JPH0649067B2 - Skin patch sheet - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a skin patch sheet, that is, plaster. More specifically, an adhesive containing a drug is firmly adhered onto a polyethylene terephthalate film, and the surface has a warm touch. The present invention relates to an adhesive skin patch sheet which has no discomfort and is excellent in feeling and skin compatibility.

[0002]

2. Description of the Related Art Heretofore, an adhesive skin patch sheet obtained by laminating an adhesive containing a drug such as a skin stimulant or an anti-inflammatory analgesic on a base sheet has been used for medical purposes. In such a patch, for example, JP-A-54 is used.
As described in JP-A-138124, not only does it have good adhesiveness when the patch is applied to the skin, compatibility with the skin and appropriate elasticity, but also does not cause irritation to the skin during peeling, It is known that a diene-based copolymer, particularly a diene-based block copolymer, is suitable as the adhesive because it can be easily peeled off.

On the other hand, in the above-mentioned patch, as the base material sheet, one using a polyethylene terephthalate film or an aluminum foil is known because it is excellent in the barrier property of the drug. The surface feels cold, and the feel and texture are bad. Moreover, particularly in the patch, since the diene block copolymer as the pressure-sensitive adhesive contains the higher fatty acid and the fluid paraffin as the plasticizer together with the drug, the affinity with these base materials is very poor. As a result, when a pressure-sensitive adhesive composed of a diene block copolymer is simply applied directly onto the above-mentioned base material to give a patch, the adhesiveness of the pressure-sensitive adhesive to the base material sheet is remarkably poor.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems in the conventional skin patch sheet, and is an adhesive containing a drug while using a polyethylene terephthalate film as a base material. Is firmly adhered to the base material, and the adhesive containing the drug is also firmly adhered to the base material. Furthermore, the surface has a warm touch, and there is no discomfort, and the texture and skin fit An object is to provide an adhesive skin patch sheet having excellent properties and the like.

[0005]

A skin patch sheet according to the present invention comprises a polyethylene terephthalate film, which is a substrate sheet formed by adhering a fiber sheet and a polyethylene terephthalate film having a thickness of 10 μm or less, to the surface of the polyethylene terephthalate film.
Ethylene-vinyl acetate copolymer 50 to 2 based on 100 parts by weight of (a) a first primer layer made of a saturated polyester resin, and (b) polyurethane having a terminal hydroxyl group.
A resin composition consisting of 00 parts by weight and 50 to 200 parts by weight of chlorinated rubber, and a second primer layer containing 20 to 35% by weight of anhydrous silica fine powder are laminated and adhered in this order,
Further, a pressure-sensitive adhesive layer made of a styrene-diene-styrene block copolymer containing a drug is laminated and adhered on the second primer layer.

In the present invention, the base sheet is formed by adhering a fiber sheet and a polyethylene terephthalate film, and this polyethylene terephthalate film is
It is necessary that the thickness is 10 μm or less. When the thickness of the polyethylene terephthalate film exceeds 10 μm, the obtained patch sheet is hard and remarkably unsuitable for the skin. In particular, a polyethylene terephthalate film having a thickness of 3 to 5 μm is preferably used.

Further, polyethylene terephthalate film has a breaking strength (longitudinal direction) of 25 to 35 Kgf / square millimeter, 2% (longitudinal direction) module (tensile strength) of 7.
It is preferably between 5 and 9.5 Kgf / mm 2.
Therefore, for example, the thickness is 3.5 μm, the breaking strength is 29.4 Kgf /
A polyethylene terephthalate film having a square millimeter of 2% modulus 8.6 kgf / square millimeter can be preferably used.

On the other hand, woven cloth, knitted cloth, non-woven cloth or synthetic leather is preferably used as the fiber sheet adhered to the polyethylene terephthalate film. Among these, a non-woven fabric is particularly preferable because it has a soft and warm feel and is excellent in feeling.
Of the woven cloth, a raised cloth is preferably used. The fiber sheet of the polyethylene terephthalate film is adhered to the fibrous sheet by, but not limited to, a urethane adhesive, for example.

In the present invention, a two-layer primer layer is laminated and adhered on the polyethylene terephthalate of the base sheet as described above, and a pressure sensitive adhesive comprising a styrene-diene-styrene block copolymer containing a drug thereon. The layers are laminated and bonded. The first primer layer applied on the polyethylene terephthalate film is made of saturated polyester resin. The saturated polyester resin is an aromatic dicarboxylic acid (eg, terephthalic acid, isophthalic acid, etc., or a mixture thereof), or an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid (eg, adipic acid, sebacic acid, etc., or a mixture thereof). And a saturated aliphatic diol (for example, ethylene glycol, neopentyl glycol, 1,4-cyclohexanediol, etc., or a mixture thereof) can be obtained by condensation polymerization according to a conventional method. In particular, the saturated polyester resin preferably has a molecular weight in the range of 15,000 to 20,000. Such a saturated polyester resin is commercially available, and such a commercially available product can be preferably used in the present invention.

The saturated polyester resin is dissolved in an appropriate organic solvent (for example, toluene) to prepare a primer, which is applied on the surface of polyethylene terephthalate film and dried to form a first primer layer. can do. Next, the second primer layer
A resin composition comprising 50 to 200 parts by weight of an ethylene-vinyl acetate copolymer and 50 to 200 parts by weight of a chlorinated rubber based on 100 parts by weight of a polyurethane having a hydroxyl group at the terminal, and anhydrous silica fine particles based on the resin composition. Powder 10
It contains 20% by weight.

The above-mentioned polyurethane having a hydroxyl group at the end is, for example, a diol having a molecular weight of 1,000 to 3,000 and a diisocyanate having an isocyanate group / hydroxyl group molar ratio of 1.
The reaction is carried out at 5 to 2.0 to obtain a urethane prepolymer having an isocyanate group at the terminal, and then a low molecular weight polyol as a chain extender is added to the urethane prepolymer at a hydroxyl group / isocyanate group molar ratio of 1 .4 to 2.0
Can be obtained by reacting with. The molecular weight is preferably in the range of 30,000 to 80,000.

As the diol having a molecular weight of 1,000 to 3,000, polyester diol and polyether diol are preferably used. Polyester diols include, for example, glycols such as ethylene glycol, propylene glycol, butylene glycol and diethylene glycol, saturated dicarboxylic acids such as adipic acid and sebacic acid, unsaturated dicarboxylic acids such as maleic acid and fumaric acid, phthalic acid and isophthalic acid. A linear polyester diol obtained by reacting with an aromatic dicarboxylic acid or its anhydride, etc. is preferably used. Furthermore, polyester diols obtained by ring-opening polymerization of lactones such as caprolactone and methylcaprolactone with glycols are also preferably used.

As the polyether diol, those obtained by ring-opening polymerization or copolymerization of cyclic ether compounds such as ethylene oxide, propylene oxide, epichlorohydrin, oxacyclobutane and tetrahydrofuran are preferably used. In the preparation of polyurethane, when the molecular weight of the diol used is too high,
The second primer obtained by adding the above-mentioned ethylene-vinyl acetate copolymer, rubber chloride and anhydrous silica fine powder to the obtained polyurethane has an excessively high viscosity, which causes difficulty in coating.

The diisocyanate is not particularly limited, and aromatic diisocyanates such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate are appropriately used. To be As the low molecular weight glycol as the chain extender, for example, ethylene glycol, propylene glycol, diethylene glycol and the like are preferably used.

In the present invention, the use of the second primer layer containing polyurethane having a hydroxyl group at the end as described above allows the strong adhesion between the first primer layer described above and the pressure-sensitive adhesive layer described later. Good adhesion can be achieved. As is well known, chlorinated rubber is a rubber obtained by chlorinating natural rubber and has a molecular weight of about 5,000 to 5,000.
It has 100,000 and a chlorine content of 65% by weight or more.

The fine silica powder is preferably made of high-purity silica and has a particle size of about 10 to 100 mμ. When the particle size is smaller than 10 mμ, the second obtained
If the viscosity of the primer is too high, it is difficult to apply. On the other hand, if it exceeds 100 mμ, the dispersion in the primer is not uniform, and the application is difficult. In the present invention, the second primer layer contains 50 to 200 parts by weight of ethylene-vinyl acetate copolymer and 50 to 20 parts of chlorinated rubber based on 100 parts by weight of polyurethane as described above.
In addition to containing 0 part by weight, 20 to 35% by weight of anhydrous silica fine powder is contained in the second primer layer.

In such a second primer, the polyurethane is the main component of the adhesive agent, but the adhesive strength is insufficient with polyurethane alone. Therefore, the adhesive strength can be increased by blending the ethylene-vinyl acetate copolymer with polyurethane. The content of vinyl acetate in the ethylene-vinyl acetate copolymer is 70 to 90%.
Is preferable, and the average degree of polymerization is 1500 to 4000.
Is preferred.

However, since the polyurethane and the ethylene-vinyl acetate copolymer are poorly compatible with each other, by blending chlorinated rubber therein, the compatibility is increased and the adhesive strength of the resulting primer is improved. Can also be improved. The blending ratio of each of the above-mentioned components in the second primer is selected in order to maximize the adhesive strength and compatibility of the primer.

The silica fine powder blended in the second primer reduces the blocking property of the primer layer to be formed, and when the primer layer is applied to the base sheet, it is easily spread when it is made into a roll. To do. However, when it is blended in an excessive amount, the viscosity of the primer to be obtained is remarkably increased, which makes application difficult and also reduces the adhesive force of the primer.

Polyurethanes such as those mentioned above, ethylene-
The second primer can be obtained by dissolving the vinyl acetate copolymer and the chlorinated rubber in an appropriate organic solvent (for example, toluene) and dispersing the silica fine powder therein. The second primer layer can be formed by applying such a second primer on the first primer layer made of the above-mentioned saturated polyester resin and drying it.

In the present invention, the thickness of the first primer layer is preferably in the range of 1 to 5 μm, and the thickness of the second primer layer is preferably in the range of 5 to 20 μm. When the thickness of each primer layer is too thin, the desired strong adhesive force cannot be obtained, while when it is too thick, the primer layer is hard and the flexibility required for the obtained skin patch sheet. It is not preferable because it impairs the sex.

After the first and second primer layers are formed on the polyethylene terephthalate surface of the substrate sheet as described above, a styrene-diene-styrene block containing a drug is formed on the second primer layer. By providing the pressure-sensitive adhesive layer made of the King copolymer, it is possible to obtain a pressure-sensitive adhesive skin patch sheet in which the pressure-sensitive adhesive layer is firmly adhered to the base sheet.

Specific examples of the styrene-diene-styrene block copolymer which constitutes the pressure-sensitive adhesive in the present invention include styrene-butadiene-styrene block copolymer and styrene-isoprene-styrene block copolymer. . These styrene-diene-styrene block copolymers may be used alone or as a mixture as a pressure-sensitive adhesive, or a composition containing a plasticizer, a tackifying resin, a filler, an antioxidant and the like together with these block copolymers. It may be used as a product.

Such styrene-diene-styrene block copolymers are disclosed, for example, in the above-mentioned JP-A-54-1381.
It is already known as described in detail in the publication No. 24. When A is a block of a glassy or hard non-elastic thermoplastic polymer composed of styrene and B is a block of an elastic polymer of a conjugated diene such as butadiene or isoprene, a block having a structure of ABAA. In the copolymer, block A accounts for 10 to 50% by weight of the total weight of the polymer. Such a styrene-butadiene-styrene block copolymer is manufactured by Califlex TR-110.
1, TR-1102, etc., and the styrene-isoprene-styrene block copolymer is Califlex TR.
-1107 (all manufactured by Shell Chemical Co., Ltd.) is commercially available and can be obtained.

[0025]

As described above, according to the adhesive skin patch sheet of the present invention, a fiber sheet is adhered to a polyethylene terephthalate film to form a base sheet, and the surface of the polyethylene terephthalate of the base sheet is first coated. And the second primer layer are sequentially laminated and adhered, and a pressure sensitive adhesive layer made of a styrene-diene-styrene block copolymer containing a drug is laminated and adhered thereon.

Here, the polyethylene terephthalate film functions as a nearly perfect barrier layer against the diffusion and permeation of the drug and the adhesive, so that when the drug has a strong diffusion and permeation like l-menthol and salicylates. Even at that time, the drug does not diffuse and permeate the surface of the patch, and the diffusion and permeation of the adhesive is also prevented. Furthermore, the first
Since the primer layer of 1 is firmly adhered to the polyethylene terephthalate film, and the second primer layer is firmly adhered to the adhesive layer made of a styrene-diene-styrene block copolymer containing a drug, the patch sheet is applied to the skin. No adhesive remains on the skin when peeled off.

Moreover, since the polyethylene terephthalate film has a soft, warm and tactile fiber sheet as a surface layer, it has excellent texture and skin compatibility, which are indispensable as a skin patch, and has a sticky surface. It is also excellent in usability because it does not exist. Moreover, when the base material sheet is manufactured and then wound on a roll, there is no blocking between the base material sheets, and rewinding, that is, expansion is easy.

[0028]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. Preparation of the first primer The saturated polyester resin is Vylon 20 manufactured by Toyobo Co., Ltd.
SS (20% solids) was used. Preparation of the second primer The second primer is Crisbon 4005 manufactured by Dainippon Ink and Chemicals, Inc. (polyurethane having terminal hydroxyl group, viscosity 20 to 4 poise (125 ° C.), molecular weight about 50,000, polyester-based polyurethane solution, solid as polyurethane. 25%), Sorelex S4 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. as an ethylene-vinyl acetate copolymer (EVA resin)
305 (concentration 40%) or Soarex E-830, and Adeka chlorinated rubber CR-made by Asahi Denka Co., Ltd. as chlorinated rubber
Each of 10, 40 and 50 was dissolved in toluene / methyl isobutyl ketone (MEK) (weight ratio 1/1) to a concentration of 30% by weight.

As a fine silica powder, a predetermined amount of Aerosil 130 (particle size: 16 mμ) or 200 (particle size: 12 mμ) manufactured by Nippon Aerosil Co., Ltd. and a small amount of a solvent were added to this solution.
The second primer was prepared by uniformly stirring. Examples 1 to 4 Preparation of Substrate Sheet Urethane-based two-component adhesive agent (Dainippon Ink and Chemicals, Inc.) on a polyethylene terephthalate film having a thickness of 5 μm
Crisbon NT150) manufactured by gravure coater with a wet basis weight of 12 g / square meter and then 12
It was heated and dried at 0 ° C. for 90 seconds, and the fiber sheet shown in Table 1 was attached thereto and wound up. Laminate formation of primer layer Next, the above-mentioned first primer was applied to the surface of the polyethylene terephthalate film of the substrate sheet obtained as described above by a gravure coater to obtain a wet basis weight of 1
It is applied at 0 g / square meter and dried by heating at 120 ° C. for 60 seconds to form a first primer layer having a thickness of 2 μm, and then the above-mentioned second primer layer is applied thereto by a gravure coater with a wet basis weight of 12 g. / Square meter and dried by heating at 120 ° C. for 90 seconds to form a second primer layer having a thickness of 3 μm and wound. Production of skin patch sheet 30 parts by weight of styrene-isoprene-styrene block copolymer (Califlex TR-1107 manufactured by Shell Chemical Co., Ltd.), 35 parts by weight of terpene resin (YS resin manufactured by Yasuhara Chemical Co., Ltd.), 10 parts by weight of liquid paraffin, methyl salicylate 6 parts by weight, 3 parts by weight of 1-menthol and 1 part by weight of d-camphor were mixed to obtain a pressure-sensitive adhesive containing a drug.

This pressure-sensitive adhesive was applied to a release paper, a base sheet having the above-mentioned primer layer laminated thereon was developed, and laminated on the primer layer to obtain a skin patch sheet. Comparative Examples 1 to 4 Preparation of base sheet Polyvinyl chloride (average degree of polymerization 1300) 100 parts by weight Plasticizer (polyester type, molecular weight 2600) 55 parts by weight Stabilizer (Ca-Zn type) 1.5 parts by weight The product was formed into a film having a thickness of 70 μm by the calendar method.

On a polyethylene terephthalate film having a thickness of 5 μm, a urethane two-component adhesive (Crisbon NT150 manufactured by Dainippon Ink and Chemicals, Inc.) was applied with a gravure coater at a wet basis weight of 12 g / square meter, and then 120 It was heated and dried at 90 ° C. for 90 seconds, and the above polyvinyl chloride resin film was attached thereto to obtain a base sheet. Laminate formation of primer layer Next, the above-mentioned first primer was applied to the surface of the polyethylene terephthalate film of the substrate sheet obtained as described above by a gravure coater to obtain a wet basis weight of 1
It is applied at 2 g / sqm and dried by heating at 120 ° C. for 60 seconds to form a first primer layer having a thickness of 3 μm, and then the above-mentioned second primer layer is gravure coater with a wet basis weight of 12 g. / Square meter, and dried by heating at 120 ° C. for 60 seconds to form a second primer layer having a thickness of 3 μm and wound. Manufacture of skin patch sheet The same adhesive as described above was applied to release paper, a base sheet having the primer layer laminated thereon was developed, and laminated on the primer layer to obtain a skin patch sheet.

However, in Comparative Example 2, the polyvinyl chloride resin film was directly adhered to the polyethylene terephthalate film without providing a primer layer, and in Comparative Example 3, the polyvinyl chloride resin as the surface layer was formed on the polyethylene terephthalate film. The film was not adhered, and in Comparative Example 3, the drug layer was directly laminated on polyethylene terephthalate. The following tests were carried out on each patch sheet obtained as described above. The results are shown in Tables 1 and 2.

[0033]

[Table 1]

[0034]

[Table 2]

Feeling and appearance Feeling was evaluated by a sensory test, and appearance was visually evaluated, and ⊚ was evaluated as very good, ◯ is good, Δ is slightly bad, and x is very bad. Spreading force : Base sheets having a width of 36 cm provided with a primer layer were laminated on each other, allowed to stand at 40 ° C for 1 week, and then peeled off at a speed of 200 mm / min. Adhesiveness between adhesive and base sheet The release paper is peeled off from the skin patch manufactured as described above, the pressure-sensitive adhesive layer is stuck to the bakelite plate with a roller, and after 24 hours, the bakelite plate is applied to the skin patch. The sheet was peeled off, and the presence or absence of adhesive residue on the Bakelite plate of the adhesive was examined. ○ indicates no adhesive residue, △ indicates some adhesive residue,
× indicates that the adhesive residue was remarkable. Comprehensive Evaluation The test results above were evaluated comprehensively.

Claims (6)

[Claims] 1. A surface of a polyethylene terephthalate film of a base material sheet obtained by adhering a fiber sheet and a polyethylene terephthalate film having a thickness of 10 μm or less, (a) a first primer layer made of a saturated polyester resin, and (b) ) A resin composition comprising 50 to 200 parts by weight of an ethylene-vinyl acetate copolymer and 50 to 200 parts by weight of a chlorinated rubber, and 20 to 35% by weight of anhydrous silica fine powder with respect to 100 parts by weight of a polyurethane having a hydroxyl group at a terminal. Second containing
Is laminated and adhered in this order, and a styrene containing a drug is further formed on the second primer layer.
A skin patch sheet, comprising a pressure-sensitive adhesive layer made of a diene-styrene block copolymer laminated and adhered. 2. The skin patch sheet according to claim 1, wherein the particle size of the fine silica powder is 10 to 100 mμ. 3. The skin patch sheet according to claim 1, wherein the first primer layer has a thickness of 1 to 5 μm and the second primer layer has a thickness of 5 to 20 μm. 4. The skin patch sheet according to claim 1, wherein the fiber sheet is a woven fabric, a knitted fabric or a non-woven fabric. 5. The skin patch sheet according to claim 1, wherein the fiber sheet is synthetic leather. 6. The skin patch sheet according to claim 4, wherein the woven fabric is a raised fabric.