JPH04300823A - Tacky adhesive tape or sheet for medical use and its production - Google Patents

Abstract

PURPOSE:To obtain the subject medical tacky adhesive tape or sheet having suitable water-vapor permeability and free from water-permeability by forming a tacky adhesive layer on a substrate composed of a microporous film made of a polymer having rubber elasticity. CONSTITUTION:The gas-permeable substrate to be used in the subject tape or sheet is a microporous film (preferably having a thickness of 10-2,000mum, especially 50-1,000mum) made of a polymer having rubber elasticity and selected from a polyurethane elastomer synthesized from a polyol, a diisocyanate and a chain extender, a polyvinyl chloride, a styrene-butadiene block copolymer, an acrylic rubber and a silicone rubber. A tacky adhesive layer made of acryl, rubber or silicone-based tacky adhesive is formed on the substrate. The tacky adhesive layer is preferably a coating layer having excellent gas permeability. The tape or sheet has characteristic features of high water resistance, resistance to easy peeling even in wet state, low staining tendency, sanitariness, softness, stretchability to give the skin feeling, safety to rash, free from stuffing tendency and inconspicuousness.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a medical adhesive tape or sheet having excellent gas permeability, particularly water vapor permeability.

0002

BACKGROUND OF THE INVENTION Many medical adhesive tapes or sheets, such as adhesive plasters and adhesive sheets containing drugs in the adhesive layer, have been produced in the past. When these tapes and sheets are applied to the skin for a long time (for example, for more than half a day), they often cause softening of the skin due to stuffiness, rashes, redness, and rashes. This is due to the fact that the adhesive layer constituting the medical adhesive tape or sheet and the base material such as the film supporting the same layer have poor water vapor permeability.

In order to increase the water vapor permeability of the base material of such medical adhesive tapes or sheets, the following measures have been conventionally taken.

[0004] A) A material with a large number of holes is used as a base material. Further, an adhesive layer is partially provided, for example, in a striped form, on an air-permeable base material such as a woven fabric or a non-woven fabric.

(b) An acrylic ester-based porous adhesive thin film is provided on the surface of a base material made of breathable fabric such as non-woven fabric. The obtained product is used as a surgical adhesive tape (see Japanese Patent Publication No. 39-4728).

c) As an improvement of b), a polyurethane elastic nonwoven fabric is used as the base material (Japanese Patent Publication No. 1-48019).
(see publication). In addition, a film with a high elastic modulus such as a stretchable nonwoven fabric or a polyvinyl chloride film is used.

[0007]

[Problems to be Solved by the Invention] However, the above method has the following problems.

In the case of (a), the obtained adhesive tape or sheet cannot avoid local dampness of the skin, and therefore cannot prevent the above-mentioned skin damage from occurring.

Since the pore diameter of the porous adhesive thin film formed by the method (b) is quite large, ranging from several μm to several tens of μm, not only water vapor but also liquids such as water permeate through the film. Therefore, when this adhesive tape is applied to the skin, dirt from the outside may penetrate through the adhesive tape to the wound, causing the wound to fester. In addition, there is a problem that the adhesive tape attached to the body easily peels off when taking a bath, and if the adhesive contains a drug, there is also the problem that the drug leaks out through the back side of the adhesive tape.

Furthermore, since porous fiber substrates such as non-woven fabrics do not easily stretch, the adhesive tape does not feel good on the skin at the application site during application, causing a sense of discomfort, and it is difficult for the adhesive tape to follow the movement of the skin. These factors are unavoidable causes of rashes.

In the case of c), since the polyurethane elastic nonwoven fabric, stretchable nonwoven fabric, polyvinyl chloride film, etc. as the base material have a large elastic modulus, the skin sensation at the application site during application of the adhesive sheet is poor and discomfort can be avoided. do not have. Furthermore, in most cases, a large number of large holes are provided in the base material of the gauze holding part in order to improve water vapor permeability. Therefore, the problem pointed out in b) above, that is, the penetration of dirt from the outside and the ease of peeling due to the penetration of not only water vapor but also liquids such as water, can be solved.
The issue remains unresolved. In addition, in the case of non-woven fabrics, the adhesive film is difficult to bond due to its flat surface due to overlapping fibers, and it tends to leave adhesive residue on the skin, and when adhesive tape is wrapped around the back of the fabric, it easily peels off even if it sticks. There were drawbacks. The present invention was made in view of the above-mentioned circumstances, and its purpose is to have water vapor permeability but no water permeability, and as a result, it is resistant to water and can be easily peeled off even when wet. To provide a medical adhesive tape or sheet which has various properties such as being hygienic with no stains, being soft and elastic, having good skin sensation, not causing rashes, not getting stuffy, and not being noticeable.

0012

[Means for Solving the Problems] The present invention has been devised to achieve the above object, and provides a desired medical adhesive tape or sheet by using a film made of a specific material as a gas permeable base material. It was completed based on the knowledge that it is possible.

That is, the medical adhesive tape or sheet according to the present invention is a medical adhesive tape or sheet in which an adhesive layer is formed on a gas permeable base material, and the gas permeable base material has rubber elasticity. It is characterized by the use of a microporous coating made of a polymer.

[0014] In order to solve the above-mentioned problems, the gas permeability of the adhesive tape or sheet is preferably 500 g/m2 or more per 24 hours at 40°C and 80% relative humidity, particularly preferably 1000-30
It is in the range of 00g/m2.

Polymers having rubber elasticity include polyurethane elastomers synthesized from polyols, diisocyanates, and chain extenders; polyvinyl chloride; styrene chain and diene polymers such as styrene-butadiene block copolymers; A block copolymer with: a polymer selected from the group consisting of acrylic rubber and silicone rubber may be used alone or in combination.

[0016] The thickness of the microporous coating is preferably 10~
2000 μm, particularly preferably in the range of 50 to 1000 μm.

On the other hand, the adhesive layer of the adhesive tape or sheet preferably consists of a coating layer with excellent gas permeability. Preferred adhesives constituting the adhesive layer include acrylic adhesives, rubber adhesives, silicone adhesives, and the like.

As the acrylic pressure-sensitive adhesive, in particular, a homopolymer or copolymer of an alkyl (meth)acrylic ester obtained from an aliphatic alcohol having 4 to 18 carbon atoms and (meth)acrylic acid and/or the above-mentioned Copolymers of (meth)acrylic acid alkyl esters and other functional monomers are preferably used.

The above (meth)acrylic esters include butyl acrylate, isobutyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, decyl acrylate, isodecyl acrylate, and lauryl acrylate. , stearyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, etc. Ru.

Examples of the above-mentioned functional monomers include monomers having a hydroxyl group, monomers having a carboxyl group,
Examples include monomers having an amide group and monomers having an amino group. As a monomer having a hydroxyl group,
Examples include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate. Examples of the monomer having a carboxyl group include α-β unsaturated carboxylic acids such as acrylic acid and methacrylic acid; maleic acid monoalkyl esters such as butyl maleate; maleic acid; fumaric acid; and crotonic acid. Maleic anhydride also provides the same (co)polymerization component as maleic acid. Examples of monomers having an amide group include acrylamide, alkyl (meth)acrylamides such as dimethylacrylamide and diethylacrylamide; alkyl ether methylol (meth)acrylamides such as butoxymethylacrylamide and ethoxymethylacrylamide; and diacetone acrylamide. Examples of monomers having an amino group include dimethylaminoethyl acrylate and vinylpyrrolidone.

As copolymerizable monomers other than those mentioned above, vinyl acetate, vinyl alcohol, styrene, α-methylstyrene, vinyl chloride, acrylonitrile, ethylene, propylene, butadiene, etc. can also be used. It is preferable that the adhesive contains 50% by weight or more of (meth)acrylic acid alkyl ester as a (co)polymerization component.

[0022] If necessary, a polyfunctional monomer is further added to the acrylic pressure-sensitive adhesive and copolymerized with other monomer components. The addition of this polyfunctional monomer causes very slight crosslinking between the resulting polymers, thereby increasing the internal cohesive strength of the adhesive. Therefore, the so-called adhesive residue phenomenon when the patch is removed can be almost eliminated, regardless of the properties of the skin to which it is applied or the amount of perspiration. Moreover, the addition of this polyfunctional monomer does not have any adverse effect on low skin irritation. Examples of such polyfunctional monomers include, but are not limited to, di(meth)acrylate, tri(meth)acrylate, and tetra(meth)acrylate. More specifically, di(meth)acrylate obtained by combining polymethylene glycols such as hexamethylene glycol and octamethylene glycol with (meth)acrylic acid; and polyalkylene glycols such as polyethylene glycol and polypropylene glycol. (meth)acrylic acid and di(
meth)acrylates; tri(meth)acrylates such as trimethylolpropane tri(meth)acrylate and glycerine tri(meth)acrylate; and tetra(meth)acrylates such as pentaerythritol tetra(meth)acrylate.
There are meta)acrylates. These polyfunctional monomers may be used in combination of two or more types. The polyfunctional monomer accounts for 0.005% of the total monomers used in the production of the adhesive.
It is used in a proportion of ~0.5% by weight. When the amount of the polyfunctional monomer used is less than 0.005% by weight, the effect of improving internal cohesive force due to crosslinking is small, and when it exceeds 0.5% by weight, the adhesive obtained by polymerization tends to gel. .

[0023] As the rubber adhesive, natural rubber, styrene-isoprene-styrene block copolymer, polyisoprene, polybutene, polyisobutylene, ethylene-
To 100 parts by weight of a rubber elastic body such as vinyl acetate copolymer,
20 to 200 parts by weight of tackifier, and an appropriate amount of softener,
Those with added stabilizers etc. are used.

[0024] As the silicone adhesive, one whose main component is polydimethylsiloxane or the like is used.

[0025] The above adhesive includes a tackifier such as a rosin resin, a polyterpene resin, a coumaron-indene resin, a petroleum resin, a terpene-phenolic resin;
Compounding agents such as plasticizers such as liquid polybutene, mineral oil, lanolin, liquid polyisoprene, and liquid polyacrylate; fillers; and anti-aging agents are added as necessary.

Medical adhesive tapes or sheets usually have a separator on their application surface to protect the surface of the adhesive layer until use. As a separator, a film made of polyethylene terephthalate treated with silicon is often used, but the separator is not limited to this. The thickness of the separator is 100 μm or less, preferably 5 to 50 μm.

Next, a method for manufacturing a medical adhesive tape or sheet according to the present invention will be explained.

The method for producing a medical adhesive tape or sheet according to the present invention involves dispersing a polymer having rubber elasticity in producing a medical adhesive tape or sheet by forming an adhesive layer on a gas-permeable base material. The liquid is applied to a carrier, and the polymer-coated carrier is immersed in an inert liquid that is non-solvent for the polymer and compatible with the dispersion medium to solidify the coated polymer into a film. At the same time, micropores are formed in the film, the treated product is dried, and the microporous film thus obtained is used as the gas permeable base material.

A method for producing a microporous coating made of a polymer having rubber elasticity is disclosed, for example, in Japanese Patent Publication No. 13514/1983.

A dispersion of a polymer having rubber elasticity is prepared by dissolving the polymer in a solvent to form a polymer solution, and adding an insoluble material that is a non-solvent to the polymer and is compatible with the solvent. This is done by adding an active liquid to the polymer solution. As the solvent for forming the polymer solution, a solvent that dissolves the polymer having rubber elasticity and is compatible with the above-mentioned inert liquid can be used. Particularly preferred solvents include dimethylformamide when the polymer having rubber elasticity is a polyurethane elastomer, tetrahydrofuran and the like for polyvinyl chloride, and styrene, etc.
Examples of diene block copolymers include methyl ethyl ketone. Inert liquids added to polymer solutions include:
Although any liquid that is a non-solvent for the polymer and compatible with the above-mentioned solvents may be used, water is most advantageously such liquid.

The carrier is preferably made of a high-density woven fabric of filament fibers such as nylon, polyethylene terephthalate, and vinylon.

[0032] A roll coater such as a knife-over roll coater is used to coat the carrier with a dispersion of a polymer having rubber elasticity, but other methods may also be used.

Water is usually used as the inert liquid for immersion, which is non-solvent for the polymer and compatible with the dispersion medium. By immersing the polymer coated carrier in this inert liquid, the coated polymer can be solidified into a film and micropores can be formed in the film.

[0034] The adhesive layer is coated on the entire surface or a portion of one side of the base material, for example, in a pattern such as a striped, meshed, or dotted pattern. A knife-over-roll coater is usually used to apply the adhesive to the substrate, but other methods may also be used.

In addition to forming micropores in the base sheet to impart air permeability as described above, if micropores are also formed in the adhesive layer itself applied to the base sheet,
Even if the entire surface is coated with adhesive, an adhesive tape or sheet with excellent air permeability can be obtained. Such a microporous breathable adhesive layer can be obtained, for example, as follows. That is, in this method, an organic solvent solution of an adhesive is separately applied to the surface of a releasable sheet to form an adhesive solution layer, and then, while the adhesive solution layer is in an undried state,
After spraying a predetermined amount of water in the form of fine droplets on the surface of the adhesive solution layer, this is dried to form a dry adhesive layer with micropores, and this is applied to a breathable base material. This is a method of laminating layers. According to this method, when water is sprinkled on the surface of the adhesive solution layer separately formed on the surface of the releasable sheet while it is still in an undried state, the adhering water droplets are applied to the adhesive layer. The adhesive sinks into the solution layer, thereby forming minute depressions on the surface of the adhesive solution layer. Then, when the same layer is dried in a drying device, both the water and the solvent evaporate, and the water droplets become smaller by the amount of evaporated water, so the adhesive solution flows and the recesses become slightly smaller. At this time, the adhesive solution layer also dries slightly and its thickness becomes thinner. As water evaporates through subsequent drying, the remaining water droplets become smaller than in the recesses, but the solvent also evaporates and the viscosity of the adhesive increases, making the adhesive no longer fluid. As it progresses, the adhesive layer contracts and the recess widens, and the water evaporates completely. After that, the solvent continues to evaporate, the adhesive layer continues to shrink, and the bottom of the recess is torn off, forming a vent hole.
The viscosity of the adhesive is increased to the desired viscosity. thus,
A dry adhesive layer with ventilation holes is formed. In the above method, if a predetermined amount of water is spread in two or more stages, the amount of water used in one spraying will be smaller.
The number of dispersed water droplets also decreases, making it difficult for water droplets to condense together in the air, and the particle size of each water droplet remains small. Therefore, the recesses formed by the water droplets adhering to the surface of the adhesive solution layer become smaller, and the number of recesses increases, resulting in a high density distribution. As a result, the air holes formed in the dried adhesive layer through subsequent drying are also formed at a high density, and the total area of the air holes in a predetermined range becomes sufficiently large. Furthermore, if the recesses are small due to water droplets adhering to the adhesive solution layer, air holes will be reliably formed by subsequent drying.

By using the obtained microporous film as a base material and transferring it from a carrier to an adhesive layer, a raw roll for a tape or sheet having a microporous film is manufactured. This raw roll is processed into medical adhesive tapes or sheets such as emergency bandages, drapes used in surgery, and dressing materials, depending on the site of use and purpose.

[0037]

[Function] Since the medical adhesive tape or sheet according to the present invention uses a microporous film made of a polymer having rubber elasticity as the gas permeable base material, it has water vapor permeability but no water permeability. A medical adhesive that has the following properties: is resistant to water, does not peel off easily even when wet, is hygienic with little dirt, is soft and stretchy and feels good on the skin, does not cause rashes, does not get stuffy, and is not noticeable. Tape or sheet is provided.

[0038]

EXAMPLES Next, examples of the present invention will be shown in order to explain the present invention more specifically.

Example i) Preparation of a dispersion of a polymer having rubber elasticity Polytetramethylene ether glycol having a molecular weight of about 1000 was used as the polyol, and tolylene was used as the diisocyanate.
Using 2,4-diisocyanate and methylenebis(4-phenylisocyanate), using hydrazine hydrate as a chain extender, using dimethylformamide as a solvent, and using water as an inert liquid, Japanese Patent Publication No. 40-1351
A dispersion of polyurethane elastomer was prepared according to the method of Example 4 of No. 4.

That is, 2 moles of polytetramethylene ether glycol having a molecular weight of about 1000 and 1 mole of tolylene-2,4-diisocyanate were charged into a reactor, and the charged materials were heated at a temperature of 90° C. for 3 hours. Next, 2 moles of methylene bis(4-phenylisocyanate) were added to this mixture, and the mixture was heated at 80° C. for 1 hour while stirring. Dimethylformamide was added to the resulting reaction mixture to dilute the reaction solution to a solid content concentration of 30% by weight.

A chain extender solution was prepared by dissolving 0.72 parts by weight of hydrazine hydrate (65% by weight hydrazine) in 21 parts by weight of dimethylformamide.

The above mixture was gradually added to this chain extender solution until the viscosity of the mixture reached about 150 poise to obtain a polyurethane solution.

An 80:20 mixture of dimethylformamide and water was gradually added to 200 parts by weight of this polyurethane solution under vigorous stirring to obtain a substantially colloidal polyurethane dispersion. This dispersion has a viscosity of 45 to 280 poise.

ii) Production of raw roll for tape or sheet having a microporous film A high-density woven fabric made of nylon is used as a carrier, and is a non-solvent for the polymer and compatible with the dispersion medium. A product made by using water as an inert liquid, using an acrylic adhesive as an adhesive, and siliconizing a polyethylene terephthalate film as a separator (thickness 30
A raw fabric roll for an adhesive tape or sheet having a microporous film was manufactured using the process shown in FIG.

In FIG. 1, carrier roll (1)
The carrier (2) was rewound from the carrier, and the above polyurethane dispersion was coated on its upper surface with a thickness of 220 μm using a roll coater (3). The carrier (2) carrying this polymer coating layer (4) was then immersed in water in a water tank (5). Through this treatment, the polymer coating layer (4) is coagulated into a film, and the resulting film (6)
Micropores were formed.

[0046] This microporous film (6) is coated with a carrier (
2) was passed through a dryer (7) to dry the film (6).

On the other hand, the separator (9) was rewound from the separator roll (8), and an acrylic pressure-sensitive adhesive was coated on its upper surface to a thickness of 35 μm using a knife-over roll coater (10). This adhesive layer (11) was passed through a dryer (12) together with a separator (9) to dry the adhesive layer (11).

The separator (9) having the adhesive layer (11) and the carrier (2) carrying the microporous film (6) are passed between a pair of left and right transfer rollers (13). , microporous film (6) and carrier (2)
The film was transferred to the adhesive layer (11). In this way, the microporous film (6) as a gas permeable base material and the adhesive layer (11)
A strip (16) having a sandwich structure consisting of a separator (9) and a separator (9) was wound up to obtain a raw roll (14) for a medical adhesive tape or sheet having a microporous film. Further, the carrier (2) from which the microporous film (6) had been separated was wound up and recovered as a carrier roll (15).

iii) Production of medical adhesive tape or sheet The raw roll (14) thus obtained was processed to obtain a medical adhesive tape or sheet in a desired form such as an emergency bandage, drape, dressing material, etc. The gas permeability of the adhesive tape or sheet is 1580 g/m 2 per 24 hours at 40° C. and 80% relative humidity, and the thickness of the microporous coating is 238 μm.

FIG. 2 shows a schematic diagram of an electron micrograph of a cross section of the microporous film formed. The upper side of the same figure (21
) is the side in contact with water in the aquarium, and the lower side (22) is the side supported by the carrier. Many micropores (
23) is recognized to exist.

Performance Test 1 The adhesive plaster obtained in Example, adhesive plaster constructed using a soft polyvinyl chloride film as a gas permeable base material (manufactured by Sekisui Chemical Co., Ltd., trade name "Sekisui Cuban", Comparative Example 1)
), a bandage constructed using a polyurethane film as a gas permeable base material (manufactured by Nisshinbo Co., Ltd., product name "Peachade", Comparative Example 2), diphenylmethane-4,4'-diisocyanate hexanadipate type as a gas permeable base material The performance of each item in Table 1 was evaluated for a bandage (manufactured by Kanebo Co., Ltd., trade name "Espansione UHD-75", Comparative Example 3) constructed using a nonwoven fabric of polyurethane fibers made of ester-1,4-butanediol. Examined. The test results are shown in Table 1.

[0052]

[Table 1]

As can be seen from Table 1, the test pieces of Examples using a microporous film made of polyurethane elastomer as a gas permeable base material were better in all items than the test pieces of Comparative Examples 1 to 3. It is recognized that it shows an excellent effect that is comparable to that of other methods.

Performance Test 2 Test pieces were taken from each of the raw rolls obtained in Example and Comparative Example 3, and a stress-strain curve was determined for each test piece. The results are shown in FIG.

As can be seen from FIG. 3, the test piece of Example using a microporous film made of polyurethane elastomer as a gas permeable base material had smaller hysteresis than the test piece of Comparative Example 3. It will be done.

[0056]

[Effects of the Invention] According to the present invention, since a microporous film made of a polymer having rubber elasticity is used as a gas permeable base material, it has suitable water vapor permeability and no water permeability. ,
As a result, it is resistant to water, does not peel off easily even when wet, is hygienic with less dirt, is soft and stretchy, feels good on the skin, does not cause rashes, does not get stuffy, and is not noticeable.
A medical adhesive tape or sheet having the following characteristics can be obtained.

[Brief explanation of drawings]

FIG. 1 is a process diagram showing an example of the present invention.

FIG. 2 is a schematic diagram of an electron micrograph of a cross section of a microporous film.

FIG. 3 is a graph showing a stress-strain curve.

[Explanation of symbols]

1...Carrier roll 2...Carrier 4...Polymer coating layer 5...Aquarium 6...Microporous film 7...Dryer 9...Separator 11...Adhesive layer 12...Dryer 14...Material roll 15...Carrier roll 16... Sandwich structure strip 22...Minor pores

Claims (3)

[Claims] Claim 1: A medical adhesive tape or sheet in which an adhesive layer is formed on a gas permeable base material, wherein a microporous coating made of a polymer having rubber elasticity is used as the gas permeable base material. A medical adhesive tape or sheet characterized by: 2. The medical adhesive tape or sheet according to claim 1, wherein the adhesive layer comprises a layer with excellent gas permeability. 3. When producing a medical adhesive tape or sheet by forming an adhesive layer on a gas-permeable base material, a dispersion of a polymer having rubber elasticity is coated on a carrier, and the polymer is The polymer coating carrier is immersed in an inert liquid that is non-solvent and compatible with the dispersion medium to solidify the polymer coating layer and form micropores in the coating. 1. A method for producing a medical adhesive tape or sheet, which comprises drying the product and using the thus obtained microporous film as the gas-permeable base material.