JPH0333686B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is an acidic poultice that does not cause the paste to seep into the support, has excellent shape retention, water retention, and high adhesiveness, has excellent active ingredient stability, and alleviates skin irritation. Regarding drugs. Conventional poultices are based on kaolin, gelatin, and glycerin, in addition to other water-soluble polymeric substances such as sodium polyacrylate, polyvinyl alcohol, and carboxymethyl cellulose, as well as water and
Add active ingredients and knead to form a paste.
This is applied to a support, and as it is,
Since the plaster tends to sag due to heat, sweat, etc., it is cross-linked with polyvalent metal ions (Japanese Patent Application Laid-open No. 53-15413, No. 54).
-17113, 54-26326, 54-92618, etc.), forming a urea-gelatin complex by adding urea (Japanese Patent Application Laid-open No. 45-5278, 45-12314, etc.), organic cross-linking of dialdehyde starch, etc. Cross-linked gelation is achieved by using an agent (JP-A No. 51-91318, No. 51-101119, No. 51-
104027, 52-143223, 54-143517, etc.), insolubilization by polymer-polymer complex formation (Japanese Patent Application Laid-Open No. 52-38016), etc.
It has increased water resistance and prevents sagging.
However, conventional poultices have a pH of 6 or higher, usually 7.
-9, there are problems such as poor stability of active ingredients such as salicylic acid esters and skin irritation. For this reason, an acidic plaster is desired, but in conventional poultices, organic acids such as tartaric acid and citric acid or mineral acids such as hydrochloric acid are added to stabilize the active ingredients and alleviate skin irritation to lower the pH. If it becomes acidic,
The viscosity of compounded polymeric substances (particularly gelatin and anionic polymeric substances) decreases significantly, causing sagging and bleed. Therefore, in acidic poultices, to prevent sagging, cross-linking gelation is required to be more firm. However, with conventional technology, when the pH is lower than 6, the reaction of dialdehyde starch and urea does not proceed.
With metal crosslinking, the crosslinking effect is low, and the more crosslinking agent is added, the harder the paste itself becomes, but more bleed can occur, making it extremely difficult to obtain an acidic poultice. In view of the above circumstances, the present inventors have developed an acidic plaster that does not bleed, has excellent water retention and shape retention, has strong adhesive strength, has high active ingredient stability, and has reduced skin irritation. As a result of intensive research to obtain a poultice, we found that polyacrylic acid and/or polyacrylate and one or more other highly water-soluble poultices having a functional group that reacts with polyvalent metal ions. In poultices with a pH of 3.5 to 6 containing molecular substances, by using two or more polyvalent metal salts with different metal ion types as crosslinking agents, and crosslinking each polymer substance separately. It has been found that the above objectives are effectively achieved. That is, for example, carboxymethyl cellulose contains Cr ³⁺ , Ag ⁺ ,
It forms a cross-linked gel with Fe _2+,3+ , Pb ²⁺ , Al ³⁺ , Ba ²⁺ , and Sn ²⁺ ions, but does not form a cross-linked gel with Ca ²⁺ , Mg ²⁺ , and Mn ²⁺ . On the other hand, sodium polyacrylate contains Ca ²⁺ ,
It forms a cross-linked gel with Mg ²⁺ , and also Al ³⁺ ,
Ba ²⁺ , Fe _2+,3+ are carboxymethyl cellulose,
Both sodium polyacrylate and sodium polyacrylate form a cross-linked gel, but reaction with carboxymethyl cellulose is overwhelmingly likely to occur in an acidic region.
When Al ³⁺ ions and Ca ²⁺ ions are added, only carboxymethylcellulose takes part in the crosslinking reaction with Al ³⁺ ions, and sodium polyacrylate virtually does not react with Al ³⁺ ions, and sodium polyacrylate results in crosslinking by Ca ²⁺ ions, and the present inventors have found that by combining two or more types of metal ions in this way, the crosslinking of various blended polymeric substances is complete. It was discovered that an acidic poultice with excellent properties without sagging or bleeding can be obtained even in the acidic region, and this led to the present invention. The present invention will be explained in more detail below. In the poultice of the present invention, the plaster is acidic with a pH of 3.5 to 6, and the polyacrylic acid and/or polyacrylate and the other water-soluble polymer substance are different metal ion species. It is characterized by being crosslinked with a polyvalent metal salt having the following. In this case, the type of polyacrylic acid is not particularly limited in the present invention, and polyacrylic acids of linear, branched, or crosslinked types with various molecular weights can be used. Specifically, as a commercially available product, Jurimer AC-
10H, AC-10SH, Jinron PW-110, 111 (all manufactured by Nippon Pure Chemical Industries, Ltd.), Aron A-10H (manufactured by Toagosei Co., Ltd.), etc. are preferably used. In addition, any salt can be used as the polyacrylate, but sodium polyacrylate, potassium polyacrylate, alkanolamine polyacrylate, etc. are particularly preferably used, and commercially available products include Aronbis S, SS,
GL, M (manufactured by Nippon Pure Chemical Industries), Viscomate P-480,
F-480, F-460 (manufactured by Showa Denko), Aron A-
20P, A-20PG, A-20PH (manufactured by Toagosei Co., Ltd.), etc. can be used. The blending amount of polyacrylic acid and polyacrylate is 0.5 to 20% of the entire poultice.
(wt%, the same applies hereinafter), especially preferably 1 to 10%; if it is less than 0.5%, sufficient viscosity will not be obtained, shape retention will decrease and cause sag, and 20%
If the amount is more, the viscosity becomes too high and the workability of kneading, coating, etc. may deteriorate. In addition, when polyacrylic acid and polyacrylate are used together, the blending ratio (weight ratio) is preferably 9:1 to 3:7, and if there is too little polyacrylate, the PH
is lower than 3.5, and conversely, if it is too high, the PH may be higher than 6. Furthermore, other water-soluble polymeric substances having functional groups that react with polyvalent metal ions include gelatin, pectin, sodium alginate, carboxymethyl cellulose, polyvinyl alcohol, methyl vinyl ether/maleic anhydride copolymer, etc. One species or two or more species are preferably used.
In this case, the amount of the water-soluble polymer compound is preferably 1 to 15%, especially 1 to 10% of the entire poultice.If it is less than 1%, the viscosity will be insufficient and the shape retention will not be maintained. On the other hand, if it exceeds 15%, the viscosity will increase and workability during kneading and coating may decrease. The present invention provides a poultice containing the above-mentioned water-soluble polymeric substance, in which a polyvalent metal salt for crosslinking polyacrylic acid and/or polyacrylate as a crosslinking agent, and a polyvalent metal salt and a metal ion species are used as a crosslinking agent. However, water-soluble polymer substances other than the polyacrylic acid and polyacrylates (carboxymethyl cellulose,
gelatin, etc.) in combination with one or more polyvalent metal salts, in which case the former is Ca salt, Mg salt, etc., and the latter is Al salt,
Fe salts (Fe ²⁺ , Fe ³⁺ ), Sn salts (Sn ⁴⁺ , Sn ²⁺ ), and the like are particularly preferably used. Note that these polyvalent metal salts may be soluble, slightly soluble, or slightly soluble in water, and specifically include calcium chloride, magnesium chloride, aluminum chloride, potassium alum, ammonium alum, iron alum, Aluminum sulfate, ferric sulfate, magnesium sulfate, EDTA-calcium,
EDTA-aluminum, EDTA-magnesium,
Soluble salts such as tin chloride and stannic chloride, calcium hydroxide, ferric hydroxide, aluminum hydroxide,
Calcium carbonate, magnesium carbonate, calcium phosphate, magnesium stearate, aluminum stearate, calcium citrate, barium sulfate, barium hydroxide, aluminum allantoinate, aluminum acetate, aluminum glycinal, stannous hydroxide, orstannic acid, α - Two or more selected from slightly soluble or hardly soluble salts such as stannic acid can be used in combination. In addition, the total blending amount is preferably 0.005 to 10%, especially 0.01 to 5% of the entire poultice. If it is less than 0.005%, a sufficient crosslinking effect cannot be obtained, causing sagging, and if it is less than 10%. If the amount is too high, the paste will become too hard, resulting in poor adhesion to the skin and sometimes causing water separation. The poultice of the present invention is prepared into a paste by thoroughly kneading each of the above components with other appropriate ingredients, and the poultice thus obtained can be applied to paper, woven fabric, non-woven fabric, plastic film, etc. It is used by coating it on a support (backing) and covering it with a facing such as polyethylene film if necessary. As other components of the present invention, commonly used appropriate components are used, such as one or more polyhydric alcohols such as propylene glycol, polyethylene glycol, glycerin, and sorbitol (the amount usually 5-60% of the total.5%
If it is less than 60%, the moisturizing effect will be insufficient, and although there is no particular upper limit, if it is more than 60%, the solubility of the polymer and the amount of water mixed may decrease. ), kaolin,
One or more inorganic powders such as bentonite, montmorillonite, zinc oxide, titanium oxide, and silicic anhydride (compounding amount is usually 0 to 30%. If it exceeds 30%, the paste becomes too hard and does not fit well to the skin. ), water (compounding amount is usually 10 to 80%).
%. If it is less than 10%, the compressive effect will be insufficient, and if it is more than 80%, the plaster may become soft and sag. ), methyl salicylate, glycol salicylate, indomethacin, l-menthol, pepper oil, eucalyptus oil, dl-camphor, capsicum extract, vanillylamide nonylic acid, vitamin E, diphenhydramine, chlorpheniramine maleate, thymol, etc. One or more active ingredients (compounding amount usually 0 to 20%), as well as physical properties of the paste (softness,
Guar gum, xanthan gum, gum arabic, starch derivatives,
Polymer substances such as polybutene, latex, vinyl acetate emulsion, acrylic resin emulsion,
Stabilizing agents for active ingredients include lanolin, liquid paraffin, vegetable oil, lard, beef tallow, higher alcohol,
Higher fatty acids, activators, etc. are appropriately blended as necessary. Accordingly, the present invention provides that the plaster is acidic with a pH of 3.5 to 6, and that polyacrylic acid and/or polyacrylate and other water-soluble polymer substances are mixed with different metal ions. It is characterized by being cross-linked with a polyvalent metal salt having seeds, which prevents sag or bleed even in the acidic range of pH 3.5 to 6, and because it is acidic, the active ingredient is stable. It has low skin irritation, and has high adhesion to the skin due to the combination of polyacrylic acid and/or polyacrylate. Next, the present invention will be specifically explained by showing Examples and Comparative Examples. [Example 1, Comparative Example 1] A poultice with the following formulation was prepared according to the following manufacturing method. [Prescription]

【table】

[Manufacturing method]

Dissolve (1) in (12) by heating, and add (2), (7), (8), and (9) to this.
Add and knead to disperse well. Then this (6)
A well-dispersed mixture of (3), (4), (5), (10), and (11) was added to the mixture and kneaded uniformly to obtain a paste-like poultice. This is applied onto a non-woven fabric and faced with polyethylene film. The poultice of Example 1 had excellent adhesive strength (Ball Tack No. 10), and the pH of the plaster was around 4.2, and the active ingredients such as glycol salicylate were extremely stable. [Example 2, Comparative Example 2] A poultice having the following formulation was prepared according to the following manufacturing method. [Prescription]

【table】

[Manufacturing method]

Mix (1), (7), (8), (9), (10), and (13) and stir well to disperse uniformly. Next, add (6) to this dispersion.
Add a dispersion of (2), (3), (4), (5), (11), and (12) to the mixture and mix thoroughly to obtain a paste-like poultice. This was applied onto a nonwoven fabric and faced with polyethylene film. The poultice of Example 2 has strong adhesive strength, has a pH of around 4.6, and has excellent stability of the active ingredient.
Furthermore, since no heating was required during the manufacturing process, it was extremely useful for blending volatile active ingredients (l-menthol, dl-camphor). [Example 3, Comparative Example 3] A poultice having the following formulation was prepared according to the following manufacturing method. [Prescription]

【table】

[Manufacturing method]

Mix and stir (1), (2), (6), (7), (8), (12),
Distribute evenly. Next, add (5) to (3) to this dispersion,
Add the dispersion of (4) and (9) and mix well to form a paste. A solution prepared by dissolving (10) and (11) is added to this while kneading, and the mixture is further kneaded to obtain a paste-like poultice. This was applied onto a nonwoven fabric and faced with polyethylene film. The poultice of Example 3 had a pH of around 4.8, and had excellent properties similar to those of Examples 1 and 2. [Example 4] A poultice having the following formulation was prepared according to the following manufacturing method. [Formulation] (1) Gelatin 2.0% (2) Polyacrylic acid 20% aqueous solution 15.0 (Jyurimer AC10H) (Solid content 3.0%) (3) Polyacrylic acid (Jiyunron PW-110)
1.0 (4) Sodium polyacrylate (Aronbis SS)
1.5 (5) Carboxymethyl cellulose (Daicel
CMC1350) 3.0 (6) Kaolin 10.0 (7) Glycerin 20.0 (8) Active ingredients Glycol salicylate 1.0 L-menthol 1.0 dl-camphor 1.0 (9) Active agent Polysorbate 80 0.5 (10) Magnesium stearate 0.5 (11) Aluminum dihydroxy allantoinate
0.2 (12) 5% potassium alum solution 1.0 (13) Water Total remaining 100.0 [Production method] (1), (2), (3), (6), (8), (9), (13) Stir and mix to obtain a uniform dispersion. Next, add to this dispersion
A solution of (4), (5), (10), (11), and (12) dispersed in (7) is added and kneaded to obtain a paste-like poultice. A poultice was obtained in the same manner as in Examples 1 to 3. This poultice also had excellent properties similar to Examples 1-3. [Comparative Example 4] A conventional poultice having the following formulation was prepared according to the following manufacturing method. [Formulation] (Parts by weight) (1) Gelatin 3.5 parts (2) Carboxymethylcellulose (Daicel)
CMC1260) 3.5 (3) Sodium polyacrylate (Aronbis SS)
4.0 (4) Glycerin 25.0 (5) Kaolin 10.0 (6) Active agent (polysorbate 80) 1.0 (7) Active ingredients Glycol salicylate 1.0 L-menthol 1.0 DL-camphor 1.0 Vitamin E 0.5 (8) Citric acid 0.07 (9) 5% ammonium alum aqueous solution 6.0 (10) Water balance 100.0 [Production method] Heat (1) and dissolve in (10). Add (5), (6), and (7) to this aqueous gelatin solution and disperse uniformly. Next, (4) with (2) and (3) previously dispersed is added to this and kneaded uniformly. Finally, a solution in which (8) was dissolved was added to (9) and further kneaded to form a paste, which was applied onto a nonwoven fabric, and the surface was faced with polyethylene film. The surface pH of this plaster was approximately 8.5. Next, using the poultices of Examples 1 to 3, Comparative Examples 1 to 3, and the conventional poultice of Comparative Example 4, their seepage and active ingredient stability were investigated. In this case, to prevent seepage from the back, place the polyethylene film-covered side of the sample on top, apply a pressure of 10 g/cm ² and leave it at room temperature for one week. A sensory evaluation was conducted to determine whether or not a portion of the sample had oozed out.
The sample was stored for several days, and the residual rate of salicylic acid ester after storage was determined. The results are shown in the table. The evaluation criteria for back seepage and active ingredient stability are as follows.

【table】

[Table] From the results in the table, it was found that by using two or more types of polyvalent metals in combination, an excellent acidic poultice that does not cause oozing from the back can be obtained.

Claims (1)

[Scope of Claims] 1. The plaster is acidic with a pH of 3.5 to 6, and polyacrylic acid and/or polyacrylate and other water-soluble polymeric substances different from this are made of different metal ion species. A poultice characterized by being crosslinked with polyvalent metal salts having the following. 2 Claims in which the other water-soluble polymeric substance is one or more selected from gelatin, pectin, cellulose derivatives, alginates, polyvinyl alcohol, and methyl vinyl ether/maleic anhydride copolymers. The poultice according to item 1. 3 Combinations of polyvalent metal salts having mutually different metal ion species include Ca salt and Al salt, Ca salt and Fe salt, Mg salt and Fe salt, Ca salt and Sn salt, Mg salt and Sn salt, or Mg salt and
The poultice according to claim 1 or 2, which is an Al salt.