KR102806052B1 - Medical Silicone Gel Composition And Method For Manufacturing The Same - Google Patents

Abstract

The present invention relates to a medical silicone gel composition and a manufacturing method thereof, and more specifically, the composition of the medical silicone gel used as an adhesive according to the present invention comprises 60 to 85 wt% of a main agent composed of a polysiloxane polymer and a silicate resin, 0.1 to 1.5 wt% of a crosslinker, 8 to 38 wt% of dimethicone as a thickener, 0.1 to 5 wt% of 1-ethylcyclohexanol as a retarder, 0.2 to 1 wt% of 1,4-butanediol as a chain extender, 0.4 to 2 wt% of a platinum catalyst as a hardener, and 0.1 to 10 wt% of a zinc oxide-carbon nanotube polymer (ZnO-CNT polymer) as an antibacterial agent, and the manufacturing method thereof comprises: a) a polysiloxane polymer and a silicate resin; A mixing step of mixing 60 to 85 wt% of a main body composed of a silicate resin, 0.1 to 1.5 wt% of a crosslinking agent, 8 to 38 wt% of dimethicone as a thickener, 0.1 to 5 wt% of 1-ethylcyclohexanol as a retarder, and 0.2 to 1 wt% of 1,4-butanediol as a chain extender; b) a first depressurizing step of mixing and drying under a reduced pressure of 0.1 to 1 atm, 50 to 60°C, and 17 to 19 hours; c) a first defoaming step of removing air bubbles at a pressure of 0.1 to 0.9 atm; d) a second mixing step of mixing 0.4 to 2 wt% of a platinum-based catalyst as a curing agent; e) a second depressurizing step of mixing at 0.8 to 1 atm. The present invention relates to a medical silicone gel composition and a method for manufacturing the same, characterized by comprising: f) a second defoaming step of removing air bubbles at a pressure of 0.1 to 0.9 atm; g) an antibacterial agent mixing step of mixing 0.1 to 10 wt% of a zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer), which is an antibacterial agent; and h) a third mixing and defoaming step.

Description

Medical Silicone Gel Composition And Method For Manufacturing The Same

The present invention relates to a medical silicone gel composition and a manufacturing method thereof, and more specifically, the composition of the medical silicone gel used as an adhesive according to the present invention comprises 60 to 85 wt% of a main agent composed of a polysiloxane polymer and a silicate resin, 0.1 to 1.5 wt% of a crosslinker, 8 to 38 wt% of dimethicone as a thickener, 0.1 to 5 wt% of 1-ethylcyclohexanol as a retarder, 0.2 to 1 wt% of 1,4-butanediol as a chain extender, 0.4 to 2 wt% of a platinum catalyst as a hardener, and 0.1 to 10 wt% of a zinc oxide-carbon nanotube polymer (ZnO-CNT polymer) as an antibacterial agent, and the manufacturing method thereof comprises: a) a polysiloxane polymer and a silicate resin; A mixing step of mixing 60 to 85 wt% of a main body composed of a silicate resin, 0.1 to 1.5 wt% of a crosslinking agent, 8 to 38 wt% of dimethicone as a thickener, 0.1 to 5 wt% of 1-ethylcyclohexanol as a retarder, and 0.2 to 1 wt% of 1,4-butanediol as a chain extender; b) a first depressurizing step of mixing and drying under a reduced pressure of 0.1 to 1 atm, 50 to 60°C, and 17 to 19 hours; c) a first defoaming step of removing air bubbles at a pressure of 0.1 to 0.9 atm; d) a second mixing step of mixing 0.4 to 2 wt% of a platinum-based catalyst as a curing agent; e) a second depressurizing step of mixing at 0.8 to 1 atm. The present invention relates to a medical silicone gel composition and a method for manufacturing the same, characterized by comprising: f) a second defoaming step of removing air bubbles at a pressure of 0.1 to 0.9 atm; g) an antibacterial agent mixing step of mixing 0.1 to 10 wt% of a zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer), which is an antibacterial agent; and h) a third mixing and defoaming step.

Conventionally, medical adhesives are used in disposable bandages, plasters, surgical adhesive tapes, and attachments. The raw materials for the adhesives include acrylate and silicone, and ester rubber, phenol resin, etc. are used as auxiliary agents. Low molecular weight substances such as pajama oil and polyisobutylene are combined to create sticky adhesiveness, so unlike adhesives, they can be easily attached and removed.

Recently, adhesives that contain drugs inside the adhesive and supply the drugs to the human body through the skin when attached to the skin are being researched and developed. The main key points of such adhesives are that they maintain adhesiveness when re-adhesived and that they do not cause skin irritation, toxicity, allergies, or unpleasant odors. In particular, they must have the essential function of a medical product, which is antibacterial properties that include preventing bacterial invasion from the outside. However, since the wound surface undergoes a sterilization process in the pretreatment stage, most medical adhesives focus on wettability and moisture permeability to prevent drying and festering of the wound surface rather than antibacterial properties. Development is currently being focused on the function of maintaining adhesiveness when re-adhesive.

However, medical adhesives must inevitably have basic bacterial invasion prevention and antibacterial properties from the outside. Regarding this, Korean Patent Publication No. 10-1731612 discloses a medical silicone adhesive composition manufactured by mixing a block silicone hydrogen polymer as a crosslinking agent, a linear silicone hydrogen polymer as a chain extender, a vinyl mequinol resin as an adhesion enhancer, and ethylcyclohexanol as a retarder to a silicone vinyl polymer to form a main agent, and mixing a platinum-based catalyst as a hardener thereto. However, due to the characteristics of the vinyl mequinol resin used as an adhesion enhancer, although high adhesion can be implemented when attached to a dry surface, the hardness of the adhesive surface increases, which can cause pain to the skin when removed after attachment to the skin. This has the problem that it is closer to an adhesive than an adhesive, and above all, it focuses on adhesion rather than antibacterial properties.

Therefore, there is an urgent need for research on an antibacterial functional medical silicone gel composition and a method for manufacturing the same, which can maintain an improved antibiotic or antibacterial effect in medical adhesives used on human wounds or areas where bacterial invasion is easily possible.

No. 10-1731612 (Title of invention: Medical silicone adhesive composition, Publication date: May 23, 2017)

The medical silicone gel composition and its manufacturing method of the present invention have the following purposes.

(1) The purpose of the present invention is to provide a medical composition used as an adhesive that has improved antibacterial properties and can maintain the antibacterial properties even after long-term use, thereby inhibiting bacterial infection or the formation of a biofilm that is the source of bacterial infection, and a method for producing the same.

(2) Another object of the present invention is to provide a polymer having improved antibacterial properties without side effects such as antibiotic resistance, and having a lifespan that can be easily determined based on the electrostatic capacity of the polymer, and thus having adhesive performance determined accordingly, so that it can be used for various medical purposes.

(3) Another object of the present invention is to provide a medical silicone gel composition and a method for manufacturing the same, which is free from irritation, toxicity, allergic phenomena, and unpleasant odor that may occur in medical adhesives, and which maintains adhesive performance when re-adhesive.

The medical silicone gel composition of the present invention is characterized by comprising: 60 to 85 wt% of a main agent composed of a polysiloxane polymer and a silicate resin, 0.1 to 1.5 wt% of a crosslinker, 8 to 38 wt% of dimethicone as a thickener, 0.1 to 5 wt% of 1-ethylcyclohexanol as a retarder, 0.2 to 1 wt% of 1,4-butanediol as a chain extender, 0.4 to 2 wt% of a platinum-based catalyst as a curing agent, and 0.1 to 10 wt% of a zinc oxide-carbon nanotube polymer (ZnO-CNT polymer) as an antibacterial agent.

It is characterized in that the mixing order of the above composition is preferably in the order of the subject, chain extender, thickener, retardant, crosslinking agent, hardener, and antibacterial agent.

a) The above antibacterial agent, zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer), is composed of zinc oxide, carbon nanotubes, and a nitrate complex as shown in the structural formula 1 below,

b) The above antibacterial agent is a pretreated zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer), and the pretreatment process is characterized by mixing the zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) with one selected from among methanol, ethanol, xylene, toluene, distilled water, hexane, acetone, and isobutyl alcohol as a solvent, irradiating the ZnO-CNT Polymer with 5 to 23 kGy of electron beam, and then extracting the zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) by a reduced pressure drying method.

[Structural formula 1]

The present invention relates to a method for manufacturing a medical silicone gel composition used as an adhesive.

a) A mixing step (S10) of mixing 60 to 85 wt% of a main component composed of a polysiloxane polymer and a silicate resin, 0.1 to 1.5 wt% of a crosslinker, 8 to 38 wt% of dimethicone as a thickener, 0.1 to 5 wt% of 1-ethylcyclohexanol as a retarder, and 0.2 to 1 wt% of 1,4-butanediol as a chain extender;

b) 1st depressurization step (S20) of mixing and drying under reduced pressure at 0.1 to 1 atm, 50 to 60 ℃, for 17 to 19 hours;

c) Primary defoaming step (S30) to remove air bubbles at a pressure of 0.1 to 0.9 atm;

d) Second mixing step (S40) of mixing 0.4 to 2 wt% of a platinum catalyst as a curing agent;

e) Second depressurization stage (S50) mixing at 0.8 to 1 atm;

f) Secondary defoaming step (S60) for removing air bubbles at a pressure of 0.1 to 0.9 atm;

g) Antibacterial agent mixing step (S70) mixing 0.1 to 10 wt% of zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer), which is an antibacterial agent; and

h) It consists of a third mixing and defoaming step of first mixing the mixed composition using a homomixer under conditions of less than 1 atm at 1,000 to 10,000 rpm, 18 to 22°C, for 1 to 4 hours, and second mixing at 300 to 800 rpm, 18 to 22°C, for 4 to 8 hours.

The above mixing step is characterized by mixing the subject, chain extender, thickener, retarder, and cross-linking agent in that order.

The above antibacterial agent uses a pretreated zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer), and the pretreatment process is characterized by mixing the zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) with one selected from among solvents such as methanol, ethanol, xylene, toluene, distilled water, hexane, acetone, and isobutyl alcohol, irradiating the mixture with electron rays at 5 to 23 kGy, and then extracting the zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) by a reduced pressure drying method.

The present invention has the following effects.

(1) The present invention provides a medical composition used as an adhesive that has improved antibacterial properties and can maintain antibacterial properties even after long-term use, thereby inhibiting bacterial infection or the formation of a biofilm that is the source of bacterial infection, and a method for producing the same.

(2) The present invention has improved antibacterial properties without the addition, application or coating of a separate antibiotic, and has no side effects such as antibiotic resistance. Its lifespan can be easily determined based on the electrostatic capacity of the polymer, and its adhesive performance is determined accordingly, so it can be used for various medical purposes.

(3) The present invention provides a medical silicone gel composition and a method for manufacturing the same, which minimizes skin irritation, toxicity, allergic phenomena, and odor causing rejection that may occur from medical adhesives, and maintains adhesive performance not only during initial adhesion but also during re-adhesion.

(4) In addition to its use as an adhesive, the present invention can be used as a drug delivery silicone gel by adding a drug, and can deliver a drug directly through the skin.

(5) The present invention provides a medical adhesive composition having improved adhesive strength and reduced cytotoxicity by removing air bubbles generated during composition mixing and uniformly distributing the molecules of the mixture through multiple depressurization and defoaming processes.

FIG. 1 is a diagram showing a time-series manufacturing method of a medical silicone gel composition according to a preferred embodiment of the present invention.
FIG. 2 is a photograph of an antibacterial test for several examples manufactured according to a method for manufacturing a medical silicone gel composition according to a preferred embodiment of the present invention.

First, before going into a detailed description of the present invention, if it is determined that a detailed description of a known technology or configuration related to the present invention may unnecessarily obscure the gist of the present invention, the detailed description will be omitted.

In addition, the terms described below are terms defined in consideration of their functions in the present invention, and may vary depending on the intention or custom of the user or operator, and therefore, their definitions should be made based on the contents of the entire specification describing the “medical silicone gel composition and its manufacturing method” according to the present invention.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. The singular forms used herein also include the plural forms unless the phrases clearly indicate the opposite.

The term "comprising" as used herein specifies particular characteristics, regions, integers, steps, operations, elements and/or components, but does not exclude the presence or addition of other particular characteristics, regions, integers, steps, operations, elements, components and/or groups.

All terms, including technical and scientific terms, used in this specification have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs. Terms defined in the dictionary are additionally interpreted as having a meaning consistent with the relevant technical literature and the presently disclosed content, and are not interpreted in an ideal or very formal sense unless defined.

The medical silicone gel composition of the present invention is characterized by comprising: 60 to 85 wt% of a main agent composed of a polysiloxane polymer and a silicate resin, 0.1 to 1.5 wt% of a crosslinker, 8 to 38 wt% of dimethicone as a thickener, 0.1 to 5 wt% of 1-ethylcyclohexanol as a retarder, 0.2 to 1 wt% of 1,4-butanediol as a chain extender, 0.4 to 2 wt% of a platinum-based catalyst as a curing agent, and 0.1 to 10 wt% of a zinc oxide-carbon nanotube polymer (ZnO-CNT polymer) as an antibacterial agent.

The above-mentioned subject matter consists of two components: a polysiloxane polymer and a silicate resin. The siloxane polymer is a high molecular weight polydimithylsiloxane (PDMS) having SiOH at the siloxane terminal, and the silicate resin has a structure with three-dimensional trimethylsiloxy and SiOH at both terminals.

The cross-linking agent may be at least one selected from the group consisting of aluminum hydroxide, hydrous aluminum silicate, kaolin, aluminum acetate, lactic acid, aluminum, aluminum stearate, calcium chloride, magnesium chloride, aluminum chloride, magnesium aluminometasilicate, magnesium aluminosilicate, sodium polyacrylate, cellulose gum, polyacrylate, and polyacrylamide. If the content of the cross-linking agent is less than 0.1 wt%, the cross-linking reaction may not be sufficient and the main composition may be suspended. If the content exceeds 1.5 wt%, the speed of the cross-linking reaction may become fast and the gel composition may gel unevenly.

The above thickener is dimethicone, which is linear dimethicone (CH3)3SiO[(CH3)2SiO]nSi(CH3)3, and has an average polymerization degree n of 3 to 650. It is mainly used as a thickener for skin protection agents and skin conditioning agents, and prevents skin damage caused by adhesives in the present invention.

The above-mentioned retarder, ethylcyclohexanol (1-Ethylcyclohexanol), delays curing and ensures that the composition is well mixed before crosslinking and curing to achieve even dispersion.

The above chain extender, 1,4-butanediol, is formed with a total of 16 atoms in a molecule composed of 10 hydrogen atoms, 4 carbon atoms, and 2 oxygen atoms, and there are a total of 15 chemical bonds in the 1,4-butanediol molecule, which are composed of 5 non-hydrogen bonds, 3 single bonds, 2 hydroxyl groups, and 2 primary alcohols. 1,4-butanediol is a low-molecular-weight chain extender, and when it reacts with isocyanate, the tendency of the solid block regions to cohere with each other increases and the elasticity increases.

The above platinum catalyst is a catalyst for producing a medical silicone adhesive in sheet form, and it is preferable to use 1,3-divinyldisiloxane platinum, and to use 0.4 to 2 wt% of the mixture of the main agent, chain extender, thickener, retarder, and crosslinking agent.

The zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) mixed as the above antibacterial agent uniformly maintains the bioelectrical effect induction of the carbon nanotube polymer in the composition, thereby inactivating bacteria that adhere to the skin or externally, thereby imparting antibacterial properties. As a result, there is no need to add or apply or coat a separate antibiotic, and there are no side effects such as resistance of conventional antibiotics, and the lifespan is determined by the electrostatic charge of the carbon nanotube polymer. In addition, due to its unique high thermal conductivity, it has the effect of minimizing rejection during the adhesion process to the affected area, reducing additional replacement costs, and preventing increased medical costs due to infection.

It is characterized in that the mixing order of the above composition is preferably in the order of the subject, chain extender, thickener, retardant, crosslinking agent, hardener, and antibacterial agent.

The above mixing order is performed in the order in which the molecules of the composition are uniformly mixed, by uniformly dispersing the chain extender and the thickener between the main molecules, delaying the increase in viscosity with the retarder, and then injecting the crosslinking agent to react with the dispersed chain extender and hardening with the hardener.

a) The above antibacterial agent, zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer), is composed of zinc oxide, carbon nanotubes, and a nitrate complex as shown in the following chemical formula 1,

b) The above antibacterial agent uses a pretreated zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer), and the pretreatment process is characterized by mixing the zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) with one of methanol, ethanol, xylene, toluene, distilled water, hexane, acetone, and isobutyl alcohol solvents, irradiating it with electron beams at 5 to 23 kGy, and then extracting it by a reduced pressure drying method.

[Structural formula 1]

In the above chemical formula 1, m, n, and p represent the number of molecules of zinc oxide (ZnO), carbon nanotubes (CNT), and nitrate complexes, and it is preferable that m is in the range of 7 to 30, n is in the range of 10 to 50, and p is in the range of 50 to 300. However, the present invention is not limited thereto, and of course, the composition is formed, and therefore, m, n, and p may be set differently from each other.

Carbon nanotubes (CNTs) are cylindrical crystals made of carbon atoms, with a diameter of 2–20 nm (1 nm is 1/1,000,000 m) and a length of several hundred to several thousand nm. In a carbon nanotube, each carbon atom forms an sp2 bond with three other carbon atoms around it to form a hexagonal honeycomb pattern, and since the diameter of this tube is extremely small, approximately several nanometers (nm), it is also commonly called a nanotube.

A carbon nanotube polymer (CNT Polymer) is a polymer in which carbon nanotubes (CNT) and zinc oxide (ZnO) are combined. The carbon nanotubes (CNT) and zinc oxide (ZnO) can be polymerized at the same ratio, or the zinc oxide (ZnO) can be polymerized at a higher ratio than the carbon nanotubes (CNT), and vice versa can be possible if necessary.

These zinc oxide-carbon nanotube polymers (ZnO-CNT Polymers) react to the micro-electrical potential of the adhered area to have a constant electrostatic capacity, and this electrostatic capacity is harmless to the human body but has a fatal electrostatic effect (galvanic effect) on bacteria and biofilms, resulting in an antibacterial effect, preventing the formation of biofilms caused by bacteria, and minimizing the patient's rejection during the adherence process due to the high thermal conductivity of carbon nanotubes.

Furthermore, in the case of adhesive compositions coated or applied with existing antibiotic substances, the antibacterial properties weaken over time, so that they cannot be used for more than a week at most, but the silicone gel composition according to the present invention can have a use life of at least 4 to 5 weeks, as long as the zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) is not dissolved and washed away by water, etc.

According to one embodiment of the present invention, the zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) may be a multi-walled carbon nanotube (MWNT).

Referring to Figure 1, the method for manufacturing a medical silicone gel composition used as an adhesive according to the present invention is

a) A mixing step (S10) of mixing 60 to 85 wt% of a main component composed of a polysiloxane polymer and a silicate resin, 0.1 to 1.5 wt% of a crosslinker, 8 to 38 wt% of dimethicone as a thickener, 0.1 to 5 wt% of 1-ethylcyclohexanol as a retarder, and 0.2 to 1 wt% of 1,4-butanediol as a chain extender;

b) 1st depressurization step (S20) of mixing and drying under reduced pressure at 0.1 to 1 atm, 50 to 60 ℃, for 17 to 19 hours;

c) Primary defoaming step (S30) to remove air bubbles at a pressure of 0.1 to 0.9 atm;

d) Second mixing step (S40) of mixing 0.4 to 2 wt% of a platinum catalyst as a curing agent;

e) Second depressurization stage (S50) mixing at 0.8 to 1 atm;

f) Secondary defoaming step (S60) for removing air bubbles at a pressure of 0.1 to 0.9 atm;

g) Antibacterial agent mixing step (S70) mixing 0.1 to 10 wt% of zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer), which is an antibacterial agent; and

h) It consists of a third mixing and defoaming step of first mixing the mixed composition using a homomixer under conditions of less than 1 atm at 1,000 to 10,000 rpm, 18 to 22°C, for 1 to 4 hours, and second mixing at 300 to 800 rpm, 18 to 22°C, for 4 to 8 hours.

The method for manufacturing a medical silicone gel of the present invention can more effectively perform uniform mixing and bubble removal by performing a first and second depressurization step and a defoaming step, respectively, when mixing a composition under reduced pressure, thereby generating bubbles. In particular, in the first depressurization step (S20), the pressure state is made more reduced than in the second depressurization step (S50), thereby reducing the amount of bubbles generated during initial mixing of the composition and performing uniform mixing.

The above mixing step is characterized in that the main component, chain extender, thickener, retarder, and crosslinking agent are mixed in that order, and the hardener is mixed in the second mixing step. The mixing step or the second mixing step is performed at a low speed of 10 to 200 rpm, and the second depressurization step and the second defoaming step are performed at a high speed of 400 to 600 rpm.

The above antibacterial agent uses a pretreated zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer), and the pretreatment process is characterized by mixing the zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) with one selected from among solvents such as methanol, ethanol, xylene, toluene, distilled water, hexane, acetone, and isobutyl alcohol, irradiating the mixture with electron rays at 5 to 23 kGy, and then extracting the zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) by a reduced pressure drying method.

In the above pretreatment process, the process of extracting zinc oxide-carbon nanotube polymer (ZnO-CNT polymer) by mixing with a solvent and drying under reduced pressure is considered to be a generally known technology, so it will not be described in detail below.

In the pretreatment process, when zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) is mixed in a solvent and irradiated with electron rays (gamma rays) at 5 to 23 kGy, the surface is modified according to the change in molecular structure to make it hydrophobic, which has the effect of making the dispersion uniform when mixed with the main subject composed of polysiloxane polymer and silicate resin. However, when the electron beam is irradiated at less than 5 kGy, the effect of changing to hydrophobicity is minimal, so the dispersion does not occur uniformly, and from 23 kGy or higher, the effect of changing to hydrophobicity is the same for all cases, so irradiation with electron rays exceeding 23 kGy is meaningless.

The above-mentioned third mixing and defoaming step is a process in which mixing and defoaming are performed simultaneously because bubbles are generated during the mixing step when the raw materials being mixed have powder properties. In particular, in the case of a zinc oxide-carbon nanotube polymer (ZnO-CNT polymer) that has been irradiated with electron beams (gamma rays) in a pretreatment process to ensure good dispersion, the surface is modified to be hydrophobic, so that a process in which mixing and defoaming are performed simultaneously is possible, which is a characteristic of the present invention.

Example 1: Preparation of medical silicone gel used as adhesive

80 wt% of polysiloxane polymer and silicate resin, 1.3 wt% of crosslinker, 10 wt% of dimethicone, 4.7 wt% of 1-ethylcyclohexanol, and 1 wt% of 1,4-butanediol were mixed, mixed at 50 rpm under a reduced pressure of 0.5 atm, and then the first decompressing was performed to remove air bubbles at 0.5 atm, and then 1 wt% of platinum catalyst was mixed, and the second decompressing was performed at 400 rpm under 0.9 atm, and then air bubbles were removed at 0.8 atm, and then 2 wt% of zinc oxide-carbon nanotube polymer (ZnO-CNT polymer), an antibacterial agent (mixed with xylene in a 1:1 ratio and irradiated with 30 kGy of electron beam) was added. The silicone gel composition obtained by first mixing (which went through a pretreatment process of extracting by a reduced pressure drying method) using a homomixer at 6000 rpm and 20℃ for 3 hours and then second mixing at 500 rpm and 20℃ for 6 hours was used in the following test examples.

Test Example 1: Initial adhesion and re-adhesion

(Initial adhesion) The specimens manufactured in the above examples and the control specimens were attached by removing the release paper and placing the adhesive surface on a stainless steel test plate, and moving it back and forth once on the specimen. After 20 minutes, the specimens were measured at a load cell of 50 N, a specimen width of 20 mm, a specimen length (Gauge Length) of 15 mm, and a crosshead speed of 300 mm/min.

(Re-adhesion) Same as the initial adhesion test method above, 20 adult men and women were selected, and after waiting for 5 hours under the conditions of 24 to 26℃ and 40 to 50% relative humidity, the specimen was attached, and after 1 hour of attachment under the above conditions, it was removed and measured in the same manner as the initial adhesion test method above, and the average values were calculated and the results are as shown in Table 1 below. As a result of the hydrophobic zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) being uniformly distributed in the bond with the subject, the re-adhesion strength was slightly improved.

Meanwhile, Control Group 1 used domestic NeoDumTM, and Control Group 2 used an adhesive manufactured with a prior art medical silicone adhesive composition presented by Taekyung Hi-Tech Co., Ltd.

division Adhesion (kgf/25mm) Initial adhesion (kgf/25mm) Re-adhesion (kgf/25mm) Control group 1 1.6 0.4 Control group 2 2.2 1.71 Example 2.5 1.95

Test Example 2: Cytotoxicity and antibacterial effect test

Using the specimens manufactured in the above examples, a cytotoxicity test was conducted as follows. The cytotoxicity of the test substance was evaluated using L-929 mouse fibroblasts, and the test method was the Test on extracts method in ISO 10993-5:2009(E) Tests for in vitro cytotoxicity. The test material was the cell line L-929 mouse fibroblasts (ATCC CCL, NCTC Clone 929). The culture conditions were (5±1)%CO2(37±1)℃. A cell suspension was prepared, cells were counted using a hemacytometer, and cultured in an incubator for more than 24 hours. Each well treated with the test, negative control, and positive control was observed under a microscope.

In addition, the grade was determined based on the cytotoxicity judgment criteria by observing cell morphology, vacuolation, weak attachment or cell suspension, cell lysis, cell membrane destruction, etc., and, if necessary, staining was performed using neutral red and then observed.

The test results showed that the test solution was grade 0, the negative control solution grade 0, the elution solvent grade 0, and the positive control solution grade 4 based on the qualitative analysis results of the cells. In the cells treated with the test substance, cell rounding, cell granulation abnormalities, and cell lysis were not observed. The test solution was judged to have no cytotoxicity, and the cytotoxicity reactivity was judged to be 0.

Example 2: Verification of antibacterial effect of medical silicone gel used as adhesive

Through the process of the above example, a silicone gel composition having the following contents (the values in the table are in wt%) was manufactured, and E coli (Escherichia coli) was cultured for 3 and 7 days, respectively, and used in the following experiment, and the bacterial activity was tested on a plate medium for a period of 7 days.

Example 1 Example 2 Example 3 Example 4 Example 5 subject 82 80.91 80.9 72 71 Crosslinking agent 1.3 1.3 1.3 1.3 1.3 Dimethicone 10 11 11 10 10 Ethylcyclohexanol 4.7 4.7 4.7 4.7 4.7 1,4-butanediol 1 1 1 1 1 Platinum catalyst 1 1 1 1 1 Zinc oxide-carbon nanotube polymer [pretreatment process] 0 0.09 0.1 10 11

Referring to FIG. 2, for Example 1 that did not include a zinc oxide-carbon nanotube polymer and Example 2 that used a content outside the numerical limitation range according to the present invention, when E coli (Escherichia coli) was cultured for 3 and 7 days, respectively, it was confirmed that the pathogenic bacteria colonies, that is, bacterial activity, were high, indicating that there was no or weak antibacterial activity.

Referring to FIG. 2, it was confirmed that in Example 3, the pathogen colony hardly grew, and in Examples 4 and 5, it was confirmed that the pathogen colony did not grow at all to the point that no trace of the pathogen colony could be found, and furthermore, no significant difference could be found between these two examples. Therefore, it is considered clear that there is no need to use a zinc oxide-carbon nanotube polymer mixed in excess of 10 wt%.

On the additional side,

The above crosslinking agent can be manufactured using a hydrogen polymer (Methylhydrosiloxane-dimethysiloxane Copolymer, Trimethylsiloxy terminated), and when the hydrogen polymer is used as a crosslinking agent, a chain extender does not need to be used. It is preferable to use the hydrogen polymer having a block form, a hydrogen content of 0.05 to 2 mmol/g, and a viscosity of 50 to 1,000 cps.

In addition, the above-mentioned subject matter may further include alginate-silicate hybrid materials, and the alginate-silicate is a natural polysaccharide polymer in the form of an odorless, tasteless, white-yellow powder extracted from brown seeweed (algae, Undaria pinnatifida), and its structure is a polyuronic polysaccharide in the form of a linear heteropolymer in which two types of uronic acids, mannuronate (β-D-mannuronate (M)) and gluuronate (α-L-guluronate (G)), are linked at various ratios through (1-4)-linkage, and it is named alginate because it is a salt mixed state of algin and metal, and the sodium type is mainly used. Sodium Alginate is liquid at room temperature and dissolves readily in water.

When a sodium alginate aqueous solution is added dropwise to a calcium chloride (CaCl2) aqueous solution, the sodium atoms forming a salt with the alginate are replaced by calcium ions due to an ion exchange reaction, thereby producing an insoluble gel. The gel produced in this way can be used as a carrier or part of the subject of a drug in addition to the subject of the present invention.

The present invention has the following effects.

(1) The present invention provides a medical composition used as an adhesive that has improved antibacterial properties and can maintain antibacterial properties even after long-term use, thereby inhibiting bacterial infection or the formation of a biofilm that is the source of bacterial infection, and a method for producing the same.

(2) The present invention has improved antibacterial properties without the addition, application or coating of a separate antibiotic, and has no side effects such as antibiotic resistance. Its lifespan can be easily determined based on the electrostatic capacity of the polymer, and its adhesive performance is determined accordingly, so it can be used for various medical purposes.

(3) The present invention provides a medical silicone gel composition and a method for manufacturing the same, which minimizes skin irritation, toxicity, allergic phenomena, and odor causing rejection that may occur from medical adhesives, and maintains adhesive performance not only during initial adhesion but also during re-adhesion.

(4) In addition to its use as an adhesive, the present invention can be used as a drug delivery silicone gel by adding a drug, and can deliver a drug directly through the skin.

(5) The present invention provides a medical adhesive composition having improved adhesive strength and reduced cytotoxicity by removing air bubbles generated during composition mixing and uniformly distributing the molecules of the mixture through multiple depressurization and defoaming processes.

Claims (6)

In a composition of medical silicone gel used as an adhesive,
The above composition
A composition comprising 60 to 85 wt% of a main component consisting of a polysiloxane polymer and a silicate resin, 0.1 to 1.5 wt% of a crosslinker, 8 to 38 wt% of dimethicone as a thickener, 0.1 to 5 wt% of 1-ethylcyclohexanol as a retarder, 0.2 to 1 wt% of 1,4-butanediol as a chain extender, 0.4 to 2 wt% of a platinum catalyst as a curing agent, and 0.1 to 10 wt% of a zinc oxide-carbon nanotube polymer (ZnO-CNT polymer) as an antibacterial agent.
a) The antibacterial agent, zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer), is composed of zinc oxide, carbon nanotubes, and a nitrate complex as shown in the structural formula 1 below.
b) A medical silicone gel composition characterized in that the antibacterial agent is a pretreated zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer), and the pretreatment process comprises mixing the zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) in one selected from among methanol, ethanol, xylene, toluene, distilled water, hexane, acetone, and isobutyl alcohol as a solvent, irradiating the mixture with 5 to 23 kGy of electron beams, and then extracting the zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) by a reduced pressure drying method.
[Structural formula 1]
In claim 1,
A medical silicone gel composition, characterized in that the mixing order of the composition is in the order of a subject, a chain extender, a thickener, a retarder, a crosslinking agent, a curing agent, and an antibacterial agent. delete A method for manufacturing a medical silicone gel composition used as an adhesive,
The above manufacturing method
a) A mixing step of mixing 60 to 85 wt% of a main component composed of a polysiloxane polymer and a silicate resin, 0.1 to 1.5 wt% of a crosslinking agent, 8 to 38 wt% of dimethicone as a thickener, 0.1 to 5 wt% of 1-ethylcyclohexanol as a retarder, and 0.2 to 1 wt% of 1,4-butanediol as a chain extender;
b) First depressurization step of mixing and drying under reduced pressure of 0.1 to 1 atm, 50 to 60 ℃ for 17 to 19 hours;
c) Primary defoaming step to remove air bubbles at a pressure of 0.1 to 0.9 atm;
d) Second mixing step of mixing 0.4 to 2 wt% of a platinum catalyst as a curing agent;
e) Second depressurization stage mixing at 0.8 to 1 atm;
f) Secondary defoaming step to remove air bubbles at a pressure of 0.1 to 0.9 atm;
g) The antibacterial agent, zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer), is composed of zinc oxide, carbon nanotubes, and a nitrate complex as shown in the structural formula 2 below, and is used after being pretreated, wherein the pretreatment process comprises mixing the zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) in one selected from among methanol, ethanol, xylene, toluene, distilled water, hexane, acetone, and isobutyl alcohol as a solvent, irradiating the zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) with 5 to 23 kGy of electron beams, and then extracting the zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer) by a reduced pressure drying method, and an antibacterial agent mixing step of mixing 0.1 to 10 wt% of the extracted zinc oxide-carbon nanotube polymer (ZnO-CNT Polymer); and
h) A method for manufacturing a medical silicone gel, characterized by comprising a third mixing and defoaming step of first mixing the mixed composition using a homomixer under conditions of less than 1 atm at 1,000 to 10,000 rpm, 18 to 22°C, and 1 to 4 hours, and second mixing at 300 to 800 rpm, 18 to 22°C, and 4 to 8 hours;
[Structural formula 2]
In claim 4,
A method for manufacturing a medical silicone gel, characterized in that the above mixing step comprises mixing a subject, a chain extender, a thickener, a retarder, and a crosslinking agent in that order. delete