xylene, polyethylene glycol, diallyl ether, diallyl phthalate, ethylene glycol methacrylic ester and the like.

The acrylic acid-sodium acrylate cross-linked copolymer is a block polymer having a molecular weight of 2,000,000 to 4,000,000 and used in an amount of 1 to 10% by weight, preferably 3 to 7% by weight based on the total weight of the base. If it is less than 1%, the shape retention property is poor, and if it is more than 10%, the viscosity becomes too high and the workability is deteriorated.

Examples of the aluminum compound used in the present invention include normal salts of inorganic or organic acids such as aluminum chloride, aluminum sulfate, aluminum acetate, and aluminum stearate, or basic salts thereof, double salts such as aluminum alum, and sodium aluminate. Incorporating an aluminate inorganic aluminum complex salt such as, an organic aluminum chelate compound, aluminum hydroxide, magnesium aluminometasilicate, and synthetic aluminum silicate. Even if these aluminum compounds are easily soluble, they can be made hardly soluble by appropriate treatment, so that the solubility of the aluminum compound itself as a starting material does not matter. Further, these aluminum compounds may be blended alone or in combination of two or more, and the blending amount thereof is within the range of 0.01% to 1% by weight based on the total weight of the base, and the polycarboxylic acid type. It may be increased or decreased as appropriate depending on the amount of the crosslinked copolymer compounded. If the blending amount is less than 0.01%, dripping or trowel may occur and satisfactory shape retention may not be obtained.
Further, if it is blended in an amount of more than 1%, the crosslinking becomes too strong and it becomes difficult to obtain a satisfactory adhesive strength.

The medicinal component of methyl salicylate decomposes rapidly when PH is 7 or more, and deteriorates stability over time. It is best to adjust the pH between 3.0 and 4.0 to minimize its decomposition, but the skin PH is usually 4.5 to 6.5, and if it is out of this range, side effects such as skin irritation and rash will occur. Therefore, the pH of the poultice is 4.5 to 6.5, particularly preferably 4.8 to 6.0.
And In the present invention, a polycarboxylic acid-based cross-linking copolymer having a PH of 8 or less is blended, which is compared to a fully neutralized sodium polyacrylate having a PH of about 9 in which all carboxylic acids are completely replaced with sodium. PH with a small amount of acid 4.
It can be adjusted to 8 to 6.0, and at the same time, it is effective in reducing the amount of low molecular weight salt produced as a by-product during the adjustment. Low molecular weight salts are not preferable because they cause itching on the skin and cause water separation of the gel.

The role of the oxyacid used in the present invention is to neutralize the polycarboxylic acid-based cross-linked copolymer, but at the same time, by gradually solubilizing the poorly soluble aluminum salt by its chelating action, It also serves to prevent the polycarboxylic acid-based cross-linked copolymer and aluminum ions from reacting instantaneously when mixed to form a non-uniform gel. Such oxyacids include lactic acid, tartaric acid, malic acid,
Examples thereof include citric acid, gluconic acid, and glucuronic acid, but lactic acid and tartaric acid are particularly preferable for the purpose of promoting aluminum crosslinking.

A PO4.8-6.0 poultice containing a cross-linked product obtained by cross-linking a polycarboxylic acid-based cross-linked copolymer and a sparingly soluble aluminum compound in the presence of an oxy acid is itself a stable retention of the medicinal component. It has strength, is excellent in shape retention and water retention, and has stability over time without causing shrinkage or sagging even when sweating or humid, and has extremely strong adhesiveness, but it also has a water candy content of 5-40. When blended by weight%,
The modification effect is enhanced in terms of moisturizing and tackiness.

The water candy referred to here is a mixture of sugars containing maltose as a main component, and also contains reduced maltose water candy. Conventionally, glycerin, propylene glycol, sorbit, etc. have been blended as moisturizers in poultices, but these components have moisturizing properties but are not tacky, so it is necessary to add a tacky component separately. However, since water candy has a moisturizing property and at the same time it is tacky, it is necessary to mix it with a poultice to increase the adhesive force, especially after several minutes to several hours after application to the affected area. Especially effective.

In the present invention, methyl salicylate, ethylene glycol salicylate, camphor, in addition to medicinal ingredients such as menthol, further glycerin, propylene glycol, humectants such as sorbit, sodium carboxymethyl cellulose, sodium alginate, polyvinylpyrrolidone, carboxy, if necessary. Although water-soluble polymers such as vinyl polymers can be blended, the aluminum cross-linking degree of the polycarboxylic acid-based cross-linked copolymer can be adjusted to an appropriate level without blending gelatin, kaolin, etc., which have been conventionally required. If the plaster is spread on a support such as a non-woven fabric, the plaster does not exude or squeeze out from the non-woven fabric by providing such viscoelasticity.

The poultice of the present invention can be used by directly applying it to the skin of the affected area, but it is preferably in the form of being preliminarily spread on a support such as a non-woven fabric or a woven fabric. In that case, even if the patch has a strong adhesive force, the adhesive force will be diminished unless the support is supple and stretchable in order to be applied to the elbows, knees, etc. without discomfort. A support which is stretchable in both directions is preferably used. An example of such a support is a non-woven fabric formed by needle punching a fiber layer of polyester, rayon and / or polyolefin on both sides and one side of a layer made of a water-swellable vinylon film. Usually, when spreading a plaster for poultice, the plaster is spread on a non-woven fabric with a coater, and immediately after that, the product covered with a peelable plastic film is cut into a certain size to make it a product, but it is stretchable from the beginning. In the case of a flexible nonwoven fabric, the nonwoven fabric stretches due to the mechanical tension at the time of spreading, and it is extremely difficult to cut it into a certain size. However, the above-mentioned non-woven fabric does not have elasticity when the vinylon film is in a dry state, but since it has the property of absorbing moisture after application of the adhesive and expanding and contracting in the length and width directions, it is easy to spread the adhesive. At the same time, it is very convenient since it expands and contracts in both directions when used on the affected skin after spreading. The degree of expansion and contraction can be adjusted by changing the grade of the vinylon film, the fiber composition, and the needle punching conditions.

〔Example〕

Next, examples will be shown and described in more detail, but the present invention is not limited to the examples.

The poultices having the formulations shown in Table 1 were prepared by the following production method.

Manufacturing method of Examples 1, 2, 3 and Comparative Example 1: After dispersing in, the liquid in which is dispersed is added and stirred. Then, a liquid in which is dispersed is added and kneaded, and after further adding, a liquid in which a part of is dissolved is added and kneaded to obtain a poultice.

Manufacturing method of Comparative Example 2: After dispersing in, is gradually added and dissolved by stirring.
Then, the liquid in which is dispersed is added and stirred, and the liquid in which is dispersed is further added and kneaded. Then, is added, and the liquid in which a part of is dissolved is added and kneaded to obtain a poultice.

Manufacturing method of Comparative Example 3: is dispersed in, dissolved by heating, and added. Then, the liquid in which is dispersed is added and stirred, and the liquid in which is dispersed is further added and kneaded. Then, is added and kneaded to obtain a poultice.

Examples 1, 2, 3 and Comparative Example 1, obtained as described above,
Each patch of No. 2 was spread on a non-woven fabric and cut into 10 cm x 14 cm to make a sample. The sample was sealed in an aluminum bag and aged at 25 ° C for 1 week. The re-adhesion strength after drying for 4 hours at 37 ° C and a humidity of 30% was measured. For measurement, cut the sample to a size of 2 cm × 9 cm to expose the plaster surface, attach the exposed surface to waterproof paper, crimp it with a crimping roller, and peel it 180 degrees with a constant-speed tension type tensile tester. The adhesive strength was measured. The measurement results are shown in Table 2.

From the results of Table 2 above, Example 1 in which the acrylic acid-sodium acrylate cross-linked copolymer was blended was prepared by using sodium polyacrylate and a 10% aqueous solution of polyacrylic acid, or sodium polyacrylate and carboxyvinyl polymer in Example 1. It can be seen that it has a stronger adhesive force as compared with Comparative Example 1 and Comparative Example 2 which were compounded in the same ratio. In addition, Examples 1 and 2 show that the addition of water candy clearly enhances the re-adhesion force.

Next, a bidirectionally stretchable non-woven fabric made by needle punching polyester, rayon and oriolefin on both sides of a water-swellable vinylon film layer, and a poultice in the form in which the non-woven fabric is spread with the poultice of Example 1. , And the strength-elongation curve thereof was measured. The longitudinal strength-elongation curve of the bidirectional elastic nonwoven fabric itself is shown in FIG. 1, and the transverse strength-elongation curve thereof is shown in FIG. 2 as curve (a). The strength-elongation curve in the longitudinal direction of the expanded form of the poultice of Example 1 is shown in FIG. 3, and the strength-elongation curve in the transverse direction is shown in FIG. 4 as curve (A). For comparison, the strength-elongation curves of a normal non-stretchable non-woven fabric (b) and a non-woven fabric (B) in which the poultice of Example 1 is spread are also shown. From the measurement results of FIGS. 1 to 4, it is shown that the bidirectionally stretchable non-woven fabric hardly expands when it is a non-woven fabric alone, but it expands in a form in which the patch adhesive paste is spread.

Next, each of the poultices of Example 1 and Comparative Example 3 was spread on a non-woven fabric and cut into a sample of 3 cm × 5 cm to obtain a sample. The sample was sealed in an aluminum bag, aged at 25 ° C. for 1 week, and then opened. , Put the sample in a beaker of hot water
When left for 20 minutes, the poultice of Comparative Example 3 melted and became only the non-woven fabric, whereas the poultice of Example 1 cross-linked with aluminum had a plaster-like water absorption and formed a dango-like troche. There wasn't.

Furthermore, each of the poultices of Examples 1 and 2 was spread on the bidirectionally stretchable nonwoven fabric, and the non-stretchable nonwoven fabric was spread on the elbow and the knee, respectively. After 50 flexing and stretching exercises, some of the stretched non-woven non-woven fabrics were partially removed from the attachment site, but did not fall off without fixing with adhesive tape. . On the other hand, the bidirectional stretchable non-woven fabric was adhered without any partial peeling.

[Brief description of drawings]

1 and 2 are graphs comparing the elongations of the supports on which the poultices are spread, FIG. 1 is a longitudinal elongation comparison graph, and FIG. 2 is the same lateral elongation graph. Comparison graph,
Further, FIGS. 3 and 4 are graphs comparing the elongations of poultices spread on a support, FIG. 3 is a longitudinal elongation comparison graph, and FIG. It is an elongation comparison graph.

Claims (4)

[Claims] 1. A general formula (In the formula, R represents H, COOH or COOX, and R ₁ is H, C
Indicates H ₃ , CH ₂ COOH or CH ₂ COOX ₁ . X and X ₁
Indicates an alkali metal. ) Α-β-unsaturated carboxylic acid represented by (In the formula, R ₂ represents H, COOH or COOX ₃ , and R ₃ represents H, C
Indicates H ₃ , CH ₂ COOH or CH ₂ COOX ₄ . Note that X ₂ X ₃ and X
₄ indicates an alkali metal. ) A polycarboxylic acid-based cross-linking copolymer having a PH of 8 or less, which is obtained by polymerizing a mixed monomer consisting of an α / β-unsaturated carboxylic acid alkali metal salt in the presence of a polyfunctional crosslinking agent. Combined 1 to 10% by weight, and poorly soluble aluminum compound 0.01
-1% by weight and a bridge product crosslinked in the presence of an oxyacid, and a PH of 4.8-6.0. 2. A poultice according to claim 1, wherein 5 to 40% by weight of water candy is added as a moisturizing and adhesive agent. 3. The poultice according to claim 1 or 2, which is in the form of being spread on a support having stretchability in both directions. 4. A bidirectional stretchable support is a non-woven fabric in which a layer made of a water-swellable vinylon film is formed on both sides or one side of a layer made of fibers containing polyester, rayon and / or polyolefin. The poultice according to claim 3, characterized in.