KR20100049280A - Biodegradable polymer film, biodegradable polymer-ceramic complex film, preparation method thereof and usage thereof - Google Patents

Abstract

PURPOSE: A method for manufacturing biodegradable polymer-ceramic complex film is provided to quickly and simply manufacture and to control thickness and penetrability of the film. CONSTITUTION: A method for manufacturing biodegradable polymer film comprises: a step of dissolving biodegradable polymer in organic solvent to obtain polymer solution(1); a step of uniformly mixing salt particle in the polymer solution; a third step of dropping the polymer solution using a syringe to form a layer on the water; a step of folding the film using a glass bar to obtain a polymer tube; and a step of cutting the polymer tube to form polymer film.

Description

Biodegradable polymer self-supporting film, biodegradable polymer-ceramic complex self-supporting film, preparation method thereof and use thereof {Biodegradable polymer film, biodegradable polymer-ceramic complex film, preparation method about and usage}

The present invention relates to a biodegradable polymer self-supporting membrane prepared using a sleep development method, a biodegradable polymer-ceramic composite self-supporting membrane, a method for preparing the same, and a use thereof.

The present invention relates to a biodegradable polymer self-supporting membrane prepared using a sleep development method, a biodegradable polymer-ceramic composite self-supporting membrane, a method for preparing the same, and a use thereof.

The surface development method is a method of forming a solid thin film insoluble in water by dropping a small amount of polymer solution onto a clean surface and gelling on the surface like an oil film. The prior art related to the preparation of a polymer thin film using such a sleep development method is described below.

U.S. Patent No. 3,874,986 discloses a thin film having a thickness of 0.1 micrometers by dispersing a polymer solution prepared by dissolving a polysiloxane / polycarbonate copolymer in a tetrachlorogropan / tetrachloroethane mixed solvent onto a water surface.

U.S. Patent No. 4,155,793 discloses the preparation of thin films having a thickness of 0.05 micrometers with a polymer solution of a polysiloxane / polycarbonate copolymer branded with polyphenylene oxide and dissolved in tetrachloropentene.

Korean Patent No. 163176 discloses an olefin polymer, a cellulose derivative, an acrylate polymer, a liquid crystal polymer, and a phase plate used as a liquid crystal display device manufactured by developing a polymer solution obtained by dissolving a copolymer of the polymers in a solvent on the water surface. have.

Korean Patent No. 056018 discloses an apparatus for producing a polymer ultrathin film having excellent strength and heat resistance using a surface development method of a polymer solution in which monomer a-octadecyl acrylic acid and monomer w-tricosenoic acid are dissolved in chloroform. The polymer ultra thin film is expected to be applied to organic conductors, photochromic devices, biosensors, artificial corneas, and the like.

U.S. Patent No. 5,342,432 describes the preparation of a polymer solution using a surface expansion method in which a polymer solution in which an amphiphilic molecule having one to two alkyl chains having 8 to 18, especially 8 to 16 carbon molecules per hydrophilic group is dissolved in a solvent. A composite membrane is disclosed.

U.S. Patent No. 5,135,678 discloses an alignment film that can be used in a liquid crystal display device in which a polymer solution obtained by dissolving an amphiphilic polymer material (molecular weight 2,000 to 300,000) in a solvent is prepared by using a surface expansion method.

U.S. Patent No. 5,067,797 discloses an alignment film that can be used in a liquid crystal display cell in which an organic polymer solution prepared by dissolving various polymers such as polyimide-based polymers, polyesters, polyamides, and the like in an organic solvent is produced using a surface expansion method. have.

Japanese Laid-Open Patent Publication No. 2006-231100 discloses a thin film that can be used in various optoelectronic devices in which a polymer solution prepared by using a hydrocarbon, an oxygen-containing organic solvent, a halogenated hydrocarbon, or the like is produced using a surface development method. have.

In Japanese Patent Application Laid-Open No. 7-68214, an amphiphilic polymer layer is polymerized by photopolymerization on a liquid surface in advance, and the substrate is vertically raised with respect to the molecular layer to attach a polymer layer on the substrate, and irradiates and photopolymerizes the organic layer. The manufacturing method of a thin film is disclosed.

In Japanese Patent Laid-Open No. 6-246143, a polydiphenyl acetylene polymer solution is prepared by laminating one or more layers on a porous support membrane using a surface expansion method, and by laminating one or more layers of a polymer solution composed of siloxane polymer on the support membrane. A method for producing a separation composite membrane is disclosed.

The present inventors, unlike the prior art of manufacturing a thin film used for a liquid crystal display device using the surface development method, to prepare a polymer solution by dissolving the biodegradable polymer in different organic solvents, and then spread it on the surface of the biodegradable In the case of preparing the polymer self-supporting film and the biodegradable polymer-ceramic composite self-supporting film, a nano-thick self-supporting film can be manufactured by a very fast and simple process, and the thickness of the self-supporting film can be controlled by using a dielectric constant difference between the organic solvent and water. The organic-inorganic composite self-supporting membrane can be prepared by mixing the nanoporous bioactive ceramics with the biodegradable polymer solution, and can also control their bioactivity, and the organic-inorganic composite self-supporting membrane can be prepared by adsorbing the drug to the nanoporous bioactive ceramics. It can be used as a self-supporting film having a drug release function, salt By uniformly dispersing the mixture in a polymer solution or a polymer-ceramic composite solution, it was found that micropores were formed in the self-supporting membrane to control the permeability of the self-supporting membrane, thereby completing the present invention.

An object of the present invention is to provide a biodegradable polymer self-supporting film and a method of manufacturing the same.

Another object of the present invention is to provide a biodegradable polymer-ceramic composite self-supporting film and a method of manufacturing the same.

It is still another object of the present invention to provide a biodegradable polymer self-supporting membrane and a biodegradable polymer self-supporting membrane having different reactivity with respect to a living body having both surfaces laminated with a biodegradable polymer self-supporting membrane and a method for preparing the same, and to induce tooth or bone formation using the same It is to provide a shielding film for.

In order to achieve the above object, the present invention is a biodegradable polymer self-supporting membrane, biodegradable polymer prepared by developing a polymer solution mixed with a biodegradable polymer, an organic solvent, nanoporous ceramic particles, salt particles and a mixture thereof on the water surface The present invention provides a ceramic composite self-supporting film, a method of manufacturing the same, and a shielding film prepared using the same.

The present invention is a very fast and simple process using the sleep development method, the biodegradable polymer self-supporting membrane and the biodegradable polymer-ceramic which can control the thickness and permeability of the biodegradable polymer self-supporting membrane and the biodegradable polymer-ceramic composite self-supporting membrane It provides a method for producing a composite self-supporting film. The self-supporting film manufactured using the manufacturing method may be applied to various application fields such as a living body (shielding film, dialysis filter, image regeneration / protective film), environment, and electrons.

Hereinafter, the present invention will be described in detail.

The present invention,

Dissolving the biodegradable polymer in an organic solvent to prepare a polymer solution (step 1);

Mixing the salt particles to be uniformly dispersed in the polymer solution prepared in step 1 (step 2);

Dropping the polymer solution mixed in step 2 onto distilled water using a syringe to form a film on the water surface (step 3);

Preparing a polymer tube by rolling up the membrane formed in step 3 using a glass rod (step 4); And

It provides a method for producing a biodegradable polymer self-supporting film comprising the step (step 5) of forming a polymer self-supporting film by cutting the polymer tube in step 4.

In addition, the present invention,

Dissolving the biodegradable polymer in an organic solvent to prepare a polymer solution (step 1);

Mixing the nanoporous ceramic particles, the salt particles, and a mixture thereof to the polymer solution prepared in step 1 so as to be uniformly dispersed (step 2);

Dropping the polymer solution mixed in step 2 onto distilled water using a syringe to form a film on the water surface (step 3);

Preparing a polymer tube by rolling up the membrane formed in step 3 using a glass rod (step 4); And

It provides a method for producing a biodegradable polymer-ceramic composite self-supporting membrane comprising a step (step 5) of cutting the polymer tube in step 4 to form a polymer self-supporting membrane.

1 is a view schematically showing a method for producing a biodegradable polymer self-supporting film and a biodegradable polymer-ceramic composite self-supporting film of the present invention.

The biodegradable polymer self-supporting film and the method of preparing a biodegradable polymer-ceramic composite self-supporting film using a sleep development method, as shown in FIG. 1, of the biodegradable polymer self-supporting film and biodegradable polymer-ceramic composite self-supporting film Permeability, bioactivity, composition, thickness and the like can be adjusted.

The biodegradable polymer self-supporting film and the method for preparing the biodegradable polymer-ceramic composite self-supporting film according to the present invention will be described in detail step by step.

In the method for preparing a biodegradable polymer self-supporting membrane and a biodegradable polymer-ceramic composite self-supporting membrane, step 1 is a step of preparing a polymer solution by dissolving the biodegradable polymer in an organic solvent. The biodegradable polymer is based on an organic solvent It is preferably included in 1 to 20% by weight. The thickness of the polymer self-supporting film produced by adjusting the concentration of the polymer dissolved in the organic solvent within the range of the content of the biodegradable polymer can be adjusted.

Specific examples of biodegradable polymers that can be used in the present invention include poly ε-caprolactone (PCL), poly lactide-co-caprolactone (PLCL), polylactic acid (Poly (lactic acid); PLA), polylactic-co-glycolic acid (Poly (lactic-co-glycolic acid); PLGA), polyamino acid, polyglycolic acid (PG), aliphatic polyester alone and Synthetic polymers such as composites thereof; Natural polymers having biodegradability such as cellulose, lignin, starch and alginic acid; And biological products such as bio polyesters, bio celluloses, polysaccharides, polyamine acids, and the like, but are not necessarily limited thereto.

In addition, PCL, which is typically used in the embodiment of the present invention, can be used in various biomaterials fields due to its good mechanical strength and biocompatibility. It is actively underway. Conventional PCL production methods include a solvent development method, a spin casting method, a two roll milling method, and a biaxially oriented film method, but all of them have difficulty in controlling the film thickness to 1 micrometer or less. In the case of using the PCL self-supporting film production method according to the surface development method of the present invention, it is possible to manufacture an ultra-thin film (<0.1 micrometer) of 1 micrometer or less that overcomes the limitation of PCL self-supporting film thickness control in a very simple manner. The thickness of the self-supporting film is determined by the development characteristics of the polymer solution on the water surface, and in the present invention, it was confirmed that the thickness control of the self-supporting film can be controlled by controlling the surface development characteristics of the solvent in which the polymer is dissolved. Specific examples of the organic solvent that can be used in the present invention are Solvents capable of dissolving biodegradable polymers, such as chloroform, ethyl acetate, dichloromethane, acetone, and the like. The organic solvents have different dielectric constants and solubility in water, and the thicknesses of the biodegradable polymer self-supporting membrane and the biodegradable polymer-ceramic composite self-supporting membrane prepared in consideration of the dielectric constant of the organic solvents to be used may be adjusted. More specifically, it was confirmed that the greater the dielectric constant difference between the organic solvent used and the distilled water, the more excellent the development of the membrane and the thin film production was possible. That is, the dielectric constant is related to the viscosity and surface tension that influence the development degree, and the smaller the dielectric constant, the lower the viscosity, the larger the diffusion coefficient, and the smaller the surface tension. Thus, nonpolar solvents have high dielectric constants, i.e. low dielectric constants for water, which is a polar substance. .

In the method for preparing a biodegradable polymer self-supporting film, step 2 is a step of mixing the salt particles to be uniformly dispersed in the polymer solution prepared in step 1. The salt particles are Sodium chloride, ammonium bicarbonate, sodium bicarbonate, saccharin and the like can be granulated and mixed in the polymer solution. remind Salt particles are preferably contained in 10 to 60% by weight based on the polymer solution. Permeability can be controlled by adjusting the content of salt particles mixed in the polymer solution within the content range of the salt particles.

In addition, in the method for preparing a biodegradable polymer-ceramic composite self-supporting membrane, step 2 is a step of mixing the nanoporous ceramic particles, salt particles, and mixtures thereof uniformly in the polymer solution prepared in step 1 above.

The nanoporous ceramic particles include nanoporous bioactive glass, Low-crystalline apatite, tricalcium phosphate (TCP), such as calcium and phosphorus, including calcium and phosphorus to induce the production of apatite, a bone-like component and may be used a ceramic that induces in vivo degradation of the support, the salt particles Is Sodium chloride, ammonium bicarbonate, sodium bicarbonate, saccharin and the like can be granulated and mixed in the polymer solution. remind Nanoporous ceramics, salt particles and mixtures thereof are preferably contained in 10 to 60% by weight based on the polymer solution. Mixed with the polymer solution The permeability, composition, bioactivity, etc. of the biodegradable polymer-ceramic composite self-supporting membrane prepared by adjusting the content of the nanoporous ceramic particles, the salt particles, and mixtures thereof in the above range can be adjusted. More specifically, to be mixed in the polymer solution The biodegradability of the biodegradable polymer-ceramic composite self-supporting membrane prepared by controlling the content of the nanoporous ceramic particles can be controlled, and the permeability can be controlled by controlling the content of salt particles mixed in the polymer solution. These are mixed in the polymer solution It is easy for those skilled in the art to control the permeability, composition, and bioactivity by adjusting the content of nanoporous ceramic particles, salt particles, and mixtures thereof.

As described above, by mixing the nanoporous bioactive glass powder with the biodegradable polymer solution, high bioactivity can be imparted to the biodegradable polymer-ceramic composite self-supporting membrane to be prepared. And by adsorbing and releasing a bone formation factor, etc., the drug release function can be imparted, and by mixing salt particles as described above, the biodegradable polymer self-supporting membrane is formed into a micro-sized pore structure to control the permeability of the material into the self-supporting membrane. Functions such as permeability and shielding can be adjusted. As described, the nanoporous ceramic particles, salt particles, and mixtures thereof mixed in the polymer solution may be adjusted in kind and content depending on the field of application.

In the method for preparing a biodegradable polymer self-supporting film and a biodegradable polymer-ceramic composite self-supporting film, step 3 is a step of dropping the polymer solution mixed in step 2 onto distilled water using a syringe to form a film on the water surface (Fig. 1). The polymer solution on distilled water It is preferable to drip on 1-10 mm and to develop on water surface. When the polymer solution is dropped at a height greater than 10 mm above the distilled water, it is difficult to form a film on the water surface, and there is a problem that the polymer gel may be stagnated at the bottom of the distilled water in the form of agglomerates.

In the method for producing a biodegradable polymer self-supporting film and a biodegradable polymer-ceramic composite self-supporting film, step 4 is a step of preparing a polymer tube by rolling the film formed in step 3 using a glass rod. The thickness of the polymer tube manufactured in this step may be adjusted in consideration of the number of times the film formed in step 3 is rolled on the glass rod and the thickness of the formed film, and the diameter of the polymer tube may be adjusted according to the diameter of the glass rod to be used. Can be. In addition to the method of manufacturing such a polymer tube, the film can be recovered by slowly passing the film on the water surface using a substrate or a network that can be separated from the film, and can be recovered by controlling from a single layer film to a multilayer film according to the number of laminations.

In the method of manufacturing a biodegradable polymer self-supporting film and a biodegradable polymer-ceramic composite self-supporting film, step 5 is a step of cutting the polymer tube in the step 4 to form a biodegradable polymer self-supporting film and a biodegradable polymer-ceramic composite self-supporting film to be. The tube thus prepared may be excised to obtain a biodegradable polymer self-supporting membrane and a biodegradable polymer-ceramic composite self-supporting membrane having a desired size.

The present invention provides a biodegradable polymer self-supporting film and a polymer-ceramic composite self-supporting film prepared according to the above-described manufacturing method. The biodegradable polymer self-supporting membrane and the polymer-ceramic composite self-supporting membrane according to the present invention have a nano-sized pore structure and / or bioactivity, which can be used for drug release by applying to a living body, and also in fields such as in vitro environment and electrons. Can be applied.

In addition, the present invention provides a method for producing a backside polymer self-supporting film having different characteristics on both sides.

The manufacturing method of the back surface self-supporting film,

Dissolving the biodegradable polymer in an organic solvent to prepare a polymer solution (step A);

Dropping the polymer solution prepared in step A on distilled water using a syringe to form a film on the water surface (step B);

Preparing a polymer tube by rolling up the polymer self-supporting film prepared in step B using a glass rod (step C);

Mixing the biodegradable polymer in a polymer solution prepared by dissolving it in an organic solvent to uniformly disperse the nanoporous ceramic (step D);

Dropping the nanoporous ceramic-polymer solution mixed in step D onto distilled water using a syringe to form a nanoporous ceramic-polymer composite self-supporting film (step E);

Preparing a tube composed of a polymer alone on one side and a nanoporous ceramic-polymer composite on the opposite side by rolling the nanoporous ceramic-polymer composite self-supporting membrane formed in step E on the polymer tube prepared in step C. Step F); And

Cutting the polymer tube in step F to form a polymer / nanoporous ceramic-polymer composite self-supporting film having different components on both sides (step G).

The method for manufacturing a backside polymer self-supporting film composed of different compositions on both sides will be described step by step.

Step A is a step of preparing a polymer solution by dissolving the biodegradable polymer in an organic solvent. Step A is a step corresponding to step 1 of the method for preparing a biodegradable polymer self-supporting membrane described above, and is performed in the same manner.

Step B is a step of dropping the polymer solution prepared in step A on distilled water using a syringe to form a film on the water surface. Step B is a step corresponding to step 3 of the method for preparing a biodegradable polymer self-supporting membrane described above, and is performed in the same manner.

The step C is a step of recovering the self-supporting film developed in the step B by using a glass rod of a suitable thickness, etc. in the form of a tube, and recovering the film. It is possible to use a detachable substrate, a net, or the like.

In the step D, the nanoporous ceramic is uniformly dispersed in the polymer solution prepared by dissolving the biodegradable polymer in an organic solvent. The biodegradable polymer used in step D may be the same or different polymers as the biodegradable polymer used in step A according to the application to be applied.

Step E is a step of dropping the nanoporous ceramic-polymer solution mixed in Step D onto distilled water using a syringe to form a composite membrane on the water surface. The nanoporous ceramic-polymer solution mixed in the step D is preferably dropped at a point of 1 to 10 mm above the water surface.

In the step F, the nanoporous ceramic-polymer composite self-supporting film developed in the step E is superimposed on a tube or a film formed of the polymer self-supporting film recovered in the step C. It can be used by laminating.

The step G is a step of forming the tube into a self-supporting film shape by cutting the tube manufactured in the step F.

Steps C and F to G are steps corresponding to steps 4 and 5 of the method for preparing a biodegradable polymer self-supporting membrane, respectively, and are performed in the same manner.

In addition, sodium chloride, ammonium bicarbonate, sodium bicarbonate, saccharin in the polymer solution in the step A and step D to form a micro-sized pore structure on both sides of the prepared self-supporting polymer self-supporting film Salt particles, such as these, can be mixed further.

The present invention provides a backside polymer self-supporting film prepared according to the above-described manufacturing method.

Both sides of the backside polymer self-supporting film according to the present invention will have different characteristics. More specifically, in one embodiment of the present invention, the inside of the backside polymer self-supporting membrane is formed only of the PCL polymer self-supporting membrane with low bioactivity, and the outside of the backside self-supporting membrane is a nanoporous bioactive glass uniformly dispersed It may be formed of a PCL polymer self-supporting film. In another embodiment of the present invention, the inside of the backside polymer self-supporting film is formed of a PCL-NaCl polymer self-supporting film, and the outside of the backing polymer self-supporting film is formed of a PCL-NaCl polymer self-supporting film in which nanoporous bioactive glass is dispersed. Salts such as NaCl may be used by leaching after washing the self-supporting membrane. As described above, the backside polymer self-supporting film of the present invention may be prepared to impart bioactivity for inducing teeth or bone formation on one side and to suppress its formation on the other side, as required by the shielding film.

Therefore, the present invention can provide a shielding film manufactured using the backside polymer self-supporting film.

Hereinafter, the present invention will be described in more detail with reference to Examples and drawings. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

Example 1 Preparation of Biodegradable Polymer Self-supporting Film Using PCL

A polymer solution was prepared by uniformly dissolving 1 g of biodegradable polymer polycaprolactone (PCL) in 10 ml of chloroform, which is a nonpolar solvent. The prepared polymer solution was transferred to a syringe and dropped one drop at a point about 5 mm above the distilled water contained in the wide chaale through a needle. As a result, a very thin biodegradable polymer self-supporting film was formed at the same time as the dropping of the polymer solution, and a scanning electron microscope (SEM) photograph of the formed biodegradable polymer self-supporting film was shown in FIG. 2. The thickness of the formed film was about 80-100 nm and the width of the film was about 6-10 cm. The thickness of the membrane can be controlled according to the concentration of the polymer, and if the dropping distance of the solution is too far from the surface, the formation of the membrane is difficult and stagnated at the bottom of the distilled water in the form of a polymer gel mass.

Example 2 Preparation of Biodegradable Polymer Self-supporting Film Using PLCL

A polymer solution was prepared by uniformly dissolving 1 g of a biodegradable polymer poly lactide-co-caprolactone (PLCL) in 10 ml of chloroform, which is a nonpolar solvent. The prepared polymer solution was transferred to a syringe and dropped one drop at a point about 5 mm above the distilled water contained in the wide chaale through a needle. As a result, a very thin biodegradable polymer self-supporting film was formed at the same time as the dropping of the polymer solution, and the SEM photograph of the formed biodegradable polymer self-supporting film is shown in FIG. 3. The thickness of the formed film was about 100 nm, and the width of the film was about 5-10 cm. The self-supporting film was confirmed to have excellent elasticity according to the properties of the PLCL polymer.

Example 3 Preparation of Biodegradable Polymer-Ceramic Composite Self-supporting Film Using PCL

After dissolving the biodegradable polymer PCL in chloroform, nanoporous ceramic particles having nano-sized pores, in particular, nanopowder of nanoporous bioactive glass having excellent bioactivity (Korea Patent 10-0831348) were prepared and weighed 40 wt. It was mixed in the polymer solution in% content. The polymer solution was added dropwise onto the water surface of the Shaale using a syringe. As a result, a thin biodegradable polymer-ceramic composite self-supporting film was formed on the water surface. The SEM image of the biodegradable polymer-ceramic composite self-supporting film formed above is shown in FIG. 4. Figure 4 (a) is a SEM photograph of the side cross-section of the formed biodegradable polymer-ceramic composite self-supporting film, Figure 4 (b) is a SEM photograph of the surface of the formed biodegradable polymer-ceramic composite self-supporting film. As shown in FIG. 4, the thickness of the film (about 500-1000 nm) was increased by mixing the nanoporous ceramic, and the biodegradable polymer-ceramic composite self-supporting film having a uniform ceramic distribution was It was confirmed that it was formed.

Example 4 Preparation of Biodegradable Polymer Self-supporting Film Using PCL

A biodegradable polymer self-supporting membrane was formed in the same manner as in Example 1 except that 40% by weight of sodium chloride particles were mixed in a polymer solution in which biodegradable polymer PCL was dissolved in chloroform, and then washed with water. The SEM image of the biodegradable polymeric self-supporting membrane having a micro-sized pore structure after washing with water is shown in FIG. 5. As shown in FIG. 5, it was confirmed that a biodegradable polymer self-supporting membrane having a micro-sized pore structure reflecting the size of salt particles may be formed.

Example 5 Preparation of Biodegradable Polymer-Ceramic Composite Self-supporting Film Using PCL

The biodegradable polymer-ceramic composite self-supporting membrane was prepared in the same manner as in Example 1 except that the nanopowder of nanoporous bioactive glass and sodium chloride particles were mixed in a polymer solution in which biodegradable polymer PCL was dissolved in chloroform. Formed, and then washed with water. After washing with water, the SEM image of the biodegradable polymer-ceramic composite self-supporting membrane in which the micro-sized pore structure was formed is shown in FIG. 6. As shown in FIG. 6, when the polymer solution prepared by mixing all of the polymer, the nanoporous ceramic particles, and the salt particles was applied to the surface development method, the biodegradable polymer-ceramic composite self-supporting film was formed.

Example 6 Preparation of Biodegradable Polymer Tube Using PCL

A polymer solution was prepared by uniformly dissolving 1 g of biodegradable polymer PCL in 10 ml of chloroform, which is a nonpolar solvent, and adding sodium chloride particles to the prepared polymer solution. After mixing by weight percent content, the polymer solution was transferred to a syringe and dropped by one drop at about 5 mm above the distilled water contained in the wide chaale through a needle. As a result, a very thin transparent film was formed on the water surface simultaneously with the dropping of the polymer solution. The formed film was rolled up on a glass rod in the manner shown in FIG. 1 to prepare a polymer tube, and a photograph was taken of the prepared polymer tube and shown in FIG. 7. Photographs were taken for FIG. 8. As illustrated in FIGS. 7 and 8, the biodegradable polymer self-supporting membrane according to the present invention may be recovered in the form of a tube.

Example 7 Preparation of Backside Polymer Self-Containing Film

A polymer solution was prepared by uniformly dissolving 1 g of biodegradable polymer PCL in 10 ml of non-polar solvent, chloroform, and transferring the polymer solution into a syringe at about 5 mm above distilled water in a wide range of chalets through a needle. Dropped, and a very thin transparent film formed on the surface of the water. The formed polymer self-supporting film is rolled up to a glass rod and recovered. Thereafter, 1 g of a biodegradable polymer PCL was uniformly dissolved in 10 ml of chloroform, which is a nonpolar solvent, to prepare a polymer solution. The bioactive glass powder was mixed with the prepared polymer solution in a content of 50 wt% based on PCL, and then the polymer solution. Was transferred to a syringe and dropped one drop onto the water surface through a needle to form a polymer-ceramic composite self-supporting film. The formed polymer-ceramic composite self-supporting film is recovered by overlapping the glass rod from which the polymer film was previously collected. Photographs of both surfaces of the backside polymer self-supporting film obtained by cutting the prepared polymer tube are shown in FIG. 9. As shown in FIG. 9, the inner surface of the prepared self-supporting polymer self-supporting film was formed of PCL only, and the outer surface of the prepared self-supporting polymer self-supporting film was composed of a bioactive glass-PCL composite.

Example 8 Fabrication of Backside Polymer Self-Containing Film

After dissolving 1 g of biodegradable polymer PCL uniformly in 10 ml of chloroform, which is a nonpolar solvent, sodium chloride particles were mixed in an amount of 40% by weight relative to PCL to prepare a polymer solution, and the polymer solution was transferred to a syringe through a needle. A drop was dropped about 5 mm above the distilled water contained in the wide chaele, resulting in a very thin transparent polymer freestanding film on the surface of the water. The formed polymer self-supporting film is wound up and collected using a glass rod. Thereafter, 1 g of a biodegradable polymer PCL was uniformly dissolved in 10 ml of chloroform, which is a nonpolar solvent, to prepare a polymer solution, and sodium chloride particles and bioactive glass powder were mixed in the prepared polymer solution in a content of 50 wt% based on PCL. Thereafter, the polymer solution was transferred to a syringe and dropped one drop onto the water surface through a needle to form a polymer-ceramic composite self-supporting film. The formed polymer-ceramic composite self-supporting film is wound on a previously recovered polymer tube and recovered. As a result, a backside polymer tube made of a component having different surfaces on both sides was formed, and this was cut off to obtain a backside self-supporting film. The inner surface of the prepared backing polymer self-supporting film was formed of PCL-NaCl, and the outer surface of the prepared backing polymer self-supporting film was composed of bioactive glass-PCL-NaCl. NaCl was precipitated by washing with distilled water to form micro-sized pores in the NaCl portion.

Experimental Example 1 Bioactivity Test of a Backside Polymer Self-Containing Film

After immersing the backside self-supporting film prepared in Example 7 into the analog solution, it was observed whether apatite crystals containing the living bone and similar components were formed. 10 and 11, respectively, were photographed with SEM images after the immersion of the analogous liquid on the inner surface and the outer surface of the self-supporting polymer self-supporting film. As shown in FIG. 10, even after 24 hours of immersion in the analogous fluid, apatite crystals were hardly formed on the inner surface of the backside self-supporting polymer film formed solely of PCL. However, as shown in FIG. 11, the bioactive glass-PCL composite was used. It can be seen that apatite crystals were formed on the entire surface of the formed backside polymer self-supporting film. As a result, it was confirmed that high bioactive functions can be imparted to the backing polymer self-supporting membrane by mixing and using nanoporous bioactive ceramics.

Experimental Example 2 Bioactivity Test of the Backside Polymer Self-Containing Film

The backside polymer self-supporting film prepared in Example 8 was deposited in the analogous fluid, and then the formation of apatite crystals containing the living bone and similar components was observed. 12 and 13 were taken by SEM images at 0h and 24h after being deposited in the analogous liquid on the inner and outer surfaces of the backside self-supporting polymer self-supporting film. As shown in FIG. 12, even after 24 hours of immersion in the analog solution, almost no apatite crystals were formed on the inner surface of the backside self-supporting polymer film formed solely of PCL-NaCl, but as shown in FIG. 13, the bioactive glass-PCL It can be seen that apatite crystals were formed on the entire surface of the backside self-supporting film formed of the -NaCl complex. Thus, the backing polymer self-supporting film according to the present invention is well required for the characteristics required for the shielding film, that is, the function of inducing teeth or bone formation on one side but the function of inducing teeth or bone formation on the other side is well suppressed. It can be seen that.

Experimental Example 3 Thickness Control of Biodegradable Polymer Self-supporting Film According to Organic Solvents Used

The biodegradable polymer PCL was dissolved in an organic solvent having different dielectric constants and solubility in water, and spread on the surface of the water to form a film. The thickness of the formed film according to the organic solvent used was measured and shown in Table 1 below.

As shown in Table 1, the smaller the dielectric constant of the organic solvent used (the larger the dielectric constant difference) was, the better the development on the water surface of the prepared biodegradable polymer self-supporting film was, and the thin film was formed. PCL dissolved in chloroform (dielectric constant 4.8) has a film thickness of about 80-100 nm and forms a wide spread film, whereas PCL dissolved in acetone (dielectric constant 21) has a thickness of about 5000 nm. It was confirmed that the biodegradable polymer self-supporting film was not formed. Dimethylformamide (DMF), which has low solubility in water and a large dielectric constant, that is, has a low dielectric constant difference from water, is unable to form a biodegradable self-supporting film and has a tendency to settle down to the surface. Seemed. Thus, the thickness of the film to be prepared can be adjusted by selecting an organic solvent of 0.3 times or less with respect to the dielectric constant of water described in Table 1 above.

1 is a view schematically showing a method for producing a biodegradable polymer self-supporting film and a biodegradable polymer-ceramic composite self-supporting film of the present invention.

FIG. 2 is a SEM photograph of the side surface of the biodegradable polymer self-supporting film prepared in Example 1. FIG.

Figure 3 is a SEM photograph of the side of the biodegradable polymer self-supporting film prepared in Example 2.

Figure 4 (a) is a SEM photograph of the side cross-sectional view of the biodegradable polymer-ceramic composite self-supporting film prepared in Example 3, Figure 4 (b) is a biodegradable polymer-ceramic composite self-supporting prepared in Example 3 SEM photograph of the surface of the film.

FIG. 5 is a SEM photograph of a plane of the biodegradable polymer self-supporting film prepared in Example 4. FIG.

FIG. 6 is a SEM photograph of a plane of the biodegradable polymer-ceramic composite self-supporting film prepared in Example 5. FIG.

7 is a photograph of the polymer tube prepared in Example 6.

8 is a photograph taken after washing the polymer tube prepared in Example 6.

9 (a) is a photograph of the inner surface of the backside self-supporting polymer film prepared in Example 7, Figure 9 (b) is a photograph of the outer surface of the backside biodegradable polymer self-supporting film prepared in Example 7 One picture.

10 (a) is a SEM photograph of the inner surface of the back polymer self-supporting film immediately after depositing the back polymer self-supporting film in the analogous fluid in Experimental Example 1, and FIG. 10 (b) is the back surface self-supporting polymer in the analog fluid The SEM image of the inner surface of the backside self-supporting film after 24 hours after the film was deposited.

FIG. 11 (a) is a SEM photograph of the outer surface of the back polymer self-supporting film immediately after depositing the back polymer self-supporting film in the analogous fluid in Experimental Example 1, and FIG. 11 (b) is the back surface self-supporting polymer in the analog fluid. SEM image of the outer surface of the backside self-supporting film after 24 hours after the film was deposited.

12 (a) is a SEM photograph of the inner surface of the backside polymer self-supporting film immediately after depositing the backside polymer self-supporting film in the analogous fluid in Experimental Example 2, and FIG. 12 (b) shows the backside self-supporting polymer in the analogous fluid. The SEM image of the inner surface of the backside self-supporting film after 24 hours after the film was deposited.

FIG. 13A is a SEM photograph of the outer surface of the backside polymer self-supporting membrane immediately after depositing the backside polymer self-supporting membrane in the analogous fluid in Experimental Example 2, and FIG. 13B is the backside self-supporting polymer in the body fluid SEM image of the outer surface of the backside self-supporting film after 24 hours after the film was deposited.

* Short description for the drawing symbols *

1: polymer solution 2: distilled water

3: polymer self-supporting film 4: glass rod

5: polymer tube

Claims (32)

Dissolving the biodegradable polymer in an organic solvent to prepare a polymer solution (step 1); Mixing the salt particles to be uniformly dispersed in the polymer solution prepared in step 1 (step 2); Dropping the polymer solution mixed in step 2 onto distilled water using a syringe to form a film on the water surface (step 3); Preparing a polymer tube by rolling up the membrane formed in step 3 using a glass rod (step 4); And Cutting the polymer tube in step 4 to form a polymer self-supporting film (step 5) Method for producing a biodegradable polymer self-supporting film comprising a. The method of claim 1, wherein the biodegradable polymer in step 1 with respect to the organic solvent Method for producing a biodegradable polymer self-supporting film, characterized in that contained in 1 to 20% by weight. The method of claim 1, wherein the biodegradable polymer in step 1 is poly ε-caprolactone (PCL), poly lactide-co-caprolactone (PLCL), polylactic acid (Poly (lactic acid) PLA), polylactic-co-glycolic acid (PLGA), poly amino acid, polyglycolic acid (PG), aliphatic polyester And at least one biodegradable polymer selected from the group consisting of cellulose, lignin, starch, alginic acid, bio polyester, bio cellulose, polysaccharides, and polyamine acids. The method of claim 1, wherein the organic solvent in step 1 has a dielectric constant of 0.3 times or less relative to the dielectric constant of water to increase the degree of development of the polymeric self-supporting film that is developed on the surface of the water. . The method of claim 4, wherein the organic solvent is selected from the group consisting of chloroform, ethyl acetate, dichloromethane and acetone. The method of claim 1, wherein the salt particles in step 2 is selected from the group consisting of sodium chloride, ammonium bicarbonate, sodium bicarbonate and saccharin. According to claim 1, wherein the salt particles in step 2 is a method for producing a biodegradable polymer self-supporting film, characterized in that contained in 10 to 60% by weight relative to the polymer. The method of claim 1, wherein the polymer solution in Step 3 is dropped on 1 to 10 mm above distilled water using a syringe. Biodegradable polymer self-supporting film prepared according to the method of claim 1. Dissolving the biodegradable polymer in an organic solvent to prepare a polymer solution (step 1); Mixing the nanoporous ceramic particles, the salt particles, and a mixture thereof to the polymer solution prepared in step 1 so as to be uniformly dispersed (step 2); Dropping the polymer solution mixed in step 2 onto distilled water using a syringe to form a film on the water surface (step 3); Preparing a polymer tube by rolling up the membrane formed in step 3 using a glass rod (step 4); And Cutting the polymer tube in step 4 to form a polymer self-supporting film (step 5) Method for producing a biodegradable polymer-ceramic composite self-supporting film comprising a. The method according to claim 10, wherein the biodegradable polymer in step 1 with respect to the organic solvent Method for producing a biodegradable polymer-ceramic composite self-supporting membrane, characterized in that contained in 1 to 20% by weight. The method of claim 10, wherein the biodegradable polymer in step 1 is poly ε-caprolactone (PCL), poly lactide-co-caprolactone (PLCL), polylactic acid (Poly (lactic acid) PLA), polylactic-co-glycolic acid (PLGA), poly amino acid, polyglycolic acid (PG), aliphatic polyester And at least one biodegradable polymer selected from the group consisting of cellulose, lignin, starch, alginic acid, bio polyester, bio cellulose, polysaccharides, and polyamine acids. The self-degradable biodegradable polymer-ceramic composite of claim 10, wherein the organic solvent in step 1 has a dielectric constant of 0.3 times or less with respect to the dielectric constant of water to increase the degree of development of the polymer self-supporting film that is developed on the water surface. Method of Making Membranes. The method of claim 13, wherein the organic solvent is selected from the group consisting of chloroform, ethyl acetate, dichloromethane, and acetone. The biodegradable polymer-ceramic composite according to claim 10, wherein the nanoporous ceramic particles in step 2 are ceramic particles which induce the production of nanoporous bioactive glass powder and apatite and induce degradation of the support in vivo. Method of producing a self-supporting film. The method of claim 10, wherein the salt particles in the step 2 is selected from the group consisting of sodium chloride, ammonium bicarbonate, sodium bicarbonate and saccharin. The method of claim 10, wherein the nanoporous ceramic particles, the salt particles, and a mixture thereof are included in an amount of 10 wt% to 60 wt% with respect to the polymer. The method of claim 10, wherein the polymer solution in step 3 is dropped on 1 to 10 mm above distilled water using a syringe. Biodegradable polymer-ceramic composite self-supporting membrane prepared according to the method of claim 10. The biodegradable polymer-ceramic composite self-supporting membrane of claim 19, wherein the biodegradable polymer-ceramic composite self-supporting membrane has a drug release function due to the nanopore structure. Dissolving the biodegradable polymer in an organic solvent to prepare a polymer solution (step A); Dropping the polymer solution prepared in step A onto distilled water using a syringe to form a film on the water surface (step B); Preparing a polymer tube by rolling up the polymer self-supporting film prepared in step B using a glass rod (step C); Mixing the biodegradable polymer in a polymer solution prepared by dissolving it in an organic solvent to uniformly disperse the nanoporous ceramic (step D); Dropping the nanoporous ceramic-polymer solution mixed in step D onto distilled water using a syringe to form a nanoporous ceramic-polymer composite self-supporting film (step E); Preparing a tube composed of a polymer alone on one side and a nanoporous ceramic-polymer composite on the opposite side by rolling the nanoporous ceramic-polymer composite self-supporting membrane formed in step E onto the polymer tube prepared in step C. Step F); And Cutting the polymer tube in step F to form a polymer / nanoporous ceramic-polymer composite self-supporting film having different components on both sides (step G) Method for producing a backside self-supporting polymer film comprising a. The method of claim 21, wherein the biodegradable polymer in the step A and step D with respect to the organic solvent Method for producing a backside self-supporting film, characterized in that contained in 1 to 20% by weight. The method of claim 21, wherein the biodegradable polymer in step A is poly ε-caprolactone (PCL), poly lactide-co-caprolactone (PLCL), polylactic acid (Poly (lactic acid) PLA), polylactic-co-glycolic acid (PLGA), poly amino acid, polyglycolic acid (PG), aliphatic polyester And at least one biodegradable polymer selected from the group consisting of cellulose, lignin, starch, alginic acid, bio polyester, bio cellulose, polysaccharides, and polyamine acids. 22. The method of claim 21, wherein the organic solvent in steps A and D is selected from the group consisting of chloroform, ethyl acetate, dichloromethane and acetone. 22. The method of claim 21, wherein the biodegradable polymer in step D is the same biodegradable polymer or another biodegradable polymer as the biodegradable polymer used in step A. The method of claim 21, wherein the nanoporous ceramic particles in the step D is a ceramic particle to induce the production of nanoporous bioactive glass powder and apatite and induce the in vivo degradation of the support, the preparation of the backing polymer self-supporting film Way. 22. The method of claim 21, wherein the polymer solution in step A and step D further comprises salt particles. 28. The method of claim 27, wherein the salt particles are selected from the group consisting of sodium chloride, ammonium bicarbonate, sodium bicarbonate, and saccharin. 22. The method of claim 21, wherein the nanoporous ceramic particles in step D are included in an amount of 10 to 60 wt% based on the polymer. 22. The method of claim 21, wherein the polymer solution in step B is added dropwise on 1 to 10 mm above distilled water. A backside self-supporting film prepared according to the method of claim 21. A shielding film for inducing tooth or bone formation produced using the backside self-supporting film of claim 31.

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