JPS5818319A - Poultice composition - Google Patents

Abstract

PURPOSE:To prepare an antiphlogistic and analgesic poultice composition having improved miscibility, water-retainability and age stability, by using a specific crosslinked polycarboxylic acid polymer crosslinked with a plyfunctional crosslinking agent and obtained by peptization, as an active component. CONSTITUTION:(A) An alpha,beta-unsaturated carboxylic acid of formulaI(R is H, COOH, etc.; R1 is H, CH3, etc.; X and X1 are alkali metal) or its derivative (e.g. acrylic acid, methacrylic acid, etc.) and (B) and alpha,beta-unsasturated carboxylic acid alkali metal salt of formula II (R2 is H, COOH, etc.; R3 is H, CH3, etc.; X2-X4 are alkali metal) (e.g. sodium acrylate) are copolymerized in the presence of 10<-3>-1mol%, based on the monomer mixture, of a polyfunctional crosslinking agent (e.g. polyvinyl compound), and the copolymer is peptized to obtain a crosslinked polycarboxylic acid copolymer having a pH of <=8 and content of insoluble component of 10-70wt%. The objective poultice composition contains the crosslinked polycarboxylic acid copolymer in an amount of 0.5-15wt%.

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. There is something to do.

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. A dressing composition prepared by kneading the ingredients is spread and coated on a fabric such as flannelette or Lin F cloth, and a removable protective film such as polyethylene lyme is attached to the drug surface. There is.

This patch is a patch that can be applied to the affected area immediately after peeling off the protective film from the drug side. It is expected to promote the reduction of fever in the affected area and have overall therapeutic effects such as anti-inflammatory and analgesic effects. The quality of this kind of tomoe agent is that it is flexible, adheres well to the skin, maintains a damp state on the skin for a long time, and is not stiff as a whole, so it does not stay in close contact with the skin for a long time. In other words, it is desirable to have a tofu that has a long-lasting effect and relieves discomfort in the affected area, in other words, it has excellent water retention properties.First, so-called medicinal ingredients such as menthol, camphor, and methyl salicylate are expected to be effective during storage. It is important that it does not decompose and has a long-lasting effect when used.

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 adhesion to the skin, lack of elasticity of the dressing substrate, and stickiness and adhesion of the dressing substrate to the skin due to body swirl when applied to the human body, polyester is used. The combined addition of sodium acrylate, sodium polyacrylate, carboxymethyl sululose, gelatin, alginate, xanthan gum, etc. has been proposed and attempted, but it is not yet perfect and further quality improvements are required. To prevent the decomposition of medicinal ingredients,
Attempts have been made to incorporate a P I-1 regulator, but a fully satisfactory result has not yet been obtained.

In order to improve the water retention properties, attempts have also been made to add a crosslinked polymer to the cloth agent composition, or to add a mixture of a water bathing polymer and a crosslinked polymer. However, although these methods have achieved good results, it is desired to further improve the flow characteristics and viscosity characteristics of slurry formulations used as draperies.

The present inventors have conducted various studies in order to obtain a dressing composition with excellent miscibility and water retention, and stability of medicinal ingredients over time. By adding a specific polycarboxylic acid-based crosslinked copolymer obtained by clarifying the above as an active ingredient, it is possible to create a tofu composition with excellent miscibility and water retention, as well as excellent stability of medicinal ingredients over time. This led me to complete the present invention.

That is, the present invention is based on the general formula % (where ■ represents 11, OOQ H or C00X,
R1 represents 11, c (ro, 01 (20001-14: or 0H2a o o Xl). In addition, X and
l represents an alkali metal. ) An α/β-unsaturated carboxylic acid or a derivative thereof represented by the general formula % (wherein R2 is I], 0001 (or indicates OOOXsj, , R3hatl, Cl-15, OH200
Indicates 0H or 002COOX4. In addition, X2,
3 and X4 represent alkali metals. ) A mixed monomer consisting of an alkali metal salt of an α/β-unsaturated carboxylic acid represented by
- A polycarboxylic acid-based crosslinked material having a pH of 8 or less obtained by polymerization in the presence of 3 to 1 mole of a polyfunctional crosslinking agent and then clarification, and containing a water-soluble portion of 10 to 70% by weight. The present invention relates to a dressing composition characterized by containing 05 to 15% by weight of a copolymer as an active ingredient.

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, itaconic acid and others represented by the general formula (11). These α·β-unsaturated 40 carboxylic acid derivatives 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. , sodium maleate, sodium itaconate, and other compounds that can be represented by general formula (2). These alkali metal salts of α/β-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 P I-I of the crosslinked copolymer obtained by copolymerizing the monomer mixture in the presence of a polyfunctional crosslinking agent is 8 or less. mixed. 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 polyvinylbenzene, divinyl Toluene, divinylxylene, divinyl ether, divinyl ketone '4F),
(i:) Di- or poly-ester of unsaturated primary mono- or polycarboxylic acid and polyol [di- or polyester (meth) of polyol (ethylene glycol, trimethylolpropane, glycerin, polyethylene glycol, polypropylene glycol, etc.) acrylic ester,
Unsaturated polyester etc. of the above polyol and unsaturated carboxylic acid (maleic acid etc.) 'II, (iiD bis(meth)acrylamide (N,N'-methylenebisacrylamide etc.), Ov) polyisocyanate (T' D
carbamyl ester [hydroxyethyl (meth ) di(meth)acrylic acid carbamyl ester of acrylate and the above diisocyanate, etc.], (V) di- or poly-(meth)allyl ether (polyethylene glycol diallyl) of polyol (alkylene glycol, glycerin, polyalkylene glycol, carbohydrate, etc.) ether,
Allylated starch, allylated cellulose%), (v
[l Di- or poly(meth)allyl esters of polycarboxylic acids (diallyl phthalate, diallyl adipate, etc.)
, (ester of mono(meth)allyl ether of vl polyol and unsaturated carboxylic acid [polyethylene glycol monoallyl ether (meth)acrylate, etc.]).

These polyfunctional crosslinkers have a 10-3
-1 molar, preferably lo-2 to 10-1 molar. Outside this range, any conventionally known method may be used to obtain the water-soluble portion of the crosslinked copolymer in a range of lθ to 70% by weight, for example, using water, tetrahydrofuran, acetone, or a mixture thereof as a polymerization medium. For example, a method of polymerization using a radical polymerization catalyst such as nisezolium salt, hydrogen peroxide, benzoyl peroxide, amebisisobutyronitrile, ammonium persulfate, etc., a method of polymerization using a radical polymerization catalyst such as nisezolium salt, hydrogen peroxide, benzoyl peroxide, ambisisobutyronitrile, ammonium persulfate, etc. Although methods of polymerization using a so-called redox polymerization catalyst that combines a salt and an organic amine such as aniline, monoethanolamine, hexamethylenediamine, jetanolamine, diethylaniline, triethanolamine, or tetramethylethylenediamine are unsuccessful. In some cases, a so-called water-in-oil suspension polymerization method in which an aqueous solution is suspended in an organic medium may be used.

It is usually produced by water bath liquid polymerization.

The polycarboxylic acid crosslinked copolymer thus obtained is P
Tl is 8 or less, preferably in the range of 6-8. If P 11 of the polycarboxylic acid-based crosslinked copolymer exceeds 8, the decomposition of medicinal ingredients such as methyl salicylate will be accelerated and stability over time will be reduced.

To clarify the i% compound, either directly clarify the water-containing gel after the completion of polymerization, or add the powder recovered according to the usual polymer recovery method to water, or water and an appropriate water solution. It may be clarified in a swollen state in a mixed solution with a miscible solvent.

Water-soluble portion 1 of the crosslinked copolymer thus obtained
It is 0 to 70% by weight. If the water-soluble portion is less than 10% by weight, the miscibility of the drape composition is reduced. It has poor ductility, and when it exceeds 70% by weight, it deteriorates the water retention of the dressing composition.

The amount of the crosslinked copolymer added is 0.5 to the cloth agent composition.
It is applied in the range of ~15% by weight, and within this range, the modification effect increases in proportion to the increase in the amount added.
If the amount is less than i% by weight, there will be almost no modifying effect, and if the amount added exceeds 15% by weight, the viscosity will significantly increase, making it difficult to spread the drug onto the cloth piece during the production of a dressing.

The cloth agent composition of the present invention can be produced, for example, as follows. Namely, powder base materials such as kaolin, bentonite, and zinc oxide, wetting agents such as glycerin, propylene glycol, and tulpinotol, water, and menthol, camphor, which has direct anti-inflammatory and analgesic effects on the affected area.
Medicinal agents such as methyl salicylate are appropriately selected and used, and these and the crosslinked copolymer are kneaded to form a drug slurry, which can be used as a dressing composition.

This drape 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.

Hereinafter, the present invention will be explained in more detail with reference to non-examples.

(Production of crosslinked polycarboxylic acid copolymer) Monomers, ion-exchanged water, and crosslinking agent water bath liquid were charged in the proportions shown in Table 1 into a reaction vessel equipped with a nitrogen introduction tube and a temperature side. The mixed monomer hardness in the aqueous phase was 2.13 mol/Kg. Vacuum degassing was performed for 5 to 10 minutes and nitrogen substitution was performed for 1 hour at room temperature. Then add 1% of ammonium peroxide to the reaction vessel.
The water bath solution was added at 2 j50 ppm based on the total amount of monomers, and the 1% aqueous solution of sodium sulfite was added at 50 ppm based on the total amount of monomers.
lrlpm was added, and polymerization was carried out at 40°C for 6 hours. After the reaction was completed, the hydrogel was subjected to the following treatments.

(For 11Al-A2, it was put into a meat grinder and extruded while kneading to give it a clarifying effect.

Wash with water/methanol mixed solution and then heat at 120°C for 1 hour.
After drying with hot air for 6 hours, it was crushed to obtain a dry gel powder.

(2) For A3, a water-containing gel was made into powder according to a conventional polymer recovery method, and then the powder was swollen in ion-exchanged water, and this was stirred at high speed with a homomixer to give a clarifying effect. After the clarifying treatment, the mixture was cleaned with a water/methanol mixed bath solution, dried, and ground to obtain a dry gel powder.

(3,) l to 4. -Ya 6 (comparative example) was made into powder according to the same method as (1).

Examples 1 to 3 and Comparative Examples 1 to 3 Each of the dry gel powders obtained in the above production examples of polycarboxylic acid-based crosslinked copolymers, and a mixture of sodium polyacrylate and a crosslinked polymer of sodium polyacrylate Table 2 [-
Three weights of rice cake were added to each of the above-mentioned caramel, matte, and fabric compositions, and test fabric pieces for fabrics were prepared in the following manner.

Table 1 AA...Acrylic acid AA-Na...Sodium acrylate MAA...
... MAA methacrylate Na ... Sodium methacrylate FA / Kawa / Fumaric acid MBA ... Methylenebisacrylamide EGD
A: Ethylene glycol dimethacrylate First, gelatin is dissolved in warm water at 40 to 60°C, and then kaolin is mixed. Separately, a dispersion of dry gel powder is prepared in glycerin, and this is thoroughly kneaded with the above mixture while heating to 40 to 60°C. Next, it is cooled to 40°C, and the drainage agents methyl salicylate, camphor, and menthol are skillfully kneaded so as not to evaporate.The cloth agent is spread on flannel cloth to a certain thickness, and a polyethylene film is placed on the surface. pasted together. Table 3 shows the cohesiveness of kaolin, the miscibility and spreadability of the dressing composition, and the degree of tackiness when used as a poultice when using each dry gel powder.

Table 2 Table 3 Connection 1:1 mixture of sodium polyacrylate and sodium polyacrylate crosslinked polymer ◎ Very good ○ Good △ Fairly good When it was 1% by weight, the composition kneaded with any of the polymers produced in the above production examples of crosslinked polycarboxylic acid copolymers did not cause agglomeration of kaolin and had excellent miscibility. However, shape retention was lost and it was not possible to stably apply it to the base fabric.

Comparative Example 5 When the amount of crosslinked polymer added to the composition in Table 2 was 200% by weight, the kneaded composition had a viscosity of was high, and the miscibility and spreadability were poor.

Examples 4 to 6 and Comparative Example 6 Table 1 obtained in the production example of polycarboxylic acid-based crosslinked copolymer
Using crosslinked polymers of 0Al, 2.3 (Example), and A6 (Comparative Example), test cloth pieces obtained in the same manner as Examples 1 to 3 were stored in a sealed container at 40 ° C. The residual amount of methyl salicylate, which is the most unstable among medicinal ingredients, over time was measured by gas chromatography. The results are shown in Figure 1.

As is clear from FIG. 1, a cloth agent composition containing a polycarboxylic acid-based crosslinked copolymer having a pH of 8 or less as defined in the present invention and a water-retainable area of 10 to 70% is used. The resulting cloth agent had extremely good stability of methyl salicylate over time.

Examples 7 to 9 and Comparative Example 7 Test cloth pieces obtained in the same manner as Examples 1 to 3 were
Cut it into an area of 0z, remove the polyethylene cover film, and leave it in a constant temperature room at 37℃ and relative humidity 15℃ for 4 hours.Weigh it at each hour, and use that value to determine the amount contained in the tofu agent for each hour. The moisture content W/w was calculated. The results are shown in Table 4.

Table 4 As is clear from Table 4, the cloth agent using the crosslinked copolymer of the present invention had extremely good water retention.

[Brief explanation of drawings]

Figure 1 shows the cloth agent obtained in the present invention (the crosslinked copolymer used is
The results show the results of quantifying the amount of residual methyl salicylate in A1-A3 in Table 1) and Comparative Example (the crosslinked polymer used was 6 in Table 1) using gas chromatography at each time. Patent applicant: Showa Denko Co., Ltd. Representative: Patent attorney: Sei Kikuchi - Figure 1: Leaving time (days)

Claims (1)

[Claims] General formula % formula % (wherein R represents I(,0OOH or aoox, R1 is H, OH3, 0H2000H or 0H2C0
Indicates 0X1. Note that X and Xl represent an alkali metal. ) and the general formula (wherein R2 is H,000H or a o o X5
The axis is 11, OH5, OH2000H or 01
12000X4 is shown. 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
- A polycarboxylic acid-based crosslinked copolymer having a pH of 8 or less and containing an insoluble portion of 10 to 70% by weight after polymerization in the presence of a 3 to 1 molar polyfunctional crosslinking agent and clarification. A drape composition characterized by containing 05 to 15% by weight of a polymer as an active ingredient.