JPH0783760B2 - Breathable Casting Adhesive Material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention exerts an effect when applied to a human body at the time of surgery for medical use, particularly for surgery, which is obtained by subjecting a film of a polyamino acid-modified polyurethane resin composition to an adhesive treatment. The present invention relates to a moisture permeable casting adhesive member.

<Conventional technology and its problems> If the pressure-sensitive adhesive film that is applied to the human body during surgery does not have moisture permeability, it will not be able to release moisture to the outside air due to the sweating action from the skin, and water will be insufficient, causing itching and rashes on the skin surface. It has a problem that such symptoms occur.

As a pressure-sensitive adhesive member that has been conventionally used for this kind of application, a general-purpose film that does not show moisture permeability, that is, a polyvinyl chloride film or a polyethylene film, is subjected to fine perforation by machining, or a polyurethane resin wet-processed. The direction of forming a moisture-permeable film having a large number of continuous pores by a membrane method is practiced.

However, drilling by machining has drawbacks in waterproofness, antibacterial property, etc.In addition, in the method of producing a moisture-permeable film by the wet film-forming method, variations in film-permeability due to unevenness in film-forming speed and unevenness in thickness are caused. In addition, the opacity phenomenon of the film due to the coagulation method is unavoidable.

Adhesive members obtained by applying an acrylic, rubber, or urethane adhesive to these moisture-permeable coatings have the drawbacks of being waterproof, antibacterial, or opaque for medical use, especially for surgery.

From such a point, development of a medical adhesive member having a moisture permeable function is desired.

<Means for Solving Problems> As a result of studies to solve the above-mentioned conventional problems in the medical adhesive member, the present inventor has obtained a transparent and moisture-permeable optimum adhesive member for medical use. It is a thing.

That is, the present invention provides a moisture-permeable casting pressure-sensitive adhesive member characterized in that a polyamino acid-modified polyurethane resin composition is applied and dried on a releasable substrate, and then an adhesive layer is provided thereon. By using the polyamino acid-modified polyurethane resin composition, problems such as mechanical drilling, nonuniformity of thickness and discontinuous porosity due to the solidification method, and opacity were solved all at once. Is basically a successful development of a transparent casting adhesive material of a different type.

<Function> The polyamino acid-modified polyurethane resin composition used in the present invention can be obtained as follows.

First, a polyester diol or polyether diol, an organic diisocyanate and, if necessary, a glycol or an organic amine as a low molecular weight chain extender are polymerized by an ordinary method in an organic solvent to obtain a polyurethane resin. Amino acid N- for resin solution
5-40% by weight of carboxylic anhydride, preferably
A polyamino acid-modified polyurethane resin is provided by addition polymerization of 15 to 35% by weight.

Only the polyamino acid-modified polyurethane resin thus obtained achieves the object of the present invention.

Here, the use amount of the amino acid N-carboxylic acid anhydride is limited to 5 to 40% by weight, and when it is less than 5% by weight, the moisture permeability is insufficient, and it is unsuitable for medical use and surgery.
On the other hand, if it exceeds 40% by weight, the dry film becomes poor in recovery elasticity and lacks flexibility, and is not suitable for medical or surgical use.

Explaining the material for obtaining the polyamino acid-modified polyurethane resin composition as described above, as the polyester diols, ethylene adipate, propylene adipate, butylene adipate, hexyl adipate, polycarbonate ester diol, etc. are used, and as the polyether diol, , Polyethylene glycol, polypropylene glycol, polybutylene glycol, and copolymerized polyethers thereof can be used alone or as a copolymer.

Organic diisocyanates include non-yellowing aliphatic diisocyanates and hexamethylene diisocyanates (HD
I), isophorone diisocyanate, (IPDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI), xylene diisocyanate (XDI) and yellowing diphenylmethane diisocyanate (MDI) and toluylene diisocyanate (TDI), etc. Can be used. The low molecular weight glycols used as a chain extender include ethylene glycol, propylene glycol, butylene glycol, or hexylene glycol, and the diamines include ethylenediamine, hexamethylenediamine, isophoronediamine, piperazine, and the like. In addition, alkanolamines can also be used. As the amino acid N-carboxylic acid anhydride, γ-methyl L-glutamic acid N-carboxylic acid anhydride, γ-ethyl L-glutamic acid N-carboxylic acid anhydride, γ-benzyl L-glutamic acid N-carboxylic acid anhydride Are used.

As the main solvent used for the polymerization of polyurethane, in addition to the polymerization of polyurethane, addition polymerization of amino acid N-carboxylic acid anhydride and the polyamino acid-modified polyurethane resin composition obtained can be used to form a film by a casting method. From the standpoint of stability of the coating liquid, methyl ethyl ketone, toluene, ethyl acetate, dimethylformamide, and the like alone or a mixed solvent thereof are preferable.

When the polyamino acid-modified polyurethane resin composition thus obtained is used, an extremely flexible polyamino acid-modified polyurethane film having sufficient fit property, drape property, moisture permeability and the like for medical and surgical purposes can be obtained.

That is, the polyamino acid-modified polyurethane resin composition obtained above is adjusted to a concentration of 10 to 30% by weight, and then coated on a releasable substrate and dried to form a substrate of the moisture-permeable casting pressure-sensitive adhesive member according to the present invention. A moisture-permeable polyamino acid-modified polyurethane film is obtained. At this time, the resin solution is coated on a releasable substrate using a comma doctor, a knife coater, etc. and dried at 100 to 150 ° C., and the film thickness after drying is
Those having a range of 15 to 150 μ are preferable for medical use.

The moisture-permeable casting pressure-sensitive adhesive member of the present invention is obtained by coating the polyamino acid-modified polyurethane film on the releasable substrate obtained above with an acrylic-based, urethane-based, or synthetic rubber-based pressure-sensitive adhesive, or It is obtained by applying a pressure-sensitive adhesive onto a releasable base, drying it, and transferring it onto the film by a laminating method.

Thus, the adhesive member is has a superior performance that total thickness moisture permeability 30~165μ is 400~3000g / m ² / 24hrs, recovery modulus at 100% elongation holds 99% or more.

Adhesives used in this invention are acrylic, urethane,
It is preferable to mix and use an organic polyisocyanate and a tackifier for the purpose of improving the cohesive force in order to improve the adhesion to the film in the synthetic rubber resin.
TDI, XDI, IPDI, etc. are used as the organic polyisocyanate, and petroleum rosin, butyl rubber, acrylic polymer, ester gum, etc. are preferably used as the tackifier. The amount used is suitably 2 to 10 parts by weight with respect to 100 parts by weight of the adhesive. And as the thickness of the adhesive layer, the preferred range of 15~30μ obtain those moisture permeability 400~3000g / m ² / 24hrs. When the thickness of the pressure-sensitive adhesive layer is 15 μm or less, the water vapor permeability is improved, but the adhesive strength is lowered, and when it is 30 μm or more, the water vapor permeability is decreased, which is not preferable.

Further, there is a large difference in moisture permeability depending on the type of adhesive used, so it is necessary to consider the thickness of the adhesive layer depending on the type of adhesive used.

A member indicating the smallest ground moisture permeability and 400g / m ² / 24hrs at breathable casting adhesive member of the present invention was laminated on the skin, but did not at all rash and itching occurs after 48 hours.

In addition, the adhesive member of the present invention is used for medical purposes by sterilizing the adhesive layer after arranging it into an arbitrary shape with the releasable substrate stuck to the surface of the adhesive layer.

Further, for those having a small shape, a releasable substrate may be adhered to the adhesive surface of the adhesive member, and the releasable substrate on the side of the polyamino acid-modified polyurethane film, which is the substrate, may be removed and sterilized.

<Example> Hereinafter, an example of the present invention will be described in detail.

All parts are parts by weight.

Example 1 (1) Production of Polyamino Acid-Modified Polyurethane Resin Composition A reactor was charged with 850 parts of polybutylene-adipate for polyurethane having an average molecular weight of 1000 as a polyol component, 250 parts of diphenylmethane diisocyanate, and 742 parts of a mixed solvent of dimethylformamide and methyl ethyl ketone. Charge, hold at 70-80 ° C for 3 hours with stirring, then 1,
14 parts of 4-butanediol was added little by little to increase the viscosity.

When the viscosity of the reaction solution reached 7500 cps at the concentration of 30% of the mixed solvent, morpholine was immediately added to stop the reaction.

Next, γ-is added to 500 parts of this 30% concentration urethane resin solution.
64 parts of methyl L-glutamic acid N-carboxylic acid anhydride and 862 parts of dimethylformamide were charged, and the reaction was terminated by keeping at 50 to 60 ° C for 20 hours, solid content 15%, viscosity 1800cps / 30%.
To obtain a polyamino acid-modified polyurethane resin solution.

(2) Production of polyamino acid-modified polyurethane resin film The polyamino acid-modified polyurethane resin solution obtained in (1) is dried on a release paper (DNTP-ART, manufactured by Dai Nippon Printing Co., Ltd.) so that the film thickness after drying becomes 30 μ. And apply at 80 ℃ for 2 minutes
It was dried at 130 ° C for 4 minutes to obtain a moisture-permeable film of the resin. The obtained coating was peeled from the release paper and various physical properties of the coating were tested. The following values were obtained.

100% modulus 25 kg / cm ² Recovery elastic modulus for 100% elongation 99.5% Elongation at break 430% Tensile strength 370 kg / m ² (3) Manufacture of adhesive Acrylic resin (Crisbon 7366-SL, Dainippon Ink and Chemicals, Inc.) Charge 100 parts, 60 parts synthetic rubber (Kraton Thermoplastic Rubber, manufactured by Ciel), 20 parts natural rosin (KE 707, manufactured by Yasuhara Yushi Co., Ltd.) into a mixing container, stir at room temperature for 40 minutes, and then toluene diisocyanate 3 And the mixture was stirred for 2 hours. Then, the resin solution was diluted with a 60/40 mixed solvent of ethyl acetate / toluene so that the solid content was 40%. The solution viscosity of the obtained pressure-sensitive adhesive was 2300 cps / 30 ° C.

Example 2 The pressure-sensitive adhesive obtained in (3) of Example 1 was applied to a release paper (60S-018, manufactured by Fujimori Kogyo Co., Ltd.) having a good releasability so that the film thickness after drying was 25 μ, and the temperature was 70 ° C. And dried for 4 minutes to form a film.

Then, this was pressure-bonded to the moisture-permeable polyamino acid-modified polyurethane film with release paper obtained in Example 1 (2) at room temperature under a condition of 2.0 kg / cm ² using a laminator to give a moisture-permeable casting adhesive member having a film thickness of 55 μm. Got

The adhesive material film thus obtained was tested for various physical properties, and the following results were obtained.

100% Modulus 18.5 kg / cm ² 100% Recovery elastic modulus 98.5% Tensile strength 320 kg / m ² Breaking elongation 390% Moisture vapor transmission rate (according to JISZ-0208) 2400 g / m ² / 24hrs Moisture vapor permeable casting adhesive obtained above When the member was attached to the skin, no rash or itching was observed even after 48 hours.

Comparative Example 1 500 parts of the polyurethane resin solution having a concentration of 30% obtained in (1) of Example 1 was charged with 7.8 parts of γ-methyl L-glutamic acid N-carboxylic acid anhydride and 544 parts of dimethylformamide as a solvent. The reaction was carried out by holding at 2 ° C for 2 hours.

The resin solution obtained had a solid content of 15% and a viscosity of 1450 cps / 30.
It was ℃.

Using this resin solution, a moisture-permeable film having a thickness of 30 μm was produced in the same manner as in (2) of Example 1.

Then, using the pressure-sensitive adhesive obtained in (3) of Example 1, Example 2
A pressure-sensitive adhesive film having a thickness of 25 μm was produced in the same manner as in (1) and laminated on the moisture-permeable film to obtain a moisture-permeable casting pressure-sensitive adhesive member having a film thickness of 55 μm.

Moisture permeability of thus obtained adhesive members showed an extremely low value of 350g / m ² / 24hrs, the results of other various physical properties tested were as follows.

100% modulus 23 kg / cm ² 100% Recovery elastic modulus for elongation 95.5% Tensile strength 360 kg / m ² Moisture vapor transmission 350 g / m ² / 24hrs When this adhesive member was applied to human skin, the main component of the adhesive member Since the amount of the amino acid N-carboxylic acid anhydride in the polyamino acid-modified polyurethane resin composition described above was small, rash and itchiness were observed after 48 hours.

<Effects of the Invention> As described above, the moisture-permeable casting pressure-sensitive adhesive member of the present invention is composed of a polyamino acid-modified polyurethane resin film and a pressure-sensitive adhesive layer, and comprises a polyamino acid-modified polyurethane resin film containing a polyamino acid-modified polyurethane resin film. By adjusting the amount of the amino acid N-carboxylic acid anhydride to 5 to 40% by weight, it was confirmed that it has good adhesion to the skin for medical use, particularly for surgery, and has excellent moisture permeability and fit property.

Claims (2)

[Claims] 1. A polyamino acid-modified polyurethane resin obtained by adding 5 to 40% by weight of an amino acid N-carboxylic acid anhydride to a polyurethane resin composed of polyester diol or polyether diol and an organic diisocyanate and carrying out addition polymerization. After coating the composition on a releasable substrate and drying,
A moisture-permeable casting pressure-sensitive adhesive member, characterized in that a pressure-sensitive adhesive layer having a thickness of 15 to 30 μm is provided thereon. In 2. The resulting moisture permeable casting adhesive member has moisture permeability 400~3000g / m ² / 24hrs, the claims recovered modulus at 100% elongation is equal to or less than 99% The moisture-permeable casting pressure-sensitive adhesive member according to item 1.