JPS602253A - Tape-shaped water-containing sticking agent and production thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a tape-like patch and a method for producing the same.

Traditionally, poultices for external use for analgesic and anti-inflammatory purposes have mixed main drugs such as methyl salicylate, l-menthol, and chili pepper extract in the base material, and the herbal medicines are absorbed through the skin and improve blood circulation there. The method of treatment is as follows.

These poultices include water-based poultices based on gelatin, CMC, glycerin, pigments, etc., and oil-based poultices based on 19 synthetic (natural) combs, various elastomers, oils, tackifiers, etc. There are two types, each with its own characteristics. In water-based poultices, water forms a continuous phase, and due to its nature, adhesive strength is quite low and adhesive strength cannot be generated unless the coating thickness is increased. In addition, during long-term storage, the base material hardens due to volatilization of water over time or crosslinking of the polymer substances it contains, which impairs its adhesion to the skin and reduces the contact area, resulting in a drastic decrease in medicinal efficacy. There is a drawback that it does.

Oil-based poultices have excellent adhesive strength, but because they do not contain water, they do not have an initial cooling effect on the skin, and the base material is often hard, making them somewhat inflexible. be.

A patch that overcomes the shortcomings of the first half has been proposed (Japanese Patent Publication No. 56-43444), but this patch forms a W10 emulsion and uses a surfactant to disperse water molecules in the oily continuous phase. Therefore, continuous application to the human body may cause redness, eczema, etc.

In view of the above-mentioned drawbacks of conventional poultices, the inventors of the present invention have conducted extensive research, and as a result, the present inventors have discovered that the above-mentioned poultices can be improved by mixing and dispersing water-containing superabsorbent polymers in conventional hot-melt adhesives. discovered that it was possible to obtain a patch that solved the disadvantages of
The present invention has now been completed.

That is, the present invention provides a method in which a water-containing superabsorbent polymer is dispersed in an oily continuous phase consisting of an A, -B-A type bed vulcanized elastic teleblock copolymer, oil, and tackifier 1. The present invention provides a tape-shaped water-containing patch used as a base material.

To produce the patch of the present invention, first, the A-B-A type bed-vulcanized elastic teleblock copolymer and oil are heated and melted at 150°C, and the tackifying component is gradually added to the system while stirring. , an oily continuous phase is obtained.

Next, water is heated to 60 to 90°C, and the superabsorbent polymer is gradually added while stirring to obtain a water-containing superabsorbent polymer. The above-mentioned oily continuous phase is transported as it is or is transferred to a high-speed mixer, the temperature is lowered to about 80 to 90°C, and the water-containing superabsorbent polymer is gradually added thereto. After stirring, a topical analgesic and anti-inflammatory agent is added. Similarly, after uniform stirring, it is coated on a base fabric using various coating machines, a liner is laminated, and after cooling and solidifying, it is cut into desired sizes to obtain products.

The adhesive patch of the present invention does not lose its excellent properties of adhesiveness and flexibility even when used as a hot compress by heating it to 30 to 50° C. using some kind of device, in addition to a normal cold compress. In addition, the super absorbent polymer absorbs the sweat caused by sweating in the summer, and in order to prevent the so-called sagging phenomenon, there is no difference in adhesive strength immediately after application and after application, and the texture does not change. have.

A of the A-B-A bed vulcanized elastic teleblock copolymer (hereinafter abbreviated as elastomer) used in the present invention is:
A hard polymer with a glass transition point of 25°C or higher, approximately 1,
Styrene with an average molecular weight of 000 to 500,000,
It is a polymer such as methylstyrene, and 1 in elastomer.
It accounts for 5 to 40% (weight %, same hereinafter).

B is a conjugated diene-based elastic polymer having a glass transition point of 30° C. or higher, and is a polymer such as butadiene or isoprene having an average molecular weight of about 5,000 to 100,000. An example of an elastomer having the above characteristics is CARIFLEX (Clayton) TR1 manufactured by Shell Chemical Co., Ltd.
107, 1102, 1111, etc.

The oil components (oil) used in the present invention together with the above elastomers include paraffinic oils that are chemically incompatible with styrene, methylstyrene, etc. in the elastomer;
Naphthenic oils, medium-low molecular weight liquid rubbers, paraffin wax, etc. can be used, but care must be taken as the blending of oil components has a significant effect on the physical properties (adhesion, tack, flexibility, etc.) of the final product. There is a need to.

The tackifying component used in the present invention may be a resin that is compatible with or incompatible with either or both of the A part and B part of the elastomer to be blended. It is generally said that the A part of an elastomer controls the cohesive force and the B part controls the elastic force, and there are tackifiers that are compatible with each and tackifiers that are not compatible with both, and the desired physical properties of the final product are determined. They are used in appropriate combinations depending on the situation. From the viewpoint of thermal stability, a good product can be obtained by using a tackifier that is compatible with component B. Aromatic resins such as coumaron-indene resin and methylindene-polystyrene resin can be cited as compatible with the A portion of the elastomer. Examples of substances that are compatible with the B portion include polyterpenes, modified rosins, and non-aromatic petroleum resins. Examples of resins that are incompatible with both the A part and the B part include phenolic resins.

These resins may be used alone or in combination of two or more depending on the desired physical properties of the final product.

If necessary, various antioxidants, fillers, extenders, etc. can be added to the oil phase composed of the above three components.

In the present invention, a hydrous superabsorbent polymer is mechanically dispersed in an oil component without using a surfactant, and examples of the superabsorbent polymer used include gelatin, carboxymethyl cellulose, Water-soluble polymers such as polyacrylates, alginates, mannan, polyvinyl alcohol, and acrylic polymers can be used. Further, it is also possible to stabilize the product by adding a pH adjuster, a chelating agent, a preservative, etc. to the water component, if necessary.

The main drugs used in the present invention include those used as external analgesic and anti-inflammatory agents, such as methyl salicylate, glycol salicylate, l-menthol, dJ-camphor, nonylic acid vanillylamide, Aubaku powder, and diclofenac sodium. It should be noted that since these herbal medicines do not need to be emulsified, they can be mixed into both the oil phase and the aqueous phase, and can also be mixed into the adhesive after mixing.

When manufacturing the patch of the present invention, it can be manufactured using a Negoo-shaped mixer with Σ, Z, and Banbury type blades like a normal hot melt manufacturing machine, but it is not suitable for mixing the oil phase and the water phase. From the viewpoint of making the particle size of the water-containing superabsorbent polymer small and stable, and shortening the production time, we use chi-type or propeller-type mixers, colloid mills, pressure valve emulsifiers, ultrasonic emulsifiers, etc. It is better to use a suitable stirring device, and a patch with higher stability can be obtained. As for the manufacturing method, first, a kneader is heated to about 130°C,
Heat and melt elastomer, oil, tackifier, etc.
After mixing, reduce the temperature of the materials to about 90°C. Separately, water is heated to about 60° C., and the superabsorbent polymer is gradually added and dissolved.

The above oil component is transferred to a mixer, etc., and the temperature is maintained at approximately 90°C. Next, the above water-containing super absorbent polymer is added while stirring at high speed, and then crude drugs, etc. are mixed and stirred to form the adhesive layer of the patch. obtain.

The temperature during high-speed stirring when producing the above-mentioned patch has a great influence on the particle size distribution and, ultimately, on the stability of the product.

When stirring at a low temperature, the particle size is coarse and water may separate on the surface, so the stirring temperature is 65 to 95 °C, preferably 80 to 90 °C.
℃, rotation speed is 1. Oo O~30.00 Or p
In order to obtain the most stable product, mixing with a mixer of about 1,200 to 5 OOOrPm is recommended.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Note that parts and percentages hereinafter mean parts by weight and percentages by weight, respectively.

Example 1 Liquid paraffin (Reagent grade 1 manufactured by Hanka Kagakuyaku Co., Ltd.) 62
．． s part and styrene-isoprene-styrene block copolymer (Shell Chemical Co., Ltd.)! ! 1 Reflex TR
1107) 100 parts were placed in a kneader heated to 130°C, and heated and stirred to melt.

Next, a tackifier (Alcon P-100 manufactured by Arayo Kagaku Co., Ltd.)
．． Gradually add 125 parts of saturated alicyclic hydrocarbon resin and stir to produce an oil component. Separately, 187.5 parts of purified water was heated to about 60°C, and superabsorbent polymer polyacrylic acid was added. Gradually add 50 parts of sodium (Panakayaku manufactured by Nippon Kayaku Co., Ltd.) and dissolve with stirring to produce a water component. Next, the oil component is transferred to a propeller-type mixer, and after the temperature is lowered to about 90° C., the rotation speed is set to 1,500 rPm, the water component is gradually added, and the mixer is thoroughly homogenized by stirring at high speed.

To this mixture were added 18.75 parts of methyl salicylate, 31.25 parts of l-menthol and 0.0 parts of diphenhydramine hydrochloride.
Add 0,625 parts of the main ingredient and stir again at high speed. The adhesive base material thus obtained was coated on a silicone-treated liner to a thickness of about 0.5 rrrn, transferred to a nonwoven fabric, cooled, and cut into 10 cm x 14 pieces. patch.

Example 2 Tackifying resin (Escorets 12 manufactured by Exxon Chemical Co., Ltd.)
02 (U), aliphatic hydrocarbon resin) 120 parts, liquid rubber (Vistanetx LMMS manufactured by Exxon Chemical Co., Ltd.) 3
0 parts and styrene-isoprene-styrene block copolymer (Califlex TR11 manufactured by Shell Chemical Co., Ltd.)
Q7) Put 100 parts into a kneader heated to 130℃,
Heat and stir to melt. To this, 62.5 parts of higher alcohol (manufactured by Hanka Kagaku Yakuhin Co., Ltd., reagent primary cetyl alcohol) is added, and the mixture is further stirred. To this mixture was added 31.25 parts of glycol salicylate, dI! - Charge the main ingredient consisting of 18.75 parts of camphor and 6.25 parts of hot pepper extract, transfer this to a propeller type mixer and lower the temperature to 90°C. Separately, 190 parts of purified water was heated to about 60°C, and superabsorbent polymer sodium polyacrylate (Steel Chemical Industry Co., Ltd.) was heated to about 60°C.
Aqua Keep Co., Ltd.) was gradually added, stirred and dissolved. The mixture was gradually added to the above mixer, stirred at high speed in the same manner as in Example 1, cooled, coated, and cut to obtain the adhesive patch of the present invention. get.

Comparative Example 1 As a control drug, 3% methyl salicylate and 5 ml of l-menthol were added to a pap base material consisting of gelatin, carboxymethylcellulose, polyvinyl alcohol, sodium polyacrylate, glycerin, sintered kaolin, and purified water.
% and diphenhydramine hydrochloride 0.01% of herbal medicine were mixed, kneaded in the usual manner, coated on a nonwoven fabric to a thickness of about 1.0 m, and cut into pieces of 10 (z x 14 cm) to obtain comparative patches.

Comparative Example 2 As a control drug, 3% methyl salicylate, 5% l-menthol,
After mixing 0.01% of diphenhydramine hydrochloride as the main ingredient and kneading it using the usual hot-melt kneading method, 0.01% of diphenhydramine hydrochloride was mixed.
After coating to a thickness of 1+rn, it was cooled, transferred to a polyethylene base fabric, and cut into 1010×14 pieces to obtain a comparative patch.

Test Example 1 Each performance was tested using the patches of the above Examples and Comparative Examples and two types of commercially available patches.

That is, 20 in-house volunteers were recruited as subjects, and after a 12-hour patch test, they were asked to fill out a survey form for each performance item shown in Table 1 below. For each item, each person scored a maximum of 5 points, and the better the item, the higher the score, and the total score is shown in Table 1.

As is clear from the above results in Table 1, the six types of samples were:
Each has different characteristics, with distinct strengths and weaknesses. For example, Comparative Example 2 has excellent adhesiveness and irritation level, but is inferior in cooling sensation and texture. In addition, commercial product 1
has excellent cooling sensation and irritation level, but is inferior in adhesiveness. On the other hand, the sample of the present invention was excellent in each item and also showed a high score in the overall evaluation. Another big advantage is that there was no rash.

Test Example 2 The following test was conducted on the stability of the same product used in Test Example 1 above.

(1) Moisture retention Each sample was placed in an oven at 40°C, and the weight of the product was measured every 30 minutes from 0 to 3 hours and every hour from 3 to 12 hours. The results are shown in FIG. The measured value is
The initial weight was taken as 100%, and the weight loss was expressed. In addition, the numbers 1 and 2 for each graph in FIG. 1 correspond to Examples 1 and 2.
Comparative Examples 1 to 2 correspond to Comparative Examples 1 to 2. 5 to 6 correspond to Commercial Products 1 to 2, respectively.

(2) Holding power Cut each sample into a length of 20 m x 50 mm, and place it on a stainless steel plate about half of the upper side (20 m) as shown in Figure 2.
A weight 2009 was attached to the lower end of the sample (Fig. 2A is a front view of the test piece for the holding force test adjusted in this way, and Fig. 2B is a 1 is a stainless steel plate, 2 is a patch sample, and 2 is a side view of the same.
2" means the base fabric, 2" means the adhesive layer, and gu means the weight)
. The test piece thus prepared was placed in an oven at 60°C, and the time until the weight fell was measured, and the holding force was determined. The results are shown in Table 2.

Table 2 (note) c, ■: Coefficient of variation In the above test, the product of Comparative Example 2 did not contain any water, and the decrease was due to volatilization of the crude drug. Among the other 5 products, the products of Examples 1 and 2 of the present invention had considerably better moisturizing power (higher moisturizing properties) than the other 3 products, and therefore good results were obtained in terms of cooling sensation and product stability. .

Regarding the holding power, compared to the product of Comparative Example 1 and Commercial Product 1, which are conventional adhesives, the adhesive force on the surface was weak, so the falling time was less than 1 minute. Apart from the product of Comparative Example 2, among the other three types, the samples of Examples 1 and 2 of the present invention had sufficient holding power and were resistant to the so-called sagging phenomenon. Ta.

[Brief explanation of drawings]

FIG. 1 is a graph showing the moisture retention test results of each patch, FIG. 2 is a schematic diagram of a test piece for testing the retention force of each patch, and FIG. 2A is a front view thereof; FIG. 2B is a side view thereof. Each symbol in FIG. 2 is as follows. 1 stainless steel plate, 2: patch sample, 2: sample base fabric, 2": its adhesive layer, 2: weight Patent applicant: Teikoku Seiyaku Co., Ltd. Patent attorney: Aoyama Aoyama and 1 other person

Claims (1)

[Claims] (11A-B = A group in which a water-containing superabsorbent polymer is dispersed in an oily continuous phase consisting of an A-type unvulcanized elastic teleblock copolymer, an oil component, and a tackifying component) A tape-shaped water-containing patch characterized by using a material. (2) The patch according to item (1) above, which contains a skin irritant and analgesic and anti-inflammatory agent as medicinal ingredients in the base material. (3) Tape-shaped The patch according to item (1) above, wherein the water content in the water-containing patch is 5 to 50% by weight. (4) The medicinal ingredients include a skin irritant and an analgesic and anti-inflammatory agent, either alone or in combination. (5) The patch of item (1) above, containing 1.0 to 40.0 weight % of a super absorbent polymer in the base material. Patch. (131A-B-A unvulcanized elastic teleblock copolymer, oil component and tackifier are dissolved at high temperature, then cooled,
1. A method for producing a tape-shaped water-containing patch, which comprises mechanically mixing a drug and an aqueous continuous phase of a water-containing superabsorbent polymer, and cooling and solidifying the mixture.