JPS5815911A - Poultice composition - Google Patents

Abstract

PURPOSE:To prepare the titled composition having excellent stability with time and water retainability, effective for the antiphlogistic and analgesic treatment of e.g. bone fracture, stiffness of the shoulders, etc., and applicable pleasantly to the body, by using a specific amount of a crosslinked polycarboxylic acid copolymer having a pH of <=8 and crosslinked with a polyfunctional crosslinking agent as an active component. CONSTITUTION:A monomer mixture composed of (A) an alpha,beta-unsaturated carboxylic acid of formulaI(R is H, COOH, or COOX; R1 is H, CH3, CH2COOH, or CH2COOX1; X and X1 are alkali metal) or its derivative and (B) an alpha,beta- unsaturated carboxylic acid alkali metal salt of formula II (R2 is H, COOH, or COOX3; R3 is H, CH3, CH2COOH, or CH2COOX4; X2, X3 and X4 are alkali metal), is polymerized in the presence of 10<-4>-10<-1>mol%, based on the monomer, of a polyfunctional crosslinking agent to obtain a crosslinked polycarboxylic acid copolymer having a pH of <=8, preferably 6-8. The copolymer is used as an active component, and is mixed with powdery base, wetting agent, and other active components to obtain the objective composition containing 0.5-15wt% of the above copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for a dressing agent effective in anti-inflammatory and analgesic treatment for fractures, bruises, sprains, stiff shoulders, etc., and its purpose is to provide adequate adhesion to the skin, To provide a composition for a tofu agent that improves the elasticity of a tofu agent substrate, maintains the stability of volatile medicinal ingredients over time, has excellent water retention, and can always maintain a comfortable condition. It is in.

The so-called tofu agent is a slurry consisting of a powder base material such as kaolin, bentonite, and zinc oxide, a wetting agent such as glycerin, propylene glycol, and tulpinotol, and water, and a volatile medicinal agent such as menthol, camphor, methyl salicylate, etc. The composition is made by spreading and coating a cloth such as flannel or lint cloth, and then pasting a releasable protective film such as polyethylene film on the drug surface.

The tomoe agent is a patch that can be applied to the affected area immediately after peeling off the protective film from the drug side. It promotes the reduction of fever in the affected area, and is expected to have overall therapeutic effects such as anti-inflammatory and analgesic effects. Such a tomoe agent・
The quality of the product is that it is flexible, adheres well to the skin, maintains a moist state on the skin for a long time, and does not harden as a whole. In other words, a cloth agent with excellent water retention is desired. Also contains menthol, camphor, and salicylic acid.

In the past, many attempts have been made to realize a cloth agent having the above-mentioned performance, but none have necessarily been found to be commercially satisfactory. For example, in order to improve appropriate adhesion to the skin, lack of elasticity of the drape matrix, and stickiness and adhesion of the drape matrix to the skin due to body temperature when attached to the human body, polyacrylic acid sodium , as well as the combined addition of sodium polyacrylate, carboxymethyl cellulose, gelatin, sodium alginate, xanthan gum, etc., have been proposed and attempted, but they are not yet perfect and further quality improvements are required. In order to prevent the decomposition of medicinal ingredients, attempts have been made to incorporate pH regulators into the composition, but nothing satisfactory has yet been achieved.

In order to obtain a dressing composition with excellent water retention and stability of medicinal ingredients over time, the present inventors have developed various formulations with a pH of 6 to 8.
They discovered that by adding a polycarboxylic acid crosslinked copolymer within the range of 1 to 1, it is possible to obtain a drape composition that does not require pH adjustment and also has excellent water retention performance, leading to the completion of the present invention. .

That is, the present invention relates to the general formula (wherein R represents H, 0OOH or coox, R
1 is 11, OH5, 01 (2000H or 0112C
Shows OOXl. Note that X and Xl represent an alkali metal. ) α・β-unsaturated carboxylic acid or its derivative represented by the general formula % formula % (wherein R2 represents H,0OOH or C00X5,
R3 is i(, OH3,0H2000H or CH2C0
Indicates 0X4. Note that X2, X3 and X4 represent alkali metals. ] A mixed monomer consisting of an alkali metal salt of an α/β-unsaturated carboxylic acid represented by
The present invention relates to a drape composition containing a polycarbonate having a pH of 8 or less obtained by polymerization in the presence of 10-1 mol of a polyfunctional crosslinking agent.

The polycarboxylic acid crosslinked copolymer used in the present invention has a pH of 8 or less, more preferably in the range of 6 to 8, and when the crosslinked copolymer is added to the drape composition, the crosslinked copolymer suppresses the decomposition of medicinal ingredients such as methyl salicylate in the tofu composition, and exhibits a remarkable effect on the stability of medicinal ingredients over time compared to conventional tofu formulations. Furthermore, the rack%
By containing 0.5 to 15% by weight of the combination as an active ingredient in the dressing composition, elasticity and water retention are improved compared to conventional dressings, and a comfortable condition is maintained.

Examples of the α/β-unsaturated carboxylic acid represented by the general formula (1) or its derivatives used in the present invention include acrylic acid, methacrylic acid, fumaric acid, maleic acid, and itaconic acid. These α/β-unsaturated carboxylic acids or derivatives thereof may be used singly or in combination of two or more.

In addition, examples of the alkali metal salt of α/β-unsaturated carboxylic acid represented by the general formula (2) include sodium acrylate, potassium acrylate, lithium acrylate, sodium methacrylate, potassium methacrylate, and lithium methacrylate. etc. can be mentioned. These α and β−
The alkali metal salts of unsaturated carboxylic acids may be used alone or in combination of two or more.

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 copolymerizing the monomer mixture in the presence of a polyfunctional crosslinking agent is 8 or less. . More preferably, they are mixed so that the pH is in the range of 6 to 8.

Examples of the polyfunctional crosslinking agent include compounds having at least two polymerizable double bonds (non-conjugated) in the molecule, such as (1) di- or polyvinyl compounds (di- or trivinylbenzene, divinyltoluene, divinylxylene, divinyl ether, divinyl ketone, etc.), O
f) Di- or poly-esters of unsaturated mono- or polycarboxylic acids and polyols [di- or tri(meth)acrylic acids of polyols (ethylene glycol, trimethylolpropane, glycerin, polyethylene glycol, polypropylene glycol, etc.) ester, unsaturated polyester of the above polyol and unsaturated carboxylic acid (maleic acid, etc.), (ili) bis(meth)acrylamide (N,N'-methylenebisacrylamide, etc.), (lψ polyincyaner)'( TDI, HDl
, MDI, etc., and a NOO group-containing prepolymer obtained by reacting these with an active hydrogen-containing compound) and a hydroxyl group-containing monomer (carbamyl ester [hydroquine ethyl (meth)acrylate)] and di(meth)acrylic acid carbamyl ester with the above diisocyanate, etc.], (v) polyol (alkylene glycol, glycerin, polyalkylene glycol, carbohydrate, etc.)
(vD polycarbo/
Di- or poly(meth)allyl esters of acids (diallyl phthalate, diallyl adipate, etc.), esters of mono(meth)allyl ether of 6II# polyol and unsaturated carboxylic acids [polyethylene glycol monoallyl ether (meth)acrylate, etc.], etc. can be given.

These polyfunctional crosslinkers have a 10-
It is added in an amount of 4 to 10-1 mol, preferably 10-2 to 10-1 mol. The amount of polyfunctional crosslinking agent added is 1
If the amount is less than O-4 molt, the effect of imparting water retention performance and elasticity to the base material of the cloth agent is small, and kaolin tends to aggregate during kneading. If it exceeds 10-1 molty, not only will the thickening property be lost, but any conventionally known method may be used for spreading. Examples of such methods include polymerization using a radical polymerization catalyst, and polymerization using a so-called redox catalyst that combines persulfate and organic amine. A so-called water-in-oil suspension polymerization method may also be used.

The polymerization temperature varies depending on the type of catalyst used, but is usually in the range of 0 to 100°C, preferably 0 to 50°C.

The reaction time is suitably 1 to 9 hours, and one reaction may be carried out either in air or under a nitrogen gas atmosphere, but it is preferably carried out under a nitrogen gas atmosphere.

The reaction product is made into a powder by a precipitation operation or an evaporation operation using a water-soluble solvent such as methanol or acetone, and then used for a purpose.

The polycarboxylic acid crosslinked copolymer thus obtained is P
H is 8 or less, preferably in the range of 6 to 8. If the pH of the polycarboxylic acid-based crosslinked copolymer exceeds 8, the decomposition of medicinal ingredients such as methyl salicylate will occur within a range of 0.5 to 15% by weight, and within this range, the amount will increase in proportion to the amount added. However, if the amount is less than 0.5% by weight, there is almost no modification effect, and if it exceeds 15% by weight, the viscosity will increase significantly, so it is difficult to spread the drug onto the cloth during the production of the cloth. make work worse.

The cloth agent composition of the present invention can be produced, for example, as follows. Rqchi, powder base materials such as kaolin, bethonite, and zinc oxide, humectants such as glycerin, propylene glycol, and tulpinotol, water, and menthol, camphor, and methyl salicylate, which have direct anti-inflammatory and analgesic effects on the affected area. Appropriately select and use medicinal agents,
These and the crosslinked copolymer can be kneaded to form a slurry, which can be used as a dressing composition.

The cloth composition is spread and coated on a base fabric such as flannel or lint cloth, and a removable protective film such as cellophane or polyethylene film is attached to the drug surface, and it is commercially available. The protective film is peeled off and applied to the affected area.

I will clarify.

(Production of crosslinked polycarboxylic acid copolymer) Monomers, ion-exchanged water, and an aqueous crosslinking agent solution were charged in the proportions shown in Table 1 into a reaction vessel equipped with a nitrogen introduction tube and a thermometer. The mixed monomer concentration in the aqueous phase was 2.13 mol/Kg. Degassing with nitrogen was performed for 5 to 10 minutes at room temperature, and nitrogen was allowed to stand for 1 hour. Then, in a reaction vessel, add a 1% aqueous solution of ammonium persulfate at 250 ppm based on the total amount of monomers, and add a 1% aqueous solution of sodium sulfite at 500 ppm based on the total amount of monomers.
Add m.

Polymerization was carried out at 40°C for 6 hours. After the reaction, the reaction product was washed with a water-methanol mixed solution and incubated at 120°C for 1 hour.
After drying with hot air for 6 hours, a dry gel powder was obtained by crushing.

Table 1 (Monomers) AA...Acrylic acid MAA...Methacrylic acid AΔ-Na...Sodium acrylate MAA
-Na... Sodium methacrylate FA...
... IT Na fumarate ... Sodium itatarate (crosslinking agent) MBA ... N, N' methylene bisacrylamide EGDA ... Ethylene glycol dimethacrylate Examples 1 to 4 and comparative examples 1 to 4
2 To the general dressing composition shown in Table 2, add 3 layers of each dry gel powder obtained in Production Examples 1 to 7 of the polycarboxylic acid-based crosslinked copolymer, A test piece of cloth was prepared using the following method.

First, gelatin was dissolved in warm water at 40 to 60°C, and then kaolin was mixed. Separately, a dispersion of dry gel powder was prepared in glycerin, and this was thoroughly kneaded with the above mixture while heating to 40 to 60°C. The mixture was then cooled to 40° C., and the medicinal agents methyl salicylate, camphor, and menthol were skillfully kneaded so as not to evaporate. The obtained cloth agent composition was spread on flannel cloth to a certain thickness, and a polyethylene film was attached to the surface thereof. The fruit-making properties of kaolin when using each dry gel powder, the miscibility and spreadability of the cloth agent composition, and the degree of stickiness when used as a cloth agent are shown in Table 3.

Table 2 Table 3 Comparative Example 3 No matter which powder was used in the bridge copolymer production example, the kneaded composition did not cause kaolin aggregation and had excellent miscibility, but had poor shape retention. It was not possible to stably apply it to the base fabric.

Comparative Example 4 When the amount of dry gel powder added to the composition in Table 2 was 20% by weight, any of the powders prepared in the above production examples of crosslinked polycarboxylic acid copolymers was kneaded. The composition had high viscosity and poor miscibility and spreadability.

Examples 5 to 8 and Comparative Example 5 Test cloth pieces obtained in the same manner as Examples 1 to 4 were stored in a sealed container at 40°C, and the medicinal content of methyl salicylate, which is unstable, was measured over time. Table 4 Examples 9 to 12 and Comparative Examples 6 to 8 Table 1 obtained in the production example of polycarboxylic acid-based crosslinked copolymers
Test cloth pieces obtained in the same manner as Examples 1 to 4 using the crosslinked copolymers No., 1.2.3.4 (Example), and No. 7 (Comparative Example), and commercially available cloth agents Cut it into an area of about 14 x 10 α, remove the polyethylene cover film and leave it in a thermostatic room at 37°C and 15° relative humidity for 4 hours, measure its weight every hour, and calculate the weight for each hour. The water content %- contained in the fabric was calculated. The results are shown in Figure 1.

As is clear from the gt diagram, P H8 defined in the present invention
The residual water content at each time of the cloth agent using the cloth agent composition containing the following polycarboxylic acid crosslinked copolymer is as follows:
It can be seen that this is superior to the drape agent containing a crosslinked polycarboxylic acid copolymer outside the scope of the present invention and to the commercially available drape agent.

[Brief explanation of drawings]

Figure 1 shows the cloth agents obtained in the present invention (crosslinked copolymers used are Nos. 1 to 4 in Table 1), comparative examples (crosslinked copolymers used are Nos. 7 in Table 1), and commercially available products. at 37℃, relative humidity 1
It shows the amount of residual moisture for each hour when left in a 5% constant temperature room. Patent applicant Showa Kameko Co., Ltd. Representative Patent attorney Sei Kikuchi

Claims (1)

[Claims] General formula % formula % (wherein R represents H, 0OOH or coox, R1
■], OH3, OH2COOH or 0H2co-o
x. Note that X and Xl represent an alkali metal. ) and a derivative thereof represented by the general formula (wherein, R2 represents H, C0OH or 000X5, R3 represents H, CH3,0H2000H or 0H2
Indicates 000X4. In addition, x2. x5 and X4 represent alkali metals. ) A mixed monomer consisting of an alkali metal salt of an α/β-unsaturated carboxylic acid represented by
It is characterized by containing as an active ingredient a polycarboxylic acid-based crosslinked copolymer having a Pl-1 of 8 or less obtained by polymerization in the presence of a polyfunctional cross-linking agent of 10-1 mol. A tofu agent composition.