JPH0614957B2 - Tape-shaped hydrous patch and method for producing the same - Google Patents

Description

The present invention relates to a tape-shaped patch and a method for producing the same.

Conventionally, in a poultice drug for the purpose of external analgesic and anti-inflammatory treatment, the main drug such as methyl salicylate, l-menthol and capsicum extract is mixed in the base material, and the main drug is absorbed through the skin to improve blood circulation there. The treatment is carried out by.

This poultice is an aqueous poultice based on gelatin, CMC, glycerin, pigments, etc., and an oil-based poultice based on synthetic (natural) rubber, various elastomers, oils, and sticking agents. There are two types, each with its own characteristics. In the water-based poultice, water forms a continuous phase, and by its nature, the adhesive force is considerably low and the adhesive force is not generated unless the coating thickness is increased. Also, in the case of long-term storage, the base material hardens due to the volatilization of water over time, or the crosslinking of the contained polymeric substances, and the adhesion to the skin is impaired. There is a drawback that

Although the oil-based poultice is excellent in adhesive strength, it does not have an initial cooling effect on the skin because it does not contain water, and the base material is often hard and lacks flexibility. is there.

A patch that overcomes the drawbacks of the first half has been proposed (Japanese Patent Publication No. 56-43444), but this patch forms a W / O type emulsion, and when a water molecule is dispersed in an oil continuous phase, a surfactant is used. Since it is used, it may cause redness, eczema, etc. when continuously applied to the human body.

In view of the above-mentioned drawbacks in the conventional poultice, the present inventors have conducted intensive studies and as a result, by mixing and dispersing the water-absorbent superabsorbent polymer in the conventional hot-melt pressure-sensitive adhesive, It was found that a patch that eliminates the above-mentioned drawbacks and has an excellent medicinal effect, adhesive strength, and overall feeling of use can be obtained.
The present invention has been completed.

That is, the present invention is based on an aqueous continuous phase composed of an ABA type unvulcanized elastic teleblock copolymer, oil, and a sticking agent in which a water-containing superabsorbent polymer is dispersed. The present invention provides a tape-shaped hydrous patch used as a material.

In order to produce the patch of the present invention, first, an ABA type unvulcanized elastic teleblock copolymer and oil are heated and melted at 150 ° C., and a tackifying component is gradually added to this 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 with stirring to obtain a hydrous superabsorbent polymer. The oily continuous phase as it is or conveyed to a high speed mixer, the temperature is lowered to about 80 to 90 ° C., the water-containing superabsorbent polymer is gradually added thereto, and after stirring, an external analgesic and anti-inflammatory agent is added. Similarly, after uniform stirring, it is coated on a base cloth with various coating machines, laminated with a liner, cooled and solidified, and then cut into a desired size to obtain a product.

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

A of the ABA type unvulcanized elastic teleblock copolymer (hereinafter abbreviated as elastomer) used in the present invention is
A hard polymer with a glass transition temperature of 25 ° C or higher,
Styrene having an average molecular weight of 000 to 500,000,
Polymer such as methylstyrene, 1 in elastomer
It accounts for 5 to 40% (weight%, the same applies 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. As an elastomer having the above-mentioned properties, Califlex (Clayton) TR1 manufactured by Shell Chemical Co., Ltd.
107, 1102, 1111 and the like.

As the oil component (oil) used in the present invention together with the above elastomer, styrene in the elastomer, a paraffin-based compound which is not chemically compatible with methylstyrene,
You can use naphthenic oils, liquid rubbers of medium and low molecular weight, paraffin wax, etc., but the mixture of oil components will have a great influence on the physical properties (adhesive strength, duck, flexibility, etc.) of the final product, so it will be strictly applied. You need to be careful.

As the tackifying component used in the present invention, any resin that is compatible with either one or both of the A portion and B portion of the blended elastomer or a resin that is not compatible is used. Generally, it is said that the A part of the elastomer controls the cohesive force and the B part controls the elastic force. There are tackifiers compatible with each other and tackifiers not compatible with both, and the desired physical properties of the final product are obtained. It is used in combination as appropriate. From the viewpoint of thermal stability, a good product can be obtained by using a tackifier compatible with the component B. As compatible with A part of elastomer, coumarone
Aromatic resins such as indene resin and methylindene / polystyrene resin can be used. In addition, examples of those compatible with the B portion include polyterpenes, modified rosins, and non-aromatic petroleum resins. Examples of the resin that is incompatible with both the A portion and the B portion include a phenol resin. 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 and the like can be added to the oil phase composed of the above three components.

In the present invention, a water-containing superabsorbent polymer is mechanically dispersed in an oil component without using a surfactant, and the superabsorbent polymer used is gelatin, carboxymethyl cellulose, Water-soluble polymers such as polyacrylates, alginates, mannan, polyvinyl alcohol, and acrylic polymers can be used. If necessary, a pH adjusting agent, a chelating agent, an antiseptic agent or the like may be added to the water component to stabilize the product.

As the main drug used in the present invention, any of those used as external analgesic and anti-inflammatory agents such as methyl salicylate, glycol salicylate, 1-menthol, dl-camphor, nonyl acid vanillyl amide, powdered oat, and diclofenac sodium is used. it can. Since it is not necessary to emulsify the main drug, it can be mixed in both the oil phase and the water phase, and can also be mixed in the patch of the mixed solution.

When the patch of the present invention is produced, it can be produced by a kneader-shaped mixer having Σ · Z · Banbury type blades such as a normal hot melt producing machine, but for mixing the oil phase and the water phase, From the viewpoint of making the particle size of the water-containing super absorbent polymer small and stable, and shortening the manufacturing time, such as a Kai type or propeller type mixer, colloid mill, pressure valve type emulsifier, ultrasonic emulsifier It is better to use a stirring device, and a patch with higher stability can be obtained. As a manufacturing method, first, the kneader is heated to about 130 ° C.,
Elastomer, oil, sticking agent, etc. are heated and melted,
After mixing, reduce the temperature of the material to about 90 ° C. Separately, the water is heated to about 60 ° C., and the super absorbent polymer is gradually added and dissolved.

The above oil component was conveyed to a mixer or the like to maintain the temperature at about 90 ° C., then the above water-containing superabsorbent polymer was added while stirring at high speed, and further the main ingredient was mixed and stirred to form an adhesive layer of the patch. obtain.

The temperature at the time of high-speed stirring in producing the above-mentioned patch has a great influence on the particle size distribution, and thus on the stability of the product.
When stirred at a low temperature, the particle size is coarse and water may separate on the surface. Therefore, the temperature is 65 to 95 ° C, preferably 80 to 90 ° C.
Mixing with a mixer at a rotation speed of 1,000 to 30,000 rpm, preferably about 1,200 to 5,000 rpm is preferable for obtaining the most stable product.

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In addition,
In the following, "parts" and "%" mean "parts by weight" and "% by weight", respectively.

Example 1 Fluid paraffin (Hanai Chemical Co., Ltd. reagent first grade) 6
2.5 parts and styrene-isoprene-styrene block copolymer (Califlex TR manufactured by Shell Chemical Co., Ltd.)
1107) Put 110 parts in a kneader heated to 130 ° C., and heat and stir to melt.

Next, tackifier (Arcon P-10 manufactured by Arakawa Chemical Co., Ltd.)
0, alicyclic saturated hydrocarbon resin) 125 parts is gradually added,
The oil component is produced by stirring. Separately, 187.5 parts of purified water was heated to about 60 ° C., and 50 parts of superabsorbent polymer sodium polyacrylate (Panakayak manufactured by Nippon Kayaku Co., Ltd.) was gradually added, and dissolved by stirring to obtain a water component. To manufacture. Next, the above oil component is transferred to a propeller type mixer, the temperature is lowered to about 90 ° C., the rotation speed is set to 1,500 rpm, the above water component is gradually added, and high speed stirring is performed to sufficiently homogenize.
To this mixture were added 18.75 parts of methyl salicylate, 31.25 parts of 1-menthol and 0.
Add the main ingredient consisting of 0625 parts and stir again. The patch substrate thus obtained is applied on a silicon-treated liner to a thickness of about 0.5 mm, and then transferred to a non-woven fabric,
After cooling, the patch of the present invention is obtained by cutting into a size of 10 cm × 14 cm.

Example 2 Tackifying resin (Escollets 12 manufactured by Exxon Chemical Co., Ltd.)
02 (U), 120 parts of aliphatic hydrocarbon resin, liquid rubber (Vexanex LMMS manufactured by Exxon Chemical Co., Ltd.) 3
0 parts and styrene-isoprene-styrene block copolymer (Califlex TR11 manufactured by Shell Chemical Co., Ltd.)
07) Put 100 parts in a kneader heated to 130 ° C.,
Heat and stir to melt. To this, 62.5 parts of highly absorbed alcohol (manufactured by Hanai Chemical Co., Ltd., reagent first-grade cetyl alcohol) is added and further stirred. To this mixture was added the main ingredient consisting of 31.25 parts of glycol salicylate, 18.75 parts of dl-camphor and 6.25 parts of capsicum extract,
This is transferred to a propeller mixer and the temperature is lowered to 90 ° C. Separately, 190 parts of purified water was heated to about 60 ° C., 40 parts of highly water-absorbing polymer sodium polyacrylate (Aquakeep Co., Ltd., Iron Making Chemical Co., Ltd.) was gradually added, and the mixture was stirred and dissolved in the above mixer. To Example 1 below.
After high-speed stirring in the same manner as above, cooling, coating and cutting are carried out to obtain the patch of the present invention.

Example 3 100 parts of a styrene-isoprene-styrene block copolymer (Califlex TR-1107 manufactured by Shell Chemical Co., Ltd.) as an oil-based mixture, an alicyclic saturated hydrocarbon petroleum resin (Arcon M- manufactured by Arakawa Chemical Industry Co., Ltd.) 100) 100
Parts, 5 parts of antioxidant dibutylhydroxytoluene, and 50 parts of kaolin are put in a kneader heated to 150 ° C. and dissolved by heating and stirring. Next, 45 parts of lanolin and cetyl alcohol 2
5 parts, liquid paraffin 25 parts (manufactured by Hanai Chemical Co., Ltd.)
Add and stir to mix.

Separately, 25 parts of methyl vinyl ether maleic anhydride copolymer (Aldrich), 5 parts of N, N'-dimethylacetamide, 15 parts of 1-menthol, 5 parts of diclofenac sodium and 100 parts of purified water are melted by heating as an aqueous component.

The temperature in the kneader was lowered, water-based components were added when the oil-based mixture reached about 90 ° C., and the mixture was stirred and mixed, and then the patch of the present invention was applied to the patch of the present invention using the same knitted fabric as in Example 1. obtain.

Comparative Example 1 As a control agent, 3% of methyl salicylate, 5% of 1-menthol and 5% of diphenene hydrochloride were used in a base material made of gelatin, carboxymethyl cellulose, polyvinyl alcohol, sodium polyacrylate, glycerin, sintered kaolin and purified water. A main ingredient of hydramine 0.01% is mixed, kneaded by a usual method, coated on a non-woven fabric to a thickness of about 1.0 mm, and cut into 10 cm × 14 cm to obtain a comparative patch.

Comparative Example 2 As a control agent, 3% of methyl salicylate and 5% of 1-menthol were added to a patch base material consisting of styrene-isoprene block copolymer, fluid paraffin and a tackifier.
The main agent of 0.01% of diphenhydramine hydrochloride was mixed and kneaded by a usual hot melt kneading method, and then, on a release paper.
After coating to a thickness of 1 mm, it is cooled, transferred to a polyethylene base cloth, and cut into 10 × 14 cm 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 volunteers in the company were recruited as examinees, and after a 12-hour sticking test, they were made to fill in a survey form for each performance item shown in Table 1 below. For each item, a maximum of 5 points per person was given, and points were given such that the better the item, the higher the score, and the total score is shown in Table 1.

As is clear from the above results, the seven types of samples are
Each has different characteristics, and its strengths and weaknesses are clearly visible. For example, Comparative Example 2 is excellent in tackiness and irritation, but is inferior in cool feeling and texture. Also, a commercial product 1
Has an excellent cooling sensation and irritation, but has poor tackiness. On the other hand, the sample of the present invention is excellent in each item and shows a high score in the comprehensive evaluation. Another major advantage is that there was no rash.

Test Example 2 The following test was performed on the stability of the same product as that 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 1 hour from 3 to 12 hours. The results are shown in FIG. The measured value is
The initial weight was set to 100% and the weight loss was expressed. The numbers of the graphs in FIG. 1 correspond to Examples 1, 2, and 3, 3 to 4 for Comparative Examples 1 and 2 and 5 to 6 for Commercial Products 1 and 2, respectively.

(2) Holding power Each sample was cut into 20mm width x 50mm length, and about half of the upper side (20mm width x 20mm length) was attached to the stainless steel plate as shown in Fig. 2, and the lower end of the sample was attached. Is a weight of 200 g (FIG. 2A is a front view of a test piece for holding power test adjusted in this way, FIG. 2B is a side view thereof, 1 is a stainless steel plate, 2 is a patch sample 2 '
Means the base cloth, 2 ″ means the adhesive layer, and g means a weight.) The test piece prepared in this manner was measured in the oven at 60 ° C. for the time required for the weight to fall, and the holding force was measured. The results are shown in Table 2.

In the above test, the product of Comparative Example 2 did not contain water at all, which was a decrease due to volatilization of the main drug. Of the other 5 items, the products of Examples 1 and 2 of the present invention had considerably better moisturizing properties than the other 3 items, and accordingly, good results were also obtained with respect to cold feeling and product stability. .

Regarding the holding power, the product of Comparative Example 1 and the commercial product 1 which are conventional patches have a short drop of 1 minute or less due to the weak adhesive force on the surface, but a comparative example using a hot melt adhesive. It was found that the samples of Examples 1 and 2 of the present invention had a sufficient holding power among the other three types apart from the product No. 2 and had a strong performance against the so-called sagging phenomenon.

[Brief description of drawings]

1 is a graph showing the results of the moisturizing test of each patch, FIG. 2 is a schematic view of a test piece for testing the holding power of each patch, and FIG. 2A is its front view. FIG. 2B is a side view thereof. The symbols in FIG. 2 are as follows. 1: stainless steel plate, 2: patch sample, 2 ': sample base cloth, 2 ": its adhesive layer, g: weight

Claims (6)

[Claims] 1. A base material in which a water-containing superabsorbent polymer is dispersed in an oily continuous phase comprising an ABA type unvulcanized elastic teleblock copolymer, an oil component and a sticking component. A tape-shaped water-containing patch comprising: 2. The patch according to claim 1, which contains a skin stimulant and an analgesic and anti-inflammatory agent as medicinal components in the base material. 3. The water content of the tape-shaped hydrous patch is 5 to 5.
The patch of claim (1), which is 0% by weight. 4. A skin stimulant and an analgesic / anti-inflammatory agent as a medicinal component, either individually or in combination of 0.01-2.
The patch according to claim (3), which contains 0.0% by weight. 5. A highly water-absorbent polymer is added to the base material in an amount of 1.0 to 4
The patch of claim (1) containing 0.0% by weight. 6. An ABA type unvulcanized elastic teleblock copolymer, an oil component and a sticking agent are melted at high temperature and then cooled,
A method for producing a tape-shaped hydrous patch, which comprises mechanically mixing a drug and an aqueous continuous phase of a hydrous superabsorbent polymer and cooling and solidifying the mixture.