JPS59201849A - Polyamino acid film composite body - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyamino acid film complex useful for medical purposes, particularly as membranes for artificial lungs and artificial skin.

Polyamino acids are polymeric substances linked by the same peptide bonds as naturally occurring proteins, and are materials with excellent compatibility with living organisms, making them useful for artificial skin, contact lenses, dialysis membranes, artificial lung membranes, etc. Advantageously applied for medical purposes.

However, since such a polyamino acid film is expensive, it is desirable to use it as a film as thin as possible, but in this case, there is a problem in that the mechanical strength is low and it cannot be used as a thin film. Further, even if such a polyamino acid film is simply bonded to a normal polymer film to form a composite, a film with desired characteristics cannot be obtained.

The present inventors conducted various studies to develop a polyamino acid film composite that is suitable for medical use and has improved mechanical strength. The inventors have discovered that the object can be achieved by making it possible to achieve this goal, and have completed the present invention based on this knowledge.

That is, according to the present invention, the polyamino acid film is laminated on at least one surface of a water vapor and oxygen permeable polymer film, and the water vapor permeability is 1×10=gu・c1n/cnffi−hr or more. and oxygen permeability I
X 10-1Ocsi・an/ctl-5ec-on
A polyamino acid film composite having a HP or higher is provided.

Polyamino acids used in the present invention are conventionally known, and various amino acids can be reacted with phosgene to form N-calcexyamino acid anhydride, which is then polymerized in the presence of a base. Polyamino acids can be obtained by Examples of such polyamino acids include polyalanine, polyalanine, polyleucine, leucine/benzylglutamate copolymer, and leucine/Cal74? Benzoxyornithine copolymer, carbobenzoi 7 IJ resin benzyl glutamate copolymer,
Examples include alanine/methionine copolymer, calzepenzoxylidine/benzylglutamate/methionine copolymer, and the like.

The polyamino acids in the present invention include the above-mentioned homopolymers, copolymers, and mixtures thereof, as well as 2. The polyamino acid modifier in this case includes, for example, hydroxyl alkylamine (HO-R-NH2, RFi is an alkyl group having 1 to 8 carbon atoms), oligonucleotide Ethylene ogicide (RO(-
CH2CH20÷nH, R is an alkyl group having 1 to 8 carbon atoms, n is an integer of 1 to 50), sodium hydroxide, potassium hydroxide, hydrogen bromide/acetic acid mixture, hydrogen peroxide, and the like. The molecular weight of the polyamino acid is usually about 10,000 to 500,000, and it is sufficient that the polyamino acid has a molecular weight that can form a film.

In the present invention, the polymer used to compose the polyamino acid film has a water vapor permeability of 1 x 10-61·c?
n/cηf・hr or more, preferably 3X10-6~1X
It is in the range of l0-37・C7n/c〃f・hr, and the oxygen permeability is 1 x 10-1Or:ni・cnl/cn
i-8ec-cTnH9- or more, preferably lX10-
1゜～5×10″c171-cノ11/cnf・5CC
A material that is within the range of -an■■φ and is highly flexible is preferably applied. Polymers that provide such films include polycitadiene, styrene/butadiene copolymer, polyurethane, polytetrafluoroethylene, polyhexamethylene aziboamide (nylon 66), polyisozolene, cellulose acetate, silicone rubber, and the like.

As the polymer film in the present invention, porous polymer films such as porous Teflon films, membrane filters made of cellulose derivatives, etc. are also applicable.

Note that the water vapor permeability and oxygen permeability referred to in 1i) of this specification are based on the methods shown in the examples shown later.

To produce the polyamino acid coated composite of the present invention, the polyamino acid is dissolved in an appropriate solvent such as benzene, chloroform, tetrachloroethane, dioxane, etc. After casting this onto a smooth surface such as glass, the solvent is evaporated to form a polyamino acid film, and the desired polymer solution is similarly cast on top of it to remove the solvent. evaporation or conversely, the polymer solution is cast onto a smooth surface, the solvent is evaporated to form the desired polymer film, and then the polyamino acid solution is cast onto it and the solvent is evaporated. let In this way, a composite in which a polyamino acid film is combined with a desired polymer film can be obtained. Such a composite can also be obtained by casting a polyamino acid solution onto a preformed polymer film and evaporating the solvent. When obtaining a composite film, if the bondability between the polyamino acid coating and the polymer film is poor, both films can be composited via an adhesive layer. As the adhesive in this case, a commonly used adhesive such as polyacrylic acid butyl ester can be used.

In the composite of the present invention, the thickness of the polyamino acid film is 1
~20 μm, preferably 3-15 μm, and the thickness of the polymer film is 5-50 μm. Also, the overall water vapor permeability is 1 x 10=F-cm/c〃i・
hr or more, preferably 2 x 10-6~] X 10='
t-an/al-hr, and the oxygen permeability is 1×10
'-10cIIl-cnonn/chorn!・5CC-c1n
H1 or more, preferably lXl0-10~5X10-
9ari・aniozi asec・CrnHii'.

The polyamino acid film composite of the present invention has excellent oxygen permeability and water vapor permeability, as well as increased mechanical strength, and utilizes the affinity of the polyamino acid film for living organisms to be used as a medical material. advantageously applied as
In particular, artificial skin for covering damaged skin due to burns, etc., and membranes for oxygenators [total oxygen permeability of 20 crtl/m]
'·hr (in air at a thickness of 30 pm)] is suitable.

Next, the present invention will be explained in more detail using examples.

Example 1 Polymethionine (molecular weight approximately 320,000) 1.657-
Tetrachloroethane 20 o*+l KM solution L as a vehicle, this solution was cast onto a glass surface with a spacer placed on it, the solvent was removed by air drying, and then a bottle (1,2 - butadiene) (molecular weight approximately 100,000) dissolved in benzene as a solvent (concentration 5%) was cast, and the solvent was removed by air drying to form a composite of polymethionine and poly(1,2-cytadiene). Got the film. In this composite film, the total film thickness is 40
The thickness of the polymethionine film in μm was 5 μm, and the thickness of the poly(1,2-butadiene) film was 35 μm.

Example 2 In Example 1, a solution of styrene/citadiene copolymer (styrene weight fraction 27, molecular weight approximately 100,000) (concentration 5) was used instead of the PoIJ (1,2-citadiene) solution.
A composite film of a polymethionine film (thickness: 6 μm) and a styrene/butadiene copolymer film (thickness: 36 μm) was obtained in the same manner except that benzene was used as the solvent.

Example 3 In Example 1, leucine/benzylglutamate copolymer (copolymerization molar ratio -
A leucine/benzyl glutamate copolymer film (thickness: 5.0
μm) and poly(1,2-phtadiene) film (thickness 4
1 μm) was obtained.

Example 4 Example 1 except that a solution of methionine/benzylglutamate copolymer (copolymerization molar ratio - so/so) (a degree 1%, chloroform was used as a solvent) was used instead of the polymethionine solution. Similarly, nothione/
Benzyl glutamate copolymer film (thickness 11 μm
) and poly(1,2-citadiene) film (thickness 20μ
A composite film with m) was obtained.

Example 5 In Example 1, a solution of leucine/carbobenzoxyornithine copolymer (copolymerization molar ratio -50150) (a degree 2%, benzene used as a solvent) was used instead of the polymethionine solution, and poly( In the same manner, except that a polyurethane solution (concentration 3, methyl ethyl ketone was used as the solvent) was used instead of the 1°2-polybutadiene) solution.
Leucine/carbobenzoxyornithine copolymer film (thickness: 8 μm) and polyurethane film (thickness: 13 μm)
A composite film was obtained.

Example 6 A polymethionine film (thickness 7 μm
) and a polyurethane film (thickness: 22 μm) was obtained.

Example 7 The polymethionine portion of the composite film obtained in Example 6 was denatured by contacting with 15% hydrogen peroxide solution at room temperature for 10 minutes.

In this case, no change in appearance such as thickness or transparency was observed.

Example 8 A spacer was placed on a porous Teflon film (commercially available), and a polymethionine solution (c! degree 2, dichloroacetic acid and chloroform were used as solvents) was cast and air-dried to form a polymethionine solution. A composite film of a film (6 μm thick) and a porous Teflon film (46 μm thick) was obtained.

For each film obtained in the above manner, the film is injected to keep the film surface in constant contact with water, and the upper M part of the cylindrical tube is sealed to allow water to evaporate from the bottom surface of the film to the outside. I did it like that. The entire device was placed in a desicake (temperature: 37° C.), and the device was taken out at predetermined time intervals to measure the weight loss, and the water vapor permeability was determined using the following formula.

P (H2O) ``''''Water vapor permeability (g-CM
/C1)f・hr)ΔW ......Time Δt(hr
) Weight of water (goo) L ... Thickness of measurement film cm) A
・・・・・・Area of the film in contact with water (cat) Oxygen permeability:

Claims (3)

[Claims] (1) Consists of a polyamino acid film laminated on at least one of a water vapor and oxygen permeable polymer film, and has a water vapor permeability of I x 10"P.on/
cnf-hr or more and oxygen permeability is 1, X 10
”, crrhcnz/c, 4esec-orrl(
A polyamino acid film complex that is P or more. (2) A polyamino acid film is laminated on at least one surface of the water vapor and oxygen permeable polymer film, and the water vapor permeability is I X I CV”P-cm/cr1.-
hr and oxygen permeability is IX 1.0-10al
An artificial lung l-11 membrane consisting of a polyamino acid membrane complex which is i・an/C1!1-seC*anH'i-'-. (3) A polyamino acid film is laminated on at least one surface of the water vapor and oxygen permeable polymer film, and the water vapor permeable layer is
and the oxygen permeability is I X 10'-"ari-
Artificial skin made of a polyamino acid film complex having a rating of cm/c11·5ec-on■IP or higher.