JPH08103490A - Water absorbent polymer for medical treatment and coating material for wound formed by using the same and external material for medical treatment and their production - Google Patents

Abstract

PURPOSE: To satisfy the main characteristics in pharmaceuticals necessary for wet healing by which healing is accelerated without forming crusts by maintaining a wound moist without immersion of this wound into water and preventing the contamination by microorganisms. CONSTITUTION: This water absorbent polymer used for medical treatment consists of an acrylic copolymer obtd. by polymerizing 60 to 80wt.% alkoxyalkyl acrylate, 20 to 40wt.% N-vinyl lactam and <=10wt.% vinyl carboxylic acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-absorbent polymer for medical use, a wound covering material using the same, a medical external use material and a method for producing them, and more specifically to a wound covering material, medical external use material and the like. The present invention relates to a flexible, stretchable, and transparent water-absorbent and swellable medical water-absorbent polymer, a wound dressing using the same, and a medical external-use material, and methods for producing these.

[0002]

2. Description of the Related Art A number of research results have been reported regarding the treatment of skin wounds such as burns, skin-cutting wounds, traumatic skin defect wounds and pressure ulcer wounds, but keeping the wound moist without soaking it in water. In addition, by preventing microbial contamination, healing is promoted without forming a crust, the so-called Wet
Healing (RG Geronemus, et al., J. Dermato
l. Surg. Oncol. , 8 (10), 850 (1982)), the expectation is increasing year by year.

Most of the dressing materials applied to Wet Healing so far do not fully satisfy the desired properties for wound treatment. For example, quasi-occlusive film dressings using a polyurethane film or the like do not have water absorption retention, so when the water vapor permeability is large, the wound part gradually dries to form crusts, etc. When small, the wound is soaked in body fluids and becomes overly moist.

Also, so-called hydrocolloid dressings, which are composed of rubber elastomer and hydrocolloid components, have poor transparency, so that the condition of treatment cannot be observed from the outside, and the flexibility is slightly inferior. Is difficult to attach.

Furthermore, since hydrogel dressings containing water such as hydrophilic polymers have poor skin adhesion, leakage of body fluid occurs if water absorption and retention are insufficient, and it is difficult to prevent invasion of microorganisms from the outside. Is. In addition, the part that is not involved in water absorption gradually dries and loses its flexibility, and tends to show physical irritation.

Many water-absorbent dry sheet type dressings which become hydrogels by absorbing body fluids such as collagen film are provided in the form of mesh or non-woven fabric in order to impart flexibility, and are expected to have skin adhesion and microbial barrier properties. Can not.

The present invention keeps the wound moist without immersing it in water and prevents microbial contamination, thereby promoting healing without forming crusts, the so-called Wet H.
It is an object of the present invention to provide a water-absorbent polymer for medical use which is excellent in the main properties required for ealing in the formulation, that is, water absorbency, skin adhesion, flexibility and transparency, and a method for producing the same.

[0008] Further, conventional adhesive tapes used for fixing, medical adhesive sheets used for first aid, magnetic adhesives, etc., elastic adhesive bandages, adhesives used for drug transdermal absorption tape preparations, etc. are used to prevent stuffiness. Although the drug product is designed to have sufficient air permeability and water vapor permeability, it often causes stuffiness and irritation at the site of high sweating.

An object of the present invention is to provide a wound dressing material which does not cause stuffiness due to sufficient water absorbency and water vapor permeability, a medical external use material and a method for producing them.

As described above, the present invention is more excellent than conventional wound dressing materials, medical water-absorbing polymers applicable to medical adhesives and the like, wound dressing materials using the same, and medical external use materials. The present invention provides a method for manufacturing the same.

[0011]

The water-absorbent polymer for medical use of the present invention is a water-absorbent polymer used for medical purposes in order to achieve the above object, and the water-absorbent polymer is an alkoxyalkyl acrylate 60-80. % By weight, N-
It is composed of an acrylic copolymer obtained by polymerizing 20 to 40% by weight of vinyl lactam and 10% by weight or less of vinylcarboxylic acid.

That is, the medical water-absorbing polymer of the present invention contains alkoxyalkyl acrylate and N-vinyl lactam as essential components.

Hereinafter, the present invention will be described in detail. Examples of the alkoxyalkyl acrylate that is a monomer include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, and 3
-Methoxypropyl acrylate, 3-methoxybutyl acrylate, 3-ethoxypropyl acrylate, 3
-Ethoxybutyl acrylate, but also alkoxyalkylene glycol acrylates such as butoxytriethylene glycol, 2- (2-ethoxyethyl) ethyl acrylate, methoxytriethylene acrylate and methoxydipropylene glycol acrylate can be used. Those having a low glass transition point and high hydrophilicity such as ethyl acrylate are more preferable.

Examples of the N-vinyllactam used in the present invention include N-vinyl-2-pyrrolidone and N-
Examples thereof include vinyl-2-piperidone and N-vinyl-2-caprolactam, and N-vinyl-2-pyrrolidone is more preferable from the viewpoint of safety and versatility.

Further, examples of the vinylcarboxylic acid used in the present invention include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic acid half ester and fumaric acid half ester. Acrylic acid is more preferable from the viewpoints of properties and versatility.

The medical water-absorbing polymer of the present invention comprises an alkoxyalkyl acrylate and N-vinyl lactam as essential components, and further, if necessary, a vinyl carboxylic acid is added thereto to copolymerize the resulting acrylic copolymer. It consists of things.

That is, the acrylic copolymer is obtained by copolymerizing 60 to 80% by weight of alkoxyalkyl acrylate, 20 to 40% by weight of N-vinyllactam and 10% by weight or less of vinylcarboxylic acid.

In this acrylic copolymer, the compounding ratio of the alkoxyalkyl acrylate is 60 to 80% by weight of the whole copolymer, and when the amount of this component is less than 60% by weight, the obtained film is It is not preferable because the flexibility becomes low. On the other hand, when it exceeds 80% by weight, the film has increased tackiness and low strength, which is not preferable.

In this acrylic copolymer, N
-Vinyl lactam content is 20% of the total weight of this copolymer.
If the amount of this component is less than 20% by weight, the strength and water absorption capacity of the obtained film will be low, which is not preferable. On the other hand, if it exceeds 40% by weight, the amount of the obtained film of The flexibility is low, and the acrylic copolymer is dissolved in water or body fluid to cause flow, which is not preferable.

Further, in this acrylic copolymer,
The blending ratio of vinylcarboxylic acid is 10 based on the total amount of this copolymer.
The content of vinyl carboxylic acid is not more than 0% by weight, that is, the proportion of vinylcarboxylic acid is 0 to 10% by weight, especially 0 to
It is desirable to set it in the range of 5% by weight, and if the blending ratio of this component exceeds 10% by weight, the water absorption capacity of the film is enhanced,
It is not desirable because it has poor flexibility and may reduce wound healing ability.

By the way, in the present invention, the reason why the vinylcarboxylic acid is blended is to further improve the water absorption capacity. However, if the blending ratio exceeds 10% by weight, the hemostatic property is lowered and the wound treatment is delayed. Therefore, for this reason, it is desirable that the blending ratio of vinylcarboxylic acid be 5% by weight or less. However, this does not apply when used as a medical adhesive that does not come into contact with the wound site.

The medical water-absorbent polymer of the present invention can be produced by copolymerizing a mixture of the above-mentioned monomers by a generally known polymerization method. The copolymerization method may be any of solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization.

In this copolymerization method, for example, solution polymerization is performed by heating and stirring the monomer mixture in the presence of a medium and a polymerization initiator. Examples of the solvent include water, methanol,
Examples thereof include ethanol, isopropanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, toluene, xylene, ethylene glycol monoalkyl ether and the like, and these can be used alone or in combination of two or more kinds. In this case, examples of the polymerization initiator include benzoyl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, azobisisobutyronitrile, and the like. These may be used alone or in combination of two or more. be able to.

In this copolymerization method, the emulsion polymerization is
It is carried out by heating and stirring a dispersion liquid comprising water, an emulsifier, a water-soluble polymerization initiator and the above-mentioned monomer mixture. The emulsifier is preferably an anionic or nonionic surfactant, such as sodium lauryl sulfate, sodium lauroyl sarcosine, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate, sorbitan sesquioleate, sucrose fatty acid ester, etc. These can be used alone or in admixture of two or more.

The above water-soluble polymerization initiator is, for example,
Ammonium persulfate, potassium persulfate, hydrogen peroxide, t
-Butyl hydroperoxide and the like.

In the present invention, photopolymerization can be carried out. This photopolymerization is carried out by irradiating the monomer mixture with UV light in the presence of a photoinitiator. The photoinitiator is, for example,
4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-
Hydroxy-2-methyl-1-phenylpropane-1-
On, 1- (4-isopropylphenol) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-
1-one, 4- (2-hydroxyethoxy) -phenyl-
(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-
Acetophenone photoinitiators such as [4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether,
Benzoin-based photoinitiators such as benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4 ′
-Methyldiphenyl sulfide, 3,3'-dimethyl-
Benzophenone photoinitiators such as 4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2
-Methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,
It is a thioxanthone photoinitiator such as 4-diisopropylthioxanthone.

In this case, a photoinitiator aid may be added if necessary. Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. Ethyl, 4-dimethylaminobenzoic acid (n-butoxy)
Ethyl, isoamyl 4-dimethylaminobenzoate, 4-
Examples thereof include 2-ethylexyl dimethylaminobenzoate, and these may be used alone or in combination of two or more kinds.

The photoinitiator varies depending on the extinction coefficient and the like, but the polymerization proceeds preferably in an amount of 0.005 parts by weight or more and 0.5 parts by weight or less, particularly 0.
More preferably, it is not less than 01 parts by weight and not more than 0.2 parts by weight. In addition, the photopolymerization is carried out by sufficiently substituting the mixture of the monomer and the photoinitiator with nitrogen, then irradiating with a certain dose of UV light, coating the resulting partially polymerized syrup or casting it in a frame, and then adding sufficient U
A method of obtaining a copolymer by irradiating V light is preferable. Total irradiation dose during partial polymerization is 20 mJ / cm ² or more 30
Preferably 0 mJ / cm ² or less, completely polymerized total irradiation dose at the time of preferably 1000 mJ / cm ² or more 10000 mJ / cm ² or less, more preferably, especially 2000 mJ / cm ² or more 5000 mJ / cm ² or less.

In order to achieve the above-mentioned object, the medical water-absorbing polymer of the present invention has the above-mentioned acrylic composition,
Furthermore, a polyfunctional acrylate or methacrylate is added to 0.01
It is also advantageous to use an acrylic copolymer obtained by copolymerizing a mixture of 1 to 1% by weight.

That is, the medical water-absorbent polymer of the present invention is a water-absorbent polymer used for medical purposes,
This water-absorbing polymer comprises 60 to 80% by weight of alkoxyalkyl acrylate, 20 to 40% by weight of N-vinyllactam, 10% by weight or less of vinylcarboxylic acid, and 0.01 to 1% by weight of polyfunctional acrylate or methacrylate. It is composed of an acrylic copolymer obtained by copolymerizing the above.

In this acrylic copolymer, the compounding ratio of the alkoxyalkyl acrylate is 60 to 80% by weight of the whole copolymer, and when the amount of this component is less than 60% by weight, the obtained film is This is not preferable because it lowers flexibility, and on the other hand, when it exceeds 80% by weight, hydrophilicity decreases, which is not preferable.

In this acrylic copolymer, N
-Vinyl lactam content is 20% of the total weight of this copolymer.
-40% by weight, and if the amount of this component is less than 20% by weight, hydrophilicity decreases, which is not preferable.
If it exceeds 40% by weight, the water solubility is increased and the acrylic copolymer is dissolved in water or body fluid to cause flow, which is not preferable.

Further, in this acrylic copolymer,
The blending ratio of vinylcarboxylic acid is 10 based on the total amount of this copolymer.
The content of vinyl carboxylic acid is not more than 0% by weight, that is, the proportion of vinylcarboxylic acid is 0 to 10% by weight, especially 0 to
It is desirable to set it in the range of 5% by weight, and if the blending ratio of this component exceeds 10% by weight, the water absorption capacity of the film is enhanced,
It is not desirable because it may reduce the wound healing ability.

By the way, in the present invention, the reason why vinyl carboxylic acid is blended is to further improve the water absorption capacity. However, when the blending ratio exceeds 10% by weight, the hemostatic property is lowered and the wound treatment is delayed. Therefore, for this reason, it is desirable that the blending ratio of vinylcarboxylic acid be 5% by weight or less. However, this does not apply when used as a medical adhesive that does not come into contact with the wound site.

Further, in this acrylic copolymer,
The compounding ratio of the polyfunctional acrylate is 0.01 to 1% by weight of the whole copolymer, and the amount of this component is 0.01
If it is less than 1% by weight, the crosslinking becomes insufficient, the strength is lowered, and it becomes water-soluble, which is not preferable. On the other hand, if it exceeds 1% by weight, the flexibility and the adhesiveness are lowered, and the hydrophilicity is remarkably lowered. It is not preferable because it becomes white after absorbing water.

The medical water-absorbing polymer of the present invention comprises the above-mentioned acrylic composition further mixed with a polyfunctional acrylate or methacrylate. Therefore, the alkoxyalkyl acrylate and N-vinyllactam used here are used. Examples of the vinyl carboxylic acid include those mentioned above.

Examples of the polyfunctional acrylate or methacrylate used in the present invention include 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol diacrylate and 1,6-hexanediol diacrylate. Acrylate, 1,6
-Alkyl type diacrylate or dimethacrylate such as hexanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol 200 diacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol 6
Alkylene glycol type diacrylate or dimethacrylate such as 00 diacrylate, polyethylene glycol 200 dimethacrylate, polyethylene glycol 400 dimethacrylate, polyethylene glycol 600 dimethacrylate, polyethylene glycol 1000 dimethacrylate, polypropylene glycol 400 diacrylate, polypropylene 400 dimethacrylate, hydroxy. Pivalic acid Neopentyl glycol diacrylate and other ester type diacrylates or dimethacrylates, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane tetraacrylate and other trimethylolpropane type triacrylates. And tetraacrylate or trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetramethacrylate, etc. pentaerythritol type tri and tetraacrylates or tri and tetramethacrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, etc. Isocyanurate type triacrylate or trimethacrylate,
Examples thereof include bisphenol A-type diacrylates such as ethoxylated bisphenol A diacrylate and ethoxylated bisphenol A dimethacrylate, and dimethacrylates. From the viewpoint of hydrophilicity and safety, alkylene glycol type diacrylates or dimethacrylates are preferable, and polyethylene glycols are preferable. 600 dimethacrylate is more preferred.

The medical water-absorbing polymer of the present invention can be produced by copolymerizing the mixture of the above-mentioned monomers by the above-mentioned polymerization method.

Specifically, it can be produced by copolymerizing the mixture of the above-mentioned monomer and plasticizer by bulk polymerization, solution polymerization, UV polymerization or the like. In this copolymerization method, for example UV polymerization, the monomer and plasticizer mixture is irradiated with a sufficient amount of UV light in the presence of a photoinitiator, or
In the presence of a photoinitiator, a monomer mixture excluding polyfunctional acrylate or methacrylate is irradiated with a certain amount of UV light to form a partially polymerized syrup, and then a polyfunctional acrylate or methacrylate plasticizer is mixed to obtain a sufficient amount of UV light. By irradiating.

That is, the photoinitiator varies depending on the extinction coefficient and the like, but the polymerization proceeds preferably at 0.005 parts by weight or more and 0.5 parts by weight or less, especially 0.01 parts by weight or more and 0 parts by weight, relative to 100 parts by weight of the monomer. More preferably, it is not more than 2 parts by weight. Further, photopolymerization is performed by sufficiently substituting a mixture of monomers and photoinitiators other than polyfunctional acrylates or methacrylates with nitrogen, and then irradiating a certain dose of UV light to the resulting partially polymerized syrup to obtain polyfunctional acrylates or methacrylates, and if desired , After coating a mixture of plasticizers described below or casting in a frame, irradiate with sufficient UV light, or after thoroughly replacing the mixture of the monomer, plasticizer and photoinitiator with nitrogen, A method of obtaining a copolymer containing a plasticizer by irradiating with UV light, coating or casting the resulting partially polymerized syrup, and then irradiating with sufficient UV light is preferable.

In this case, the total irradiation dose during partial polymerization is 20.
mJ / cm ² or more 300 mJ / cm ² or less, the total irradiation dose of full polymerization at the time of 1000 mJ / cm ² or more 10000mJ
/ Cm ² or less is preferable, especially 2000 mJ / cm ² or more and 50
More preferably, it is not more than 00 mJ / cm ² .

In the medical water-absorbing polymer of the present invention, it is also beneficial to use a mixture obtained by crosslinking a mixture of 60% by weight or more of the above acrylic copolymer and 40% by weight or less of a plasticizer described later.

That is, in the present invention, 60% by weight or more of the acrylic copolymer includes a case of only the acrylic copolymer, that is, 100% by weight of the acrylic copolymer. In some cases, it may be necessary to achieve insolubilization of the copolymer and shape retention.

When the plasticizer is blended with the acrylic copolymer, if the blending ratio of the plasticizer exceeds 40% by weight in the total amount of the acrylic copolymer and the plasticizer, the acrylic copolymer is It is preferable that properties are lost, insolubilization due to radiation such as electron beam or a chemical cross-linking agent described later becomes difficult, or insolubilization due to polyfunctional acrylate or methacrylate cross-linking becomes difficult. The blending ratio is particularly preferably 30% by weight or less.

As this method, for example, electron beam or γ
Insolubilization due to radiation irradiation cross-linking such as rays may be mentioned. In this case, the irradiation dose of radiation varies depending on the water solubility of the acrylic copolymer, but it is preferably 50 kGy or less, and when the irradiation dose is 25 kGy or more. Can also serve as sterilization prescribed by medical regulations, but 50kGy
When it exceeds, the modification such as coloring is remarkable and the use is limited.

Further, in the present invention, by adding a plasticizer to the above-mentioned acrylic copolymer, the flexibility and the tackiness can be further improved. As the plasticizer, it is desirable to use a compound that has good compatibility with the above-mentioned acrylic copolymer and is hydrophilic.

Specifically, for example, ethylene glycol,
Diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin, 2,3-butanediol, 1,2-butanediol, 3-methyl-1,3-butanediol, 3
-Low molecular weight polyhydric alcohols such as methyl 1,3,5-pentanetriol, 2-ethyl 1,3-hexadiol, polyethylene glycol having an average molecular weight of 1000 or less, polypropylene glycol, polyoxyethylene butyl ether, polyoxyethylene , Polyoxypropylene, polyoxypropylene glyceryl ether,
Examples thereof include polyoxypropylene sorbitol, polyoxyethylene polyoxypropylene pentaerythritol ether, and the like, and particularly the average molecular weight of 200 or more and 800
A polyoxypropylene glyceryl ether, which is
Polyoxypropylene glycol having an average molecular weight of 200 or more and 800 or less and polyoxypropylene sorbitol having an average molecular weight of 200 or more and 800 or less are desirable.

By the way, in the present invention, the reason for blending the plasticizer is to further improve the flexibility and tackiness of the acrylic copolymer. Therefore, for this reason, the blending ratio of the plasticizer is In particular, it is desirable that the amount is 30% by weight or less.

When the water solubility is increased by adding a plasticizer to the acrylic copolymer, electron beam or γ
Although insolubilization by irradiation with radiation such as rays is necessary, the crosslinking method and crosslinking conditions are the same as those described above.

In the medical water-absorbing polymer of the present invention,
In the acrylic copolymer obtained by the above method (including those subjected to crosslinking treatment) or the acrylic mixture containing the plasticizer obtained by the above method (including those subjected to crosslinking treatment), Particularly, those having a 50% modulus of 1 g / mm ² or more and 50 g / mm ² or less and a water absorption rate of 100% or more and 5000% or less, preferably 300% or more and 3000% or less are desirable for the following reasons.

In the medical water-absorbing polymer of the present invention,
Those with a 50% modulus of 1 g / mm ² or more and 50 g / mm ² or less are flexible and stretchable, and the film does not give a feeling of strangeness to the skin, has good adhesion to the skin, and has an elbow. ,
Even in a bent part such as a knee, it is possible to keep close contact by following a vigorous exercise.

By the way, when the 50% modulus of the water-absorbent polymer for medical use of the present invention exceeds 50 g / mm ² ,
The hardness increases and does not extend, and the film gives a feeling of strangeness to the skin, causes physical irritation, and deteriorates adhesion to flexion parts such as elbows and knees. If the% modulus is less than 1 g / mm ² , it is not preferable because the strength is insufficient and it cannot withstand practical use.

In the medical water-absorbing polymer of the present invention, it is particularly desirable that the 24-hour water absorption is 100% or more and 5000% or less.

That is, the water-absorbent polymer for medical use of the present invention is adhered to a wound or the like of the outer skin, absorbs the exudate from the wound or the like and swells to be in a gel state. I mean sweat, tears,
When in contact with body tissue fluids such as urine, serum and exudates from wound sites, they gradually absorb and form hydrous gel.
In this case, the absorbed water is strongly retained by the polymer, and the leaching of water by physical compression does not easily occur.

As the water absorption rate increases, the flexibility and the stress relaxation property increase. However, when the water absorption rate exceeds 5000%, the gel strength decreases and becomes brittle, or the water tends to dissolve.
Although it becomes substantially unusable, when the water absorption rate is 5000% or less, a gel state having substantially usable strength can be obtained, and particularly at 3000% or less, a gel state having effectively usable strength can be obtained. Obtainable.

On the other hand, when the water absorption rate is less than 100%, when the obtained film is applied to normal skin, sweating causes stuffiness and skin irritation such as rash easily occurs, and when the film is applied to wound skin, Exudate is excessively accumulated on the skin surface, or exudate outside the film leaks out, which adversely affects wound healing, but when the water absorption rate is 100% or more, the above-mentioned drawbacks are ameliorated. % Or more,
Significantly improved.

By the way, in the present invention, the term "water absorption" means that a water-absorbent polymer for medical use is formed into a film or a sheet, cut into 1.5 cm x 1.5 cm, and the weight before water absorption is measured. Each cut piece was treated with phosphate buffered saline (pH).
It was immersed in 135 ml (7.4, 32 ° C.) for 24 hours. After that, each cut piece was taken out, the surface water was wiped off, the weight after water absorption was measured, and the value was calculated from the increased weight.

The water-absorbent polymer for medical use of the present invention may be used in a state of containing water in a substantially usable range in advance. As the water, distilled water, distilled water for injection, sterile purified water, physiological saline, phosphate buffered saline, etc. can be used, and a drug may be further contained.

The drug that can be contained is not particularly limited, but examples thereof include antibacterial agents such as povidone iodine, iodine, sulfadiazine, silver sulfadiazine, benzalkonium chloride, cetalconium chloride, methylbenzethonium, neomycin sulfate and hexachloro. Phen, eosin, penicillin G, cephalosin, cephaloridine, tetracycline, lincomycin, nystacin, kanamycin, penicillinase-resistant penicillin, fradiomycin sulfate, silver lactate, etc., as salicylic acid esters, menthol, camphor, peppermint, capsicum extract , Drugs for haptics such as capsaicin,
Prezonisolone, dexamethasone, steroidal drugs such as hydrocortisone, indomethacin, ketoprofen, diclofenac, nonsteroidal drugs such as ibuprofen, angina remedies such as nitroglycerin, isosorbide dinitrate, benzocaine, procaine,
Local anesthetics such as xylocaine, antihistamines such as diphenhydramine, β-blockers such as alprenol, propranol and pindolol, blood pressure lowering agents such as clonidine and nifedipine, bronchial tubes such as methylephedrine, clonaprenaline, salbutamol and terbutamine. Dilators, asthma drugs such as cromoglycic acid, immunoregulators cyclosporine A, pstaglandins such as PGE ₁ , PGE ₂ , PGI ₂ and their derivatives, TGF, FG
Growth factor hormone agents such as F, PDGF, EGF, water-soluble collagen, hyaluronic acid, chondroitin sulfate, aloe extract, loofah extract, various vitamins, eicosapentaenoic acid and its derivatives, and various Chinese herbs such as toki and shikon These may be used alone or in combination of two or more.

The water-absorbent polymer for medical use of the present invention swells into a gel state when it absorbs water, and becomes wet gel of a skin wound.
A suitable wet environment can be provided. That is, water absorption, which is the main characteristic of the formulation necessary for this Wet Healing,
It is intended to provide a wound dressing excellent in skin adhesion, flexibility and transparency.

That is, as the dressing material for wound, a material formed into a film or a sheet using the above-mentioned water-absorbing polymer for medical use, or a material formed into a film or a sheet is further physically. Examples thereof include those chemically or chemically crosslinked, and those in which the above-mentioned medical water-absorbing polymer is formed into a film or sheet and dried.

As described above, the dressing for wounds of the present invention can take various forms depending on the application, but the film or sheet form is substantially versatile, and the water absorbent for medical use is substantially used. The polymer may be formed into a film or sheet, a mesh or a porous material.

In summary, in the present invention, when a film-shaped or sheet-shaped wound dressing is formed using the above-mentioned medical water-absorbing polymer, the wound dressing may be non-porous or porous, In other words, it may be a hole.

The film-like or sheet-like wound dressing has a thickness of 10 μm or more, particularly 75 μm or more and 5000 μm or less, preferably 100 μm or more and 2000
μm or less, more preferably 200 μm or more and 1000 μm
It is set below. If this thickness is less than 10 μm,
Undesirably often causes film breakage, 5000μ
If it exceeds m, it does not feel good to use, and it is meaningless to make it thick.

By the way, since the medical water-absorbing polymer of the present invention has excellent thermoplasticity, it can be processed into a sheet by extrusion molding. This extrusion molding can use any generally known method such as inflation molding, T-die molding, lamination molding, etc., but since it can be extruded at high temperature and rapidly cooled, a film or sheet having excellent optical properties can be obtained, and the cooling efficiency is high. Therefore, the T-die molding is preferable from the viewpoints that the production speed can be increased and the sheet thickness can be easily adjusted. The extruder may be either a single-screw extruder or a twin-screw extruder. The thickness of the film or sheet can be adjusted by appropriately controlling the molding conditions such as the molding temperature, the die lip width, the extrusion speed and the take-up speed.

In this case, the molding temperature is 140 ° C. or higher and 180
℃ or less, more preferably 150 ℃ or more 17
It is 0 ° C or lower. When the molding temperature is lower than 140 ° C., non-melted matter may often be mixed and the quality may vary. On the other hand, when the molding temperature exceeds 180 ° C., film breakage and air bubble entrapment may occur, which is not preferable.

As a film forming method for the film and sheet, any generally known method such as a calendering method, a casting method and an extrusion method can be used. However, when the polymerization method is photopolymerization, a monomer mixture containing a photoinitiator, or a partially polymerized syrup thereof, or a monomer mixture containing a photoinitiator and a plasticizer, or the partially polymerized syrup on a peelable film made of a polyester film or the like. Then, the coating and the film formation are simultaneously carried out by casting and coating the same at a constant thickness, covering it with a transparent peelable film, and then sufficiently irradiating it with UV light in an inert atmosphere. The film and sheet thus obtained can be cut into an arbitrary shape and used as a wound dressing.

In this case, a wound dressing in mesh or porous form is also useful. The mesh-like shape can be obtained by punching out the film or sheet with a mold, or by molding with a mesh-like mold by a casting method, and the porous form is obtained by swelling the film or sheet with water and then freeze-drying. Can be obtained by The mesh-like and porous ones have excellent air permeability and flexibility, and are advantageous in terms of raw material cost.

In the present invention, the above-mentioned film-like or sheet-like, or mesh-like or porous form is covered with a backing material on one side to obtain strength, fixability, shape retention, adhesion, etc. Wound dressings having improved efficiencies are also beneficial.

In this case, the size of the backing material may be the same as or larger than the water-absorbent polymer for medical use of each form, and the material may be any generally known material. Can be used. Specific examples of the material include paper, non-woven fabric, cotton cloth, synthetic resin cloth, synthetic resin film, synthetic resin foam, mesh-shaped or net-shaped paper, non-woven fabric, cotton cloth, synthetic resin cloth, synthetic resin film. Alternatively, there may be mentioned surgical tapes, medical adhesive sheets, adhesive bandages, etc. using these as the base materials, and among these materials, those having excellent breathability and moisture permeability are more desirable.

In the present invention, the film-shaped or sheet-shaped material can be crosslinked by irradiating it with radiation such as γ-rays or electron beams. The irradiation dose is preferably 5 kGy or more and 50 kGy or less, 25 kGy
When it is Gy or more, it can also serve as sterilization specified by medical-related laws, but when it exceeds 50 kGy, discoloration such as coloring is remarkable, and use is restricted.

Further, in the present invention, an acrylic copolymer can be obtained by radical polymerization of a mixture of the above-mentioned monomer, solvent and polymerization initiator by an ordinary operation. The solution is cast to form a film. This film has a thickness of 1
The thickness is adjusted to 0 to 75 μm, preferably 20 to 50 μm, and when the thickness exceeds 75 μm,
It is not preferable because impurities and residual monomers cannot be removed sufficiently, or the foaming occurs remarkably at the time of drying which will be described later. On the other hand, when it is less than 10 μm, the amount of water absorption is small and the desired strength may not be obtained, which is not desirable. . The obtained film can be dried under certain conditions to obtain a film-like wound dressing from which solvents (solvent and / or prepolymer, hereinafter simply referred to as impurities) and residual monomers have been removed. it can.

In this case, the drying conditions differ depending on the thickness of the film and further drying conditions such as reduced pressure drying and atmospheric drying. In atmospheric drying, the film thickness is 10 to 75 μm and 110 to 110 μm. 30 seconds to 20 at 150 ° C
Min, particularly 1 to 15 minutes at 120 to 140 ° C. is desirable.

Specifically, for example, under a sufficient air flow,
When the thickness of the film is 25 μm or less, it is preferable that the temperature is 130 ° C. for 2 minutes or more, particularly 130 ° C. for 3 minutes, and when the film thickness is 25 to 50 μm, 130 ° C. is 5 minutes or more, particularly 130 ° C. Is preferably about 7 minutes, and in the case of 50 to 75 μm or less, at 130 ° C. for 10 minutes or more,
Particularly, it is desirable to set the temperature at 130 ° C. for about 12 minutes.

As described above, the drying time can be changed depending on the level of the drying temperature. However, when the drying temperature is higher than 150 ° C., the film surface is crusted and impurities and residual monomers can be sufficiently removed. It is not preferable because there is a risk that it will disappear or that it will significantly foam. Further, if the drying temperature is lower than 110 ° C., it takes a long time to remove impurities and residual monomers, and there is a fear that the impurities cannot be sufficiently removed, which is not preferable.

Thus, the impurities and residual monomers are removed by drying the film (wound dressing) formed of the water-absorbent polymer for medical use, resulting in stable quality and in addition to the impurities and residual monomers. Based on this, it is possible to eliminate adverse effects on the living body, thus improving safety.

When the wound dressing contains a drug during this drying, it is necessary to give sufficient consideration to decomposition of the drug by heating.

In the wound dressing of the present invention, in each of the wound dressings described above, a perforated pressure-sensitive adhesive layer is provided on the surface of the wound sticking surface, for the reason described below. , Extremely beneficial.

That is, by providing a perforated pressure-sensitive adhesive layer on the surface of the wound dressing surface on the side where the wound is adhered, the adhesiveness to the application site surface is improved and the sealing property is improved. The bodily fluid is efficiently absorbed from the pores, and in this case, the wound dressing provided with the perforated pressure-sensitive adhesive layer is chemically or physically crosslinked, if desired.

This perforated pressure-sensitive adhesive layer can be obtained by perforating a coating film of any pressure-sensitive adhesive for medical use (hereinafter referred to as a medical pressure-sensitive adhesive) at a constant porosity.
Examples of the medical pressure-sensitive adhesive include acrylic pressure-sensitive adhesives such as acrylic acid ester copolymers and acrylic oil-based gel pressure-sensitive adhesives obtained by adding a compatible liquid component to the acrylic pressure-sensitive adhesive, natural rubber, and polyisoprene rubber. , Styrene-butadiene rubber, polyisobutylene rubber, styrene-butadiene-styrene copolymer, and tackifiers and reinforcing agents for rosin, rosin derivative, terpene resin, aliphatic hydrocarbon resin, aromatic petroleum resin, etc. Although there is a rubber-based pressure-sensitive adhesive obtained by adding a filler or the like, acrylic pressure-sensitive adhesives and acrylic oil-based gel pressure-sensitive adhesives that cause less skin irritation are preferable, and those having high moisture permeability are preferably used.

The thickness of the perforated pressure-sensitive adhesive layer is preferably 5 μm or more and 100 μm or less, more preferably 10 μm or more and 50 μm or less. If the layer thickness is less than 5 μm, the adhesiveness may be insufficient, which is not preferable.
On the other hand, if it exceeds 100 μm, the adhesiveness becomes excessive, and in addition, there is a possibility that the pores may be closed due to the pressure deformation of the adhesive, which is not preferable.

The holes may be formed by any method, but perforated rolls are preferably used. The shape of the pores may be any shape such as circular or square, but the occupancy rate per unit area of the pressure-sensitive adhesive layer is preferably 5% or more and 75% or less, and more preferably 10% or more and 30% or less.
When the porosity is less than 5%, sufficient water permeability cannot be obtained, which is not preferable, while when it is more than 75%, sufficient sealing property and adhesiveness cannot be obtained, which is not preferable.

In the present invention, the perforated pressure-sensitive adhesive layer may contain a drug, if necessary. Examples of this drug include the above-mentioned drugs.

The dressing for wounds of the present invention is a film or sheet obtained by laminating a perforated pressure-sensitive adhesive layer on one surface of a medical water-absorbent polymer film or sheet, or by extruding a medical water-absorbent polymer. You can attach it to.

In the wound dressing of the present invention, as described above, the perforated pressure-sensitive adhesive layer is attached to one side of a medical water-absorbent polymer film or sheet and then irradiated or irradiated with medical water. Of a film or sheet of a water-soluble polymer, or a radiation product of a film or sheet obtained by extruding this water-absorbing polymer for medical use, by laminating a perforated pressure-sensitive adhesive layer to the wound product of the present invention. A dressing can be obtained.

In this wound dressing, the exudate from the wound passes through the pores of the perforated pressure-sensitive adhesive layer to reach the water-absorbent polymer layer and is gradually absorbed to form a hydrogel.
Since a part of the retained water gradually evaporates, the storage of the exudate is suppressed, and the moist environment suitable for wound healing is maintained. In addition, the perforated pressure-sensitive adhesive layer in contact with the normal skin around the wound edge exhibits excellent adhesiveness, and a sufficient sealing property is obtained to prevent bacterial infection.

On the other hand, in this wound dressing material, perspiration at the application site passes through the pores of the perforated pressure-sensitive adhesive layer to reach the water-absorbent polymer layer and is rapidly absorbed, so that stuffiness and accompanying inflammation and adhesion It is possible to prevent a decrease in power.

In the present invention, a backing material is provided on the opposite side of the wound dressing having the perforated pressure-sensitive adhesive layer from the side with the perforated pressure-sensitive adhesive layer, whereby strength, fixability, shape retention, adhesion, etc. Is improved, which is beneficial.

The wound dressing of the present invention can be used for healing skin wounds such as burn wounds, skin-wounds, cuts, sittings, pressure ulcers, sutures and skin ulcers.

Further, in the present invention, a medical external preparation using the above-mentioned medical water-absorbing polymer is also useful.

That is, since this medical external use material has adhesiveness to the wound of the skin and the like, appropriate adhesiveness should be exhibited by increasing or decreasing the monomer composition of the acrylic copolymer or the amount of plasticizer. Therefore, it is excellent in moisture absorption and moisture permeability, which can prevent stuffiness that often occurs in a sweaty part and the like and inflammation associated therewith.

As the medical external use material, a material formed into a film or a sheet using the above-mentioned medical water-absorbing polymer, or a material formed into a film or a sheet can be used in a physical or physical manner. Those chemically or cross-linked, further, those in which the above-mentioned medical water-absorbing polymer is formed into a film or sheet, and dried, or on the side of the wound sticking surface of these external medical products. Examples thereof include those provided with a perforated pressure-sensitive adhesive layer on the surface, those provided with a backing material on the side opposite to the perforated pressure-sensitive adhesive layer side in these medical external use materials, and the like.

In this case, a film or sheet formed by using a water-absorbent polymer for medical use, a method for crosslinking the same or a method for drying the same, one provided with a perforated pressure-sensitive adhesive layer, or one having a perforated pressure-sensitive adhesive layer or its production The method, forming method, backing material, and the like are the same as those in the above-mentioned case, and thus the description thereof is omitted.

Among these external medical products, it is particularly preferable to provide a backing material with a film or sheet formed of a medical water-absorbing polymer. In this case, the thickness of the hinoki film or sheet is preferable. Is preferably 10 μm or more and 1 mm or less, and more preferably 30 μm or more and 500 μm or less, because the strength, fixability, shape retention, adhesion, etc. are improved and the usability is good.

The method for producing a water-absorbent polymer for medical use according to the present invention is a method for producing a water-absorbent polymer used for medical purposes in order to achieve the above object. 80
By weight, N-vinyllactam 20 to 40% by weight and vinylcarboxylic acid 10% by weight or less are copolymerized, and the resulting composition is cast and then dried to remove monomers and volatile impurities. It is characterized by doing.

The alkoxyalkyl acrylate, N-vinyl lactam and vinyl carboxylic acid used in the method for producing a water-absorbing polymer for medical use of the present invention, and the concentrations thereof are the same as those in the above-mentioned case, and will be omitted.

The present invention is characterized in that these acrylic compositions are copolymerized, cast, and dried to remove monomers and volatile impurities.

This monomer remains,
Further, the impurities include a solvent and a prepolymer, and by removing them, a medical water-absorbing polymer having more stable quality can be obtained.

In the production method of the present invention, as described above, a specific acrylic composition is copolymerized, and then the monomer or impurities are removed to obtain a medical water-absorbing polymer of higher quality according to the present invention. Is obtained. The water-absorbent polymer for medical use obtained by the present invention is characterized by excellent water absorbency, flexibility and transparency, and less residual monomers and impurities as compared with the UV polymerization method.

The water-absorbing polymer for medical use obtained by the production method of the present invention can be used to obtain the wound dressing material and external medical material of the present invention by the above-mentioned method.

In this case, in particular, the method for producing a wound dressing in which the obtained water-absorbent polymer for medical use is extruded to form a sheet, and then the sheet is subjected to a crosslinking treatment to obtain a wound dressing of excellent quality. It is useful because it can be done.

Further, the method for producing a medical external use material in which the obtained water-absorbent polymer for medical use is extruded to form a sheet and then subjected to a crosslinking treatment is advantageous because a medical external use material of excellent quality can be obtained. Is.

The medical external use material of the present invention may optionally contain
By incorporating a drug into the glue (water-absorbing polymer) layer, a transdermal drug patch may be used.

Particularly, in the present invention, a wound covering material having resistance to bacteria permeation is desirable, and a medical external preparation having excellent moisture permeability is preferably used. By the way, the backing material may be introduced before or after irradiation with radiation, but is preferably before irradiation with radiation from the viewpoint of maintaining a sterile condition.

The dressing material for wound and the external medical material according to the present invention can be kept in a sterile state by, for example, enclosing it in a bacterium-blocking packaging material in a sterilized state. As the sterilization method, it is preferable to use the EOG method, electron beam method, or γ ray method.

That is, after enclosing each of the above-mentioned wound dressing materials and each medical external use material in a bacterium-blocking wrapping material, a sterilized state can be maintained, and then an electron beam or γ-ray is irradiated. By subjecting to cross-linking and sterilization treatment, the medical water-absorbent polymer of the present invention, and the wound skin material and medical external-use material using the same can be put to distribution.

In this case, the irradiation dose of radiation such as electron beams or γ-rays varies depending on the hydrophilicity of the water-absorbing polymer for medical use, but is preferably 50 kGy or less, and when the irradiation dose is 25 kGy or more, medical-related laws and regulations. However, if it exceeds 50 kGy, the denaturation such as coloring is remarkable and the use is limited. In medical water-absorbent polymers, especially 50% modulus is 1g / mm
² or more and 50 g / mm ² or less, water absorption is 100% or more and 500
It is desirably 0% or less, preferably 300% or more and 3000 or less.

The wound dressing according to the present invention is excellent in water absorption, sealability, skin adhesion, flexibility and transparency, and can provide a moist environment suitable for wet healing of skin wounds. It can be used for healing skin wounds such as skin-collecting wounds, cuts, contusions, pressure ulcers, suture wounds, and skin ulcers.

Further, the external medicine for medical use according to the present invention is excellent in skin adhesiveness, moisture absorbability and moisture permeability capable of preventing stuffiness often occurring in a perspiring site and the like and inflammation associated therewith,
It can be used for a surgical tape for fixation, a medical adhesive sheet such as a first aid band, a magnetic bandage, an elastic adhesive bandage, a drug transdermal absorption tape preparation and the like.

[0110]

The water-absorbent polymer for medical use of the present invention has the above-mentioned constitution, and is capable of moderately cross-linking the hydrophilic acrylic copolymer and its plasticizer additive or making them insoluble in water by not cross-linking. Can have excellent water absorption from
Since it is an acrylic copolymer having a low glass transition point or a plasticizer additive thereof, it also has an effect of excellent flexibility and skin adhesion.

Further, the medical water-absorbing polymer of the present invention is
Since it is an acrylic copolymer, it is also excellent in transparency. That is, the medical water-absorbing polymer of the present invention, conventionally,
It makes it possible to simultaneously satisfy water absorption, skin adhesion, flexibility, and transparency, which were not satisfied at the same time by the wound dressing and medical external use material used for wet healing. It has a healing effect.

Further, in the medical water-absorbing polymer of the present invention, when the hydrophilic acrylic mixture containing the plasticizer is cross-linked moderately with the polyfunctional acrylate or methacrylate, the water-swelling property is improved by this cross-linking. In addition to being ensured, it can be insolubilized to have excellent water absorption, and since it is an acrylic mixture having a low glass transition point, it has excellent effects on flexibility and skin adhesion.

Further, in this case, since it is an acrylic type, it is also excellent in transparency. That is, the medical water-absorbing polymer of the present invention has water-absorbing property, skin-adhesion property, flexibility, and transparency which cannot be satisfied at the same time by the conventionally used wound dressing and external medical product. At the same time, it is possible to be satisfied, and it has an action that can be expected to have an excellent healing ability.

[0114]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. Example 1 0.05 part by weight of 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2-methoxyethyl acrylate were placed in a closed reactor equipped with a stirrer.
After charging 6 parts by weight and 24 parts by weight of N-vinyl-2-pyrrolidone, the atmosphere was replaced with nitrogen at a flow rate of 10 ml / min for 2 hours.
By irradiating UV light with a total dose of about 50 mj / cm ² ,
The syrup was obtained by partially photopolymerizing.

20 parts by weight of polyoxypropylene glyceryl ether having an average molecular weight of 400 was added to this syrup, and the mixture was stirred under a nitrogen stream for 1 hour. This was applied to a silicone-treated releasable PET film having a thickness of 1.
After casting in a 2 mm silicon mold and covering it with a similar peelable PET film, under an inert atmosphere,
Irradiate UV light uniformly on the front and back so that the total dose becomes 3000 mj / cm ² while cooling with air as appropriate, and then at 130 ° C for 30 more
After drying for a minute, it was irradiated with γ-ray having a dose of 25 kGy to obtain a wound dressing of the present invention as a transparent sheet having a thickness of 1 mm. This product had a 50% modulus of 4.9 g / mm ² and a water absorption of 1240%.

Example 2 In a closed reactor equipped with a stirrer, 0.2 parts by weight of azobisisobutyronitrile, 80 parts by weight of 2-methoxyethyl acrylate, 20 parts by weight of N-vinyl-2-pyrrolidone and 150 parts by weight of toluene. Was charged, the atmosphere was replaced with nitrogen at a flow rate of 10 ml / min for 2 hours, and then the mixture was stirred for 9 hours while maintaining the inside of the reactor at 60 ° C to 62 ° C.

Subsequently, 83.3 parts by weight of toluene was added thereto, and the mixture was stirred at 70 ° C. for 2 hours to complete the reaction, and then cooled to room temperature to obtain the medical water-absorbing polymer of the present invention ( A solution of acrylic copolymer) was obtained.

After applying the solution of the water-absorbing polymer for medical use (acrylic copolymer) to a releasable paper with a certain thickness,
The solvent and unreacted monomers were removed by drying at 130 ° C. for 5 minutes to obtain a transparent film having a thickness of 90 μm.

Further, this film has a dose of 25 kGy of γ
It was irradiated with rays to obtain the wound dressing of the present invention. The wound dressing had a 50% modulus of 12.5 g / mm ² and a water absorption of 490%.

Example 3 A wound dressing of the present invention was obtained in the same manner as in Example 2 except that the monomer composition was 70 parts by weight of 2-methoxyethyl acrylate and 30 parts by weight of N-vinyl-2-pyrrolidone. It was This product has a 50% modulus of 20.0 g / m
The m ² and water absorption were 1100%.

Example 4 The procedure of Example 2 was repeated except that the monomer composition was 65 parts by weight of 2-methoxyethyl acrylate, 30 parts by weight of N-vinyl-2-pyrrolidone and 5 parts by weight of acrylic acid. A dressing for wound was obtained. This product had a 50% modulus of 23.3 g / mm ² and a water absorption of 1720%.

Example 5 In a closed reactor equipped with a stirrer, 0.05 part by weight of 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2-methoxyethyl acrylate 8 were added.
After charging 0 parts by weight and 20 parts by weight of N-vinyl-2-pyrrolidone, the atmosphere was replaced with nitrogen at a flow rate of 10 ml / min for 2 hours,
By irradiating UV light with a total dose of about 50 mj / cm ² ,
The syrup was obtained by partially photopolymerizing.

Peelability P obtained by siliconizing this syrup
After casting in a 1.2 mm-thick silicon mold applied on the ET film and covering it with the same peelable PET film, the total dose was 3000 mj / After irradiating UV light uniformly on the front and back so as to have a cm ² , the wound dressing of the present invention was obtained as a transparent sheet having a thickness of 1 mm by further drying at 130 ° C for 30 minutes. This product has a 50% modulus of 17.7 g / m
The m ² and water absorption were 370%.

Example 6 A wound dressing of the present invention was obtained in the same manner as in Example 5 except that the monomer composition was 70 parts by weight of 2-methoxyethyl acrylate and 30 parts by weight of N-vinyl-2-pyrrolidone. It was This product has a 50% modulus of 24.7 g / m
It was m ² , and the water absorption was 1900%.

Example 7 The procedure of Example 5 was repeated except that the monomer composition was 65 parts by weight of 2-methoxyethyl acrylate, 30 parts by weight of N-vinyl-2-pyrrolidone and 5 parts by weight of acrylic acid. A dressing for wound was obtained. This product had a 50% modulus of 39.2 g / mm ² and a water absorption rate of 4,850%.

Example 8 In a closed reactor equipped with a stirrer, 0.05 part by weight of 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-methoxyethyl acrylate 4 were added.
9 parts by weight and 21 parts by weight of N-vinyl-2-pyrrolidone were charged, and the atmosphere was replaced with nitrogen at a flow rate of 10 ml / min for 2 hours.
By irradiating UV light with a total dose of about 50 mj / cm ² ,
The syrup was obtained by partially photopolymerizing.

To this syrup was added 30 parts by weight of polyoxypropylene glycol having an average molecular weight of 400,
The mixture was stirred under a nitrogen stream for 1 hour. This product was cast into a 1.2 mm-thick silicon mold frame on a silicon-treated releasable PET film, and the same releasable PE was applied from above.
After covering with T film, UV light was uniformly irradiated on the front and back sides so that the total dose would be 3000 mj / cm ² in an inert atmosphere with appropriate air cooling, and after further drying at 130 ° C for 30 minutes, the dose Was irradiated with γ-rays of 50 kGy to obtain a wound dressing of the present invention as a transparent sheet having a thickness of 1 mm. This product has a 50% modulus of 2.1 g / mm ² and a water absorption of 10
80%.

Example 9 The external dressing for medical treatment of the present invention was obtained by encapsulating the wound dressing of the present invention obtained in Example 5 in a gas-permeable bacterium-resistant packaging material and sterilizing with ethylene oxide gas. Obtained.

Example 10 In Example 7, the sample before γ-ray irradiation was sealed in a packaging material, and then γ-rays with a dose of 25 kGy were irradiated to obtain a medical external-use material of the present invention.

Example 11 The copolymer solution obtained in Example 1 was coated on a releasable PET film having a thickness of 50 μm at a constant thickness, and the temperature was adjusted to 130 ° C.
After drying for 5 minutes, it was transferred onto a polyurethane film having a thickness of 75 μm to obtain a medical external-use material of the present invention having a glue thickness of 30 μm.

Example 12 The thickness of the syrup containing the plasticizer obtained in Example 8 was 50%.
Apply on a peelable PET film of μm with a certain thickness,
After covering with a similar film from above, while irradiating with UV light with a total dose of 3000 mj / cm ² while cooling in an inert atmosphere, one film was removed and dried at 130 ° C for 5 minutes. Then, it was transferred onto a polyurethane film having a thickness of 75 μm and further irradiated with γ-ray having a dose of 50 kGy to obtain a medical external-use material of the present invention having a glue thickness of 30 μm.

Example 13 In a closed reactor equipped with a stirrer, 0.05 part by weight of 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 5 parts of 2-methoxyethyl acrylate were added.
After charging 6 parts by weight and 24 parts by weight of N-vinyl-2-pyrrolidone, the atmosphere was replaced with nitrogen at a flow rate of 10 ml / min for 2 hours.
By irradiating UV light with a total dose of about 50 mj / cm ² ,
The syrup was obtained by partially photopolymerizing.

To 70 parts by weight of this syrup, 0.18 part by weight of polyethylene glycol 600 dimethacrylate and 20 parts by weight of polyoxypropylene glyceryl ether having an average molecular weight of 400 were added, and the mixture was stirred under a nitrogen stream for 1 hour. Peelable PET treated with silicon
After casting in a 1.2 mm thick silicon mold applied on the film and covering it with a similar peelable PET film, the total dose was 3000 mj / After uniformly irradiating the front and back sides with UV light so that the surface area becomes cm ² , further drying at 130 ° C. for 30 minutes
The wound dressing of the present invention was obtained as a transparent sheet having a thickness of 1 mm. This one has a 50% modulus of 2.0 g / mm ² ,
The water absorption was 740%.

Example 14 0.05 parts by weight of 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2-methoxyethyl acrylate 4 were placed in a closed reactor equipped with a stirrer.
9 parts by weight and 21 parts by weight of N-vinyl-2-pyrrolidone were charged, and the atmosphere was replaced with nitrogen at a flow rate of 10 ml / min for 2 hours.
By irradiating UV light with a total dose of about 50 mj / cm ² ,
The syrup was obtained by partially photopolymerizing.

To 70 parts by weight of this syrup, 0.18 parts by weight of polyethylene glycol 600 dimethacrylate and 30 parts by weight of polyoxypropylene glycol having an average molecular weight of 400 were added, and the mixture was stirred under a nitrogen stream for 1 hour. This product was cast into a 1.2 mm thick silicon mold frame on a silicone-treated releasable PET film,
After covering with a similar peelable PET film from above,
Total dose of 3000 while cooling appropriately in an inert atmosphere.
After irradiating UV light evenly on the front and back to mj / cm ² ,
By further drying at 130 ° C for 30 minutes, the thickness becomes 1
The wound dressing of the present invention was obtained as a transparent sheet of mm.
This product had a 50% modulus of 2.1 g / mm ² and a water absorption of 740%.

Example 15 65 parts by weight of 2-methoxyethyl acrylate as a monomer composition except polyfunctional acrylate or methacrylate, N
-Vinyl-2-pyrrolidone 30 parts by weight and acrylic acid 5
A wound dressing of the present invention was obtained in the same manner as in Example 13 except that the amount was parts by weight. This product had a 50% modulus of 3.5 g / mm ² and a water absorption of 1700%.

Example 16 The external dressing for medical treatment of the present invention was obtained by encapsulating the wound dressing of the present invention obtained in Example 13 in a gas-permeable bacterium-resistant packaging material and sterilizing with ethylene oxide gas. Obtained.

Example 17 After enclosing the wound dressing of Example 13 in a packaging material, the external dressing for medical use of the present invention was obtained by irradiating with γ rays having a dose of 25 kGy. This one has a 50% modulus of 2.5
It was g / mm ² and the water absorption rate was 630%.

Example 18 The syrup containing the polyfunctional acrylate or methacrylate obtained in Example 13 and a plasticizer was coated on a peelable PET film having a thickness of 50 μm to a certain thickness and covered with a similar film. After irradiation with UV light with a total dose of 3000 mj / cm ² while cooling in an inert atmosphere, one of the films was removed and dried at 130 ° C. for 5 minutes, then on a polyurethane film with a thickness of 75 μm. By transferring to, a medical external-use material of the present invention having a glue thickness of 30 μm was obtained.

Comparative Example 1 A polymer was obtained in the same manner as in Example 1 except that the monomer composition was 90 parts by weight of 2-methoxyethyl acrylate and 10 parts by weight of N-vinyl-2-pyrrolidone. This is obtained as a highly viscous liquid at room temperature, and
The 0% modulus could not be measured due to poor shape retention, and the water absorption rate was 15%.

Comparative Example 2 A polymer was obtained in the same manner as in Example 1 except that the monomer composition was 50 parts by weight of 2-methoxyethyl acrylate and 50 parts by weight of N-vinyl-2-pyrrolidone. This product had a 50% modulus of 70.5 g / mm ² and dissolved in the water absorption test without swelling.

Comparative Example 3 The photoinitiator, the monomer and the plastic composition were each 1- (4-
Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 0.025 parts by weight, 2-methoxyethyl acrylate 35 parts by weight, N-vinyl-2-pyrrolidone 15 parts by weight, and an average molecular weight of 400 A polymer composition was obtained in the same manner as in Example 8 except that the amount of certain polyoxypropylene glycol was 50 parts by weight.
This was a liquid viscous material having a small cohesive force, the 50% modulus could not be measured, and it dissolved without swelling in the water absorption test.

Comparative Example 4 A 30 μm thick polyether polyamide block polymer film was used as a supporting layer, and an acrylic resin containing isononyl acrylate / 2-methoxyethyl acrylate / acrylic acid (weight ratio 65/30/5) was placed on the polyether polyamide block polymer film. A film dressing in which a system adhesive layer (thickness 50 μm) was laminated was used.

Comparative Example 5 A hydrocolloid dressing was prepared by using a polyurethane film having a thickness of 30 μm as a support layer, and laminating an adhesive sheet (thickness: 1 mm) made of a kneaded product of 47 parts by weight of polyisobutylene and 53 parts by weight of hydrocolloid on the polyurethane film. Using.

As the hydrocolloid, 17.5 parts by weight of carboxymethyl cellulose-Na, 12.5 parts by weight of pectin, 19.5 parts by weight of gelatin, 3.0 parts by weight of potassium alum and 0.5 part by weight of white petrolatum were used. The composition was used.

Comparative Example 6 A hydrogel dressing having a thickness of 1 mm, which was irradiated with γ-rays in a 4% by weight aqueous solution of polyethylene oxide and in the same manner as in Example 1, was used.

Comparative Example 7 A polymer mixture was obtained in the same manner as in Example 1 except that the monomer composition was 0.005 part by weight of polyethylene glycol 600 dimethacrylate. This one is 50%
The modulus was 1.9 g / mm ² , and it dissolved without swelling in the water absorption test.

Comparative Example 8 A polymer mixture was obtained in the same manner as in Example 1 except that the monomer composition was 5 parts by weight of polyethylene glycol 600 dimethacrylate. This product had a 50% modulus of 15.0 g / mm ² , and in the water absorption test, it swelled and then whitened, resulting in a marked decrease in transparency. The water absorption is 240
%Met.

The 50% modulus and water absorption are determined by the following methods. Tensile test Using those of each Example and each Comparative Example, these were 2 cm x
Cut to 4 cm, sandwich 1 cm from both ends of the long side, and Tensilon manufactured by Toyo Baldwin (STM
-T-50BP) was used to perform a tensile test, and the stress (g / mm ² ) at 50% tension was defined as 50% modulus. In this case, the chuck distance is 20 mm and the pulling speed is 30.
It was set to 0 mm / min.

Water Absorption Test The samples of Examples and Comparative Examples were used.
After cutting into m × 1.5 cm and measuring the weight before water absorption, each cut piece was cut into phosphate buffered saline (pH 7.4, 3).
It was immersed in 135 ml (2 ° C.) for 24 hours. After that, each cut piece was taken out, the surface water was wiped off, the weight after water absorption was measured, and the water absorption rate was calculated from the increased weight.

Table 1 shows the results of relative comparison of water absorption, skin adhesion, flexibility and transparency of the above Examples 1 and 13 and Comparative Examples 4 to 6.

[0152]

[Table 1]

From the results shown in Table 1, it can be seen that Examples 1 and 13 have satisfactory water absorbency, skin adhesion, flexibility and transparency, whereas Comparative Example 4 has water absorbency. Is not satisfactory and the flexibility is not sufficiently satisfactory, and the sample of Comparative Example 5 has poor transparency.
Moreover, it cannot be said that the softness is sufficiently satisfactory, and further, that of Comparative Example 6 has poor skin adhesion, and it cannot be said that water absorption is sufficiently satisfactory.

Example 19 In a 20 l closed reactor equipped with a stirrer, 0.15 parts by weight of azobisisobutyronitrile, 70 parts by weight of 2-methoxyethyl acrylate, 30 parts by weight of N-vinyl-2-pyrrolidone and distilled water-methanol- Isopropanol mixed solvent
(Weight ratio = 32: 47: 1) Charge 250 parts by weight to 50
After purging with nitrogen at a flow rate of 0 ml / min for 2 hours, stirring and dropping of the mixed solvent (dropping amount 30 parts by weight) were conducted to 6 inside the reactor.
The reaction was carried out for 4 hours while maintaining the temperature at 0 to 70 ° C. Continued 7
After the reaction was completed by stirring at 5 ° C. for 2 hours, it was cooled to room temperature to obtain a solution of an acrylic copolymer.

The acrylic copolymer solution was dried by a coating machine to obtain a medical water-absorbing polymer layer. The drying condition is that the coating speed is 1.5 m / min in a fresh air stream,
The drying tower length is 6.0 m, and the drying temperature is 120-140 ° C.
After drying for a minute, the transparent film having a thickness of 50 μm was laminated to form a roll having a thickness of 2 cm, and then cut into strips having an appropriate size.

This strip-shaped sample was T-die molded by a single-screw extruder. That is, the shaft rotation speed is 60 rpm and the molding temperature is 15
By setting 0 to 170 ° C., die lip width 0.5 mm, die lip length 100 mm, and take-up speed 15 m / min,
A colorless transparent medical water-absorbent polymer layer having an average thickness of 400 μm was obtained.

After covering both sides with release paper, the dose was 2
The wound dressing of the present invention was obtained by irradiating with 7.7 kGy γ-rays.

This was excellent in water absorption, flexibility, transparency and moisture permeability in a healing experiment using a rat dorsal layer skin-cutting wound.

Example 20 A polyether polyamide block copolymer film having a thickness of 30 μm was used as a backing material on one side of the medical water-absorbing polymer layer of Example 19, and an acrylic pressure-sensitive adhesive layer having a thickness of 20 μm in Example 22 was used. After adhering with the interposition of γ, the wound dressing of the present invention was obtained by irradiating with γ-ray having a dose of 27.7 kGy.

This product was excellent in water absorption, flexibility, transparency and moisture permeability in a healing experiment using a rat partial back skin wound.

Example 21 0.2 part by weight of azobisisobutyronitrile, 65 parts by weight of isononyl acrylate and 2 parts by weight were placed in a closed reactor equipped with a stirrer.
-Prepare 30 parts by weight of methoxyethyl acrylate, 5 parts by weight of acrylic acid and 25 parts by weight of toluene, and 10 ml /
After purging with nitrogen at a flow rate of 2 hours for 2 hours, stirring and dropping of the mixed solvent (dropping amount 125 parts by weight) were carried out to 57 to 6 in the reactor.
The reaction was carried out for 8 hours while maintaining the temperature at 0 ° C. The reaction was completed by subsequently stirring at 80 ° C. for 2 hours, and then cooled to room temperature to obtain a solution of an acrylic copolymer.

This acrylic copolymer solution was coated on a releasable paper with a certain thickness, and then 1 in a fresh air stream.
By drying at 10 ℃ for 2 minutes, it has high moisture permeability,
An acrylic pressure-sensitive adhesive layer having a thickness of 20 μm was obtained.

This acrylic pressure-sensitive adhesive layer was perforated with a projection roll, circular holes having a diameter of 0.8 mm were arranged on a grid at intervals of 2.0 mm, and the occupancy rate per unit area was 12.6.
% Perforated pressure-sensitive adhesive layer was obtained.

This perforated pressure-sensitive adhesive film was attached to the medical covering material of Example 19, both sides were covered with release paper, and the medical water-absorbing polymer was obtained by irradiating with γ rays having a dose of 27.7 kGy. 50% modulus of the layer is 23.6 g / mm
² , the wound dressing of the present invention having a water absorption of 710% was obtained.

This product is excellent in water absorption, flexibility, transparency, moisture permeability, and sealability, and in a healing experiment using a rat back partial layer barking wound, almost no bacterial infection was observed, showing an excellent healing effect. Indicated.

Example 22 In Example 21, as a backing material, on the side opposite to the side of the perforated pressure-sensitive adhesive layer in the laminate of the sheet-like medical water-absorbing polymer layer not irradiated with γ rays and the perforated pressure-sensitive adhesive layer. Thickness is 30
After a 10 μm thick polyether polyamide block copolymer film was laminated with an acrylic pressure-sensitive adhesive layer having a thickness of 20 μm in Example 21 interposed therebetween, the dose was 27.7.
By irradiating with γ ray of kGy, a dressing for wound of the present invention having excellent bacterial resistance was obtained.

This product was excellent in water absorption, flexibility, transparency and sealing property, and in the healing experiment using the rat back partial layer bark wound, almost no bacterial infection was observed, showing an excellent healing effect. .

Example 23 In a 20-liter closed reactor equipped with a stirrer, 0.2 parts by weight of azobisisobutyronitrile, 70 parts by weight of 2-methoxyethyl acrylate, 30 parts by weight of N-vinyl-2-pyrrolidone and 66 of toluene. After adding 7 parts by weight of the mixture and purging with nitrogen at a flow rate of 500 ml / min for 2 hours, the inside of the reactor was heated to 58 to 68 ° C. by stirring and dropping a solvent (dropping amount: 166.7 parts by weight).
The reaction was carried out for 4 hours while maintaining Then, at 80 ℃ 2
The reaction was completed by stirring for a time and then cooled to room temperature to obtain a solution of an acrylic copolymer.

This acrylic copolymer solution was coated on a releasable paper with a certain thickness, and then 1 in a fresh air stream.
By drying at 30 ° C. for 5 minutes, a colorless transparent film-like water-absorbent polymer layer for medical use having a thickness of 50 μm was obtained.

On one side of this water-absorbent polymer layer for medical use, a perforated pressure-sensitive adhesive layer similar to that of Example 21 was provided, and on the other side, a polyether polyamide block copolymer film having a thickness of 30 μm was used as a backing material. A medical water-absorbing polymer was prepared by laminating an acrylic pressure-sensitive adhesive layer having a thickness of 20 μm in Example 22 and then covering both surfaces thereof with release paper, followed by irradiation with γ-rays having a dose of 26.9 kGy. 50% modulus of the layer is 21.2 g / mm
^{2. The} external medical material of the present invention having a water absorption of 1030% was obtained.

This product was applied to normal skin with a lot of sweating,
Observation of the state 8 hours after application revealed that the application site had little or no stuffiness, and no peeling of the peripheral part was observed. In addition, no skin irritation such as erythema or pruritus was observed.

Example 24 In Examples 21 and 22, the dose was 27.7 kGy after encapsulating the laminate before γ-ray irradiation in a bacterial resistant packaging material.
The wound dressing of the present invention was obtained by irradiating with the gamma ray of.

Example 25 In Example 23, after encapsulating the laminate before irradiation with γ-rays in a bacterium-resistant packaging material, irradiation with γ-rays with a dose of 26.9 kGy was carried out to obtain the external medicine for medical use of the present invention. Got The above 50% modulus and water absorption are obtained by the above-mentioned method.

Example 26 0.175 parts by weight of azobisisobutyronitrile and 2-methoxyethyl acrylate 7 were placed in a closed reactor equipped with a stirrer.
0 parts by weight, 30 parts by weight of N-vinyl-2-pyrrolidone and 250 parts by weight of distilled water-methanol-isopropanol mixed solvent (weight ratio = 16: 23: 1) were charged, and 10 ml was added.
After purging with nitrogen at a flow rate of 1 / min for 2 hours,
The mixture was stirred for 1.5 hours while maintaining the temperature at 62 ° C. Then, 7
After the reaction was completed by stirring at 5 ° C. for 2 hours, it was cooled to room temperature to obtain a solution of an acrylic copolymer.

This acrylic copolymer solution was coated on a releasable paper with a certain thickness and then dried at 130 ° C. for 5 minutes to remove the solvent and unreacted monomers, and a transparent film having a thickness of 50 μm. To obtain the medical water-absorbing polymer of the present invention. 2- in this water absorbent polymer for medical use
The amounts of methoxyethyl acrylate and N-vinyl-2-pyrrolidone are 10 wtppm or less and 200 wtpp, respectively.
It was m.

Example 27 0.175 parts by weight of azobisisobutyronitrile and 2-methoxyethyl acrylate 7 were placed in a closed reactor equipped with a stirrer.
0 parts by weight, 30 parts by weight of N-vinyl-2-pyrrolidone and 150 parts by weight of toluene were charged, and the atmosphere was replaced with nitrogen at a flow rate of 10 ml / min for 2 hours, followed by stirring for 9 hours while maintaining the inside of the reactor at 60 to 62 ° C. did. Then, add toluene 8
The reaction was completed by adding 3.3 parts by weight and stirring at 80 ° C. for 2 hours, and then cooled to room temperature to obtain a solution of an acrylic copolymer.

This acrylic copolymer solution was applied to a release paper at a constant thickness and then dried at 130 ° C. for 5 minutes to remove the solvent and unreacted monomers, and a transparent film having a thickness of 50 μm. As a result, a medical water-absorbing polymer layer was obtained. The amounts of 2-methoxyethyl acrylate and N-vinyl-2-pyrrolidone in this water absorbent polymer for medical use were 10 ppm by weight or less and 180 ppm by weight, respectively.

Example 28 0.175 parts by weight of azobisisobutyronitrile and 2-methoxyethyl acrylate 6 were placed in a closed reactor equipped with a stirrer.
Charge 5 parts by weight, 30 parts by weight of N-vinyl-2-pyrrolidone, 5 parts by weight of acrylic acid and 150 parts by weight of toluene,
After purging with nitrogen at a flow rate of 10 ml / min for 2 hours, stirring was performed for 8 hours while maintaining the inside of the reactor at 60 to 62 ° C. Subsequently, 83.3 parts by weight of toluene was added thereto, and the mixture was stirred at 80 ° C. for 2 hours to complete the reaction, and then cooled to room temperature to obtain a solution of an acrylic copolymer.

This acrylic copolymer solution was applied on a releasable paper with a certain thickness and then dried at 130 ° C. for 5 minutes to remove the solvent and unreacted monomers, and a transparent film having a thickness of 50 μm. As a result, a medical water-absorbing polymer layer of the present invention was obtained. 2 in this medical water-absorbent polymer
-Methoxyethyl acrylate, N-vinyl-2-pyrrolidone, and acrylic acid in amounts of 10 ppm by weight or less,
It was 220 parts by weight ppm and 5 parts by weight or less.

Example 29 A closed reactor equipped with a 20-liter stirrer was charged with 0.15 parts by weight of azobisisobutyronitrile, 70 parts by weight of 2-methoxyethyl acrylate, 30 parts by weight of N-vinyl-2-pyrrolidone and distilled water. -Methanol-isopropanol mixed solvent (weight ratio = 32: 47: 1) 250 parts by weight was charged and 5
After substituting with nitrogen at a flow rate of 00 ml / min for 2 hours, the reaction was carried out for 4 hours while maintaining the inside of the reactor at 60 to 70 ° C. by stirring and dropping a mixed solvent (dropping amount 30 parts by weight). Then, the reaction was completed by stirring at 75 ° C. for 2 hours and then cooled to room temperature to obtain a solution of an acrylic copolymer.

The acrylic copolymer solution was dried with a coater to obtain a medical water-absorbing polymer layer. The drying conditions are as follows: a fresh air flow, a coating speed of 1.5 m / min, a drying tower length of 6.0 m, a drying time of 4 minutes, and a drying temperature of 120 ° C to 140 ° C.
The resulting transparent film was laminated to form a roll having a thickness of 2 cm, and then cut into strips having an appropriate size. 2-methoxyethyl acrylate and N-vinyl-2 in this medical water-absorbing polymer layer
The amount of pyrrolidone was below 10 ppm by weight and below 130 ppm by weight, respectively.

This strip sample was T-die molded by a single screw extruder. That is, shaft rotation speed 60 rpm, molding temperature 1
By setting the die lip width to 0.5 mm, the die lip length to 100 mm, and the take-up speed to 15 m / min, a colorless and transparent sheet having an average thickness of 400 μm was obtained.

Further, the dose on this sheet is 27.7 kGy.
Was irradiated with γ-ray to obtain a medical external-use material according to the present invention. This medical external material has a 50% modulus of 23.6 g / mm
² , the water absorption was 710%.

Example 30 In a sealed reactor equipped with a 20-liter stirrer, 0.2 parts by weight of azobisisobutyronitrile, 70 parts by weight of 2-methoxyethyl acrylate, 30 parts by weight of N-vinyl-2-pyrrolidone and 66 of toluene. After adding 7 parts by weight of the mixture and purging with nitrogen at a flow rate of 500 ml / min for 2 hours, the inside of the reactor was adjusted to 58 to 6 by stirring and dropping a mixed solvent (dropping amount: 166.7 parts by weight).
The reaction was carried out for 4 hours while maintaining the temperature at 8 ° C. Then, 80 ℃
After the reaction was completed by stirring for 2 hours, the mixture was cooled to room temperature to obtain a solution of an acrylic copolymer.

This acrylic copolymer solution was applied to a release paper at a constant thickness and then dried at 130 ° C. for 5 minutes to remove the solvent and unreacted monomers, and a transparent film with a thickness of 50 μm was prepared. A water absorbent polymer layer for use was obtained. The amounts of 2-methoxyethyl acrylate and N-vinyl-2-pyrrolidone in this polymer layer were 10 ppm by weight or less and 130 ppm by weight, respectively.

The acrylic copolymer solution was dried with a coater to obtain a medical water-absorbing polymer layer. The drying conditions are a fresh air flow, a coating speed of 1.5 m / min, a drying tower length of 6.0 m, a drying time of 4 minutes, and a drying temperature of 120 to 140 ° C.
The film thickness was 50 μm, and the obtained transparent films were laminated to form a roll having a thickness of 2 cm, and then cut into strips having an appropriate size.

[0187] This strip-shaped sample was T-die molded by a single-screw extruder. That is, the shaft rotation speed is 40 rpm, the molding temperature is 1
A colorless and transparent sheet having an average thickness of 100 μm was obtained by setting the die lip width to 0.5 mm, the die lip length to 100 mm, and the take-up speed to 30 m / min.

Further, the dose on this sheet is 26.9 kGy.
And γ-rays were irradiated to obtain a medical covering material according to the present invention. This medical coating material (medical water absorbent polymer layer) had a 50% modulus of 21.2 g / mm ² and a water absorption rate of 1030%.

Example 31 In Example 29, three extruded sheets before γ-ray irradiation were laminated, thermocompression-bonded, and then irradiated with γ-ray having a dose of 27.7 kGy to give a sheet having a thickness of 1.1 mm. As a result, a medical covering material according to the present invention was obtained.

Example 32 In Example 29, the extruded sheet before γ-ray irradiation was encapsulated in a bacteria-resistant packaging material, and then the γ-ray having a dose of 27.7 kGy was irradiated to the wound-dressing material of the present invention. Got

Example 33 In Example 30, after a non-woven fabric having a thickness of 50 μm was thermocompression-bonded to the extruded sheet before γ-ray irradiation, the dose was 27.7 k.
By irradiating with γ ray of Gy, the medical external use material of the present invention was obtained.

Example 34 0.05 part by weight of 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2-methoxyethyl acrylate 7 were placed in a closed reactor equipped with a stirrer.
After charging 0 part by weight and 30 parts by weight of N-vinyl-2-pyrrolidone, the atmosphere was replaced with nitrogen at a flow rate of 10 ml / min for 2 hours,
Irradiation with UV light having a total dose of 50 mJ / cm ² resulted in a syrup partially photopolymerized.

Peelability P obtained by siliconizing this syrup
After casting in a 1.2 mm thick silicon mold applied on the ET film and covering with a similar peelable PET film from above, the total dose was 3000 mJ / UV evenly on the front and back to be cm ^2.
After irradiating with light, it was further dried at 130 ° C. for 30 minutes to obtain a medical external-use material of the present invention as a transparent sheet having a thickness of 1 mm. The amounts of 2-methoxyethyl acrylate and N-vinyl-2-pyrrolidone in the dried polymer were 190 ppm by weight and 1020 ppm by weight, respectively. This product has a 50% modulus of 20.0 g / m
m ² and water absorption were 1100%.

Example 35 The present invention was carried out in the same manner as in Example 34 except that the monomer composition was 65 parts by weight of 2-methoxyethyl acrylate, 30 parts by weight of N-vinyl-2-pyrrolidone and 5 parts by weight of acrylic acid. A medical external use material was obtained. 2-Methoxyethyl acrylate, N-vinyl-2- in the polymer after drying
The amount of pyrrolidone and acrylic acid are each 250 ppm by weight,
It was 1530 weight ppm and 360 weight ppm.
The amount of monomer is determined by the following method, and the 50% modulus and water absorption are determined by the method described above.

Residual monomer quantitative test (2-methoxyethyl acrylate and N-vinyl-2-
Amount of pyrrolidone) The amount of pyrrolidone used in each example is about 0.
5 g was accurately weighed, 10 ml of ethyl acetate was added thereto, and the mixture was shaken at 150 rpm for 3 hours and then left for 2 days. An HP5890A type gas chromatograph (manufactured by Yokogawa Furrett Packard) was used as the extract, and the amount of the monomer was calculated from the calibration curve prepared with the standard reagent.

(Acrylic acid content) The amount of acrylic acid used in each Example was used.
About 0.1 g of these was accurately weighed, 10 ml of acetonitrile was added thereto, and the mixture was shake-extracted at 150 rpm for 3 hours and then left for 2 days. The extract is CCPM (UV800
The amount of monomer was calculated from a calibration curve prepared with standard reagents using a 0) type high performance liquid chromatograph (manufactured by JASCO Corporation).

[0197]

The medical water-absorbing polymer of the present invention has the above-mentioned constitution, and since this polymer is obtained by copolymerizing a specific hydrophilic monomer, it has excellent flexibility and water-swelling swelling. In addition to having the properties, it has the effect of excellent skin adhesion and transparency.

Further, the medical water-absorbing polymer of the present invention, which contains a polyfunctional acrylate or methacrylate and is obtained by copolymerization of these by photopolymerization, has excellent flexibility and water-swelling property, and It has the effects of excellent skin adhesion and transparency.

The medical water-absorbing polymer of the present invention can also be obtained by subjecting a mixture of a specific hydrophilic polymer and a plasticizer to a cross-linking treatment. By controlling the conditions of this cross-linking treatment, various properties required can be obtained. The polymer has the effect that it can be obtained very easily.

The wound dressing of the present invention is formed by forming the above-mentioned medical water-absorbing polymer into a film or sheet, or forming the above-mentioned medical water-absorbing polymer into a mesh or a porous form. Therefore, the application to the outer skin is extremely easy, and the handleability is remarkably improved, which is extremely useful. In this case, by covering one side of the film formed in this way with a backing material, strength, fixability, shape retention, adhesion, etc. are improved, and it is enclosed in a bacteria-resistant packaging material in a sterilized state. By doing so, it is more useful as a wound dressing or the like that requires sterility.

Since the medical external use material of the present invention has adhesiveness to the wound site of the skin, appropriate tackiness is exhibited by increasing or decreasing the monomer composition of the acrylic copolymer or the amount of the plasticizer. Therefore, if necessary, the adhesive (water-absorbing polymer) layer may contain a drug to be used as a transdermal drug batch.

Since the wound dressing and the medical external use material of the present invention have the perforated pressure-sensitive adhesive layer, the skin adhesiveness is remarkably improved while maintaining excellent water absorption, flexibility and transparency. In addition, it is possible to prevent bacterial infection due to poor sealing property, deterioration of adhesive strength due to stuffiness, and skin irritation.

That is, by providing a perforated pressure-sensitive adhesive layer on the surface of the wound dressing of the present invention on the side where the wound is adhered,
In addition to improved sticking to the application site surface and improved sealing performance, body fluid is efficiently absorbed through the pores, and moreover, some of the retained water gradually evaporates, so the exudate is stored. Is suppressed and a moist environment suitable for wound healing is maintained. In addition, the perforated pressure-sensitive adhesive layer in contact with the normal skin around the wound edge exhibits excellent adhesiveness, and a sufficient sealing property is obtained to prevent bacterial infection.

Further, in the wound dressing having such a structure, perspiration at the application site passes through the voids of the perforated pressure-sensitive adhesive layer to reach the water-absorbent polymer layer and is quickly absorbed, so that the sweat does not get wet. It is possible to prevent the inflammation and the decrease in the adhesive force that accompany it.

Therefore, this wound dressing has a sealing property,
Wet Heali for skin wounds with excellent flexibility and transparency
Since it can maintain a wet environment suitable for ng, it can be used for healing skin wounds such as burns, skin-wounds, cuts, contusions, pressure ulcers, sutures, and skin ulcers.

Further, the medical external use material of the present invention having such a structure is excellent in skin adhesiveness, moisture absorbability and moisture permeability capable of preventing stuffiness which often occurs in a perspiration site and the inflammation associated therewith, It can be more suitably used for a surgical tape for fixation, a medical adhesive sheet for use with a first aid band, a magnetic band, an adhesive bandage having elasticity, a drug transdermal absorption tape preparation and the like.

[0207] In the wound dressing and medical external preparation obtained by the present invention, by reducing the amount of impurities and residual monomers, the quality is stabilized, and adverse effects on the living body due to these impurities and residual monomers are eliminated. Therefore, the safety is improved.

In the dressing for wounds of the present invention, by reducing the amount of impurities and residual monomers, it is excellent in water absorption, skin adhesion, flexibility and transparency, and can be used for skin wounds.
It can provide a suitable moist environment for ealing, and as a result, can be used for healing skin wounds such as burns, skin-wounds, cuts, contusions, pressure sores, sutures, and skin ulcers.

[0209] Further, in the medical external use material of the present invention, by reducing the amount of impurities and residual monomers, it is possible to prevent stuffiness that often occurs in a sweaty area and the like and inflammation associated therewith, and it is excellent in water absorption and moisture permeability. It can be more suitably used for a medical adhesive sheet such as a fixing surgical tape, a first aid band, a magnetic band, an elastic adhesive bandage, and a drug transdermal absorption tape preparation.

Claims (19)

[Claims] 1. A water-absorbing polymer used for medical purposes, wherein the water-absorbing polymer is 60 to 80% by weight of alkoxyalkyl acrylate and 20 to 4 of N-vinyllactam.
A medical water-absorbing polymer comprising an acrylic copolymer obtained by copolymerizing an acrylic composition comprising 0% by weight and 10% by weight or less of a vinylcarboxylic acid. 2. An acrylic copolymer obtained by copolymerizing the acrylic composition of claim 1 with 0.01 to 1% by weight of a polyfunctional acrylate or methacrylate. Water absorbent polymer for medical use. 3. A mixture obtained by crosslinking a mixture of 60% by weight or more of an acrylic copolymer and 40% by weight or less of a plasticizer.
Or the water-absorbent polymer for medical use according to item 2. 4. The water absorbent polymer for medical use according to claim 1, wherein the acrylic copolymer is cross-linked. 5. A wound dressing using the water-absorbing polymer for medical use according to claim 1. 6. A wound dressing comprising the medical water-absorbing polymer according to claim 1 formed into a film or sheet. 7. A wound dressing in which the medical water-absorbing polymer according to any one of claims 1 to 4 is formed into a film or sheet and cross-linked. 8. A wound dressing in which the medical water-absorbing polymer according to any one of claims 1 to 4 is formed into a film or sheet and dried. 9. A wound dressing in which the perforated pressure-sensitive adhesive layer is provided on the surface of the wound dressing according to any one of claims 5 to 8 on the side where the wound portion is attached. 10. A wound dressing in which a backing material is provided on the side opposite to the perforated adhesive layer side in the wound dressing according to claim 9. 11. A medical external use material comprising the medical water-absorbing polymer according to claim 1. 12. A medical external material comprising the medical water-absorbing polymer according to claim 1 formed into a film or sheet. 13. A medical external material in which the medical water-absorbing polymer according to any one of claims 1 to 4 is formed into a film or sheet and crosslinked. 14. A medical external-use material in which the medical water-absorbing polymer according to any one of claims 1 to 4 is formed into a film or sheet and dried. 15. A medical external preparation having a perforated pressure-sensitive adhesive layer provided on the surface of the medical external preparation according to any one of claims 5 to 8 on the side where the wound is attached. 16. A medical external-use material in which a backing material is provided on the side opposite to the perforated pressure-sensitive adhesive layer side in the medical external-use material according to claim 9. 17. A method for producing a water-absorbing polymer used for medical purposes, which comprises 60-80% by weight of alkoxyalkyl acrylate, 20-40% by weight of N-vinyllactam and 10% by weight of vinylcarboxylic acid.
A method for producing a water-absorbing polymer for medical use, comprising copolymerizing an acrylic composition comprising the following, casting the composition, and then drying the composition to remove monomers and volatile impurities. 18. A method for producing a wound dressing, which comprises extruding the water-absorbent polymer for medical use according to claim 17 to form a sheet, and then subjecting the sheet to cross-linking treatment. 19. A method for producing a medical external-use material, which comprises extruding the water-absorbent polymer for medical use according to claim 17 to form a sheet and then subjecting the sheet to cross-linking treatment.