KR102488837B1 - Self recoverable multilayer adhesive pad for the organic surface and manufacturing method of thereof - Google Patents

Abstract

One embodiment of the present invention provides an adhesive pad attached to the surface of an organic material having increased adhesive strength, including a pressure-sensitive adhesive polymer film layer/a first viscoelastic polymer film layer/a second elastic polymer film layer. It is not harmful to the human body by using alginate boronic acid polymer, and adhesive strength can be increased by using a viscoelastic polymer layer and an elastic polymer layer.

Description

Self-healing organic surface adhesive pad and its manufacturing method

The present invention relates to an adhesive pad attached to an organic surface having increased adhesive ability and a manufacturing method thereof. More specifically, it relates to an adhesive pad composed of multiple layers, which is attached to an organic surface having increased adhesive ability, and a manufacturing method thereof.

More than 90,000 cases of body parts being damaged or amputated as a result of industrial accidents occur annually, and the number is increasing by 3% every year. Tissues cut or damaged in this way require surgical operations, and sutures have been used for the purpose of joining nerves, blood vessels, tendons, and the like. However, sutures exert strong pressure on tissues, and sutures and fine wounds caused by surgery block tissue recovery pathways, causing many problems such as blocking complete recovery of nerves and immune responses. In addition, in order to suture thin nerves or blood vessels, precise surgery using such a surgical microscope is required, which increases operating time and causes fatigue of doctors and patients. , even cases where the suture was broken due to pressure from outside the organic tissue.

In order to compensate for the disadvantages of these sutures, biological tissue adhesives have been developed, and there are mainly cyanoacrylate, fibrin glue, polyethylene glycol, and the like. However, despite these developments, due to the high toxicity of these materials and the low adhesiveness and low physical properties of H ₂ O remaining on the tissue surface, most of them are used only for bonding of skin, which is an external tissue, or for hemostasis, and nerves, blood vessels, heart, etc. There is a limit in that it cannot withstand the physical stimulation for a long time by the movement of a flexible tissue with elasticity and water on the surface.

In addition, even if there is a conventional method for mitigating external impact by using an elastic layer and a viscoelastic layer to configure a multi-layer, there is a problem in that the elasticity of the adhesive pad decreases when the external impact is strong, and thus the adhesive pad Decreased adhesion was also a chronic problem.

PCT International Publication No. WO2019-229747

A technical problem to be achieved by the present invention is to provide an adhesive pad with increased adhesive strength when the adhesive pad is attached to a tissue with a lot of moisture on its surface.

In addition, it is to provide a biocompatible polymer adhesive pad.

Another object of the present invention is to provide an adhesive pad that maintains adhesive force through self-healing of the elasticity of the elastic layer and the viscoelastic layer.

The technical problem to be achieved by the present invention is not limited to the above-mentioned technical problem, and other technical problems not mentioned can be clearly understood by those skilled in the art from the description below. There will be.

In order to achieve the above technical problem, an embodiment of the present invention provides an adhesive polymer film layer, a first viscoelastic polymer film layer disposed on the adhesive polymer film layer, and a second elastic polymer film layer disposed on the first viscoelastic polymer film layer. Provided is a multilayer adhesive pad attached to the surface of an organic material including a film layer.

In addition, the adhesive polymer film layer may be characterized in that it comprises a hydrogel precursor.

In addition, when the adhesive polymer film layer is adhered to an adhesive target, the hydrogel precursor inside the adhesive polymer film layer absorbs moisture of the adhesive polymer film layer to form an adhesive hydrogel layer.

In addition, the hydrogel precursor may be characterized in that it comprises an alginate boronic acid polymer.

In addition, the Young's modulus of the polymer included in the first viscoelastic polymer film layer may be smaller than the Young's modulus of the polymer included in the second elastic polymer film layer.

In addition, since the Young's modulus of the polymer included in the first viscoelastic polymer film layer is smaller than the Young's modulus of the polymer included in the second elastic polymer film layer, the external pressure applied from the lower surface of the first viscoelastic polymer film layer causes the first viscoelasticity It may be characterized in that the force is dispersed within the polymer film layer and not transmitted to the second elastic polymer film layer.

In addition, in the polymers included in the first viscoelastic polymer film layer, the number of hydrogen bonds per functional group of the polymers included in the first viscoelastic polymer film layer is hydrogen possible per functional group of the polymers included in the second elastic polymer film layer. It may be characterized as being smaller than the number of bonds.

In addition, the adhesive polymer film layer may be characterized in that it comprises an alginate boronic acid polymer.

In addition, the first viscoelastic polymer film layer includes isophorone diisocyanate, and the second elastic polymer film layer is an elastic polymer having a Young's modulus greater than the Young's modulus of the viscoelastic polymer of the first viscoelastic polymer film layer. It may be characterized by including.

In addition, the second elastic polymer film layer includes isophorone diisocyanate, and the first viscoelastic polymer film layer comprises a viscoelastic polymer having a Young's modulus smaller than the Young's modulus of the elastic polymer of the second elastic polymer film layer. It can be characterized by including.

In addition, the second elastic polymer film layer includes phenyl isocyanate (4,4'-Methylenebis (Phenyl Isocyanate)), and the first viscoelastic polymer film layer has a Young's modulus smaller than the Young's modulus of the elastic polymer of the second elastic polymer film layer It may be characterized in that it comprises a viscoelastic polymer having a.

An embodiment of the present invention in order to achieve the above technical problem, the step of preparing a first viscoelastic polymer film layer and a second elastic polymer film layer, forming a second elastic polymer film layer on the upper surface of the first viscoelastic polymer film layer It provides a method for manufacturing a multi-layer adhesive pad attached to an organic material surface, comprising the steps of: and forming an adhesive polymer film layer on the lower surface of the first viscoelastic polymer film layer.

In addition, in the step of preparing the first viscoelastic polymer film layer and the second elastic polymer film layer, the Young's modulus of the viscoelastic polymer included in the first viscoelastic polymer film layer is greater than the Young's modulus of the elastic polymer included in the second elastic polymer film layer. It can be characterized as small.

In addition, the step of forming the adhesive polymer film layer on the lower surface of the first viscoelastic polymer film layer includes the steps of modifying the lower surface of the first viscoelastic polymer film layer to be hydrophilic by treating with oxygen plasma, and the first viscoelastic polymer film layer modified to hydrophilicity. It may be characterized in that it comprises the step of forming an adhesive polymer film layer by applying an adhesive polymer solution to the lower surface of the viscoelastic polymer film layer.

In addition, the adhesive polymer film layer may be characterized in that it comprises an alginate boronic acid polymer.

In addition, the first viscoelastic polymer film layer includes isophorone diisocyanate, and the second elastic polymer film layer is an elastic polymer having a Young's modulus greater than the Young's modulus of the viscoelastic polymer of the first viscoelastic polymer film layer. It can be characterized by including.

In addition, the second elastic polymer film layer includes isophorone diisocyanate, and the first viscoelastic polymer film layer comprises a viscoelastic polymer having a Young's modulus smaller than the Young's modulus of the elastic polymer of the second elastic polymer film layer. It can be characterized by including.

In addition, the second elastic polymer film layer includes phenyl isocyanate (4,4'-Methylenebis (Phenyl Isocyanate)), and the first viscoelastic polymer film layer has a Young's modulus smaller than the Young's modulus of the elastic polymer of the second elastic polymer film layer It may be characterized in that it comprises a viscoelastic polymer having a.

In addition, the adhesive polymer film layer may be characterized in that it comprises an alginate boronic acid polymer.

In addition, the adhesive polymer film layer contains an alginate boronic acid polymer, the first viscoelastic polymer film layer contains isophorone diisocyanate, and the second elastic polymer film layer contains isophorone diisocyanate or phenyl isocyanate. It can be characterized by including.

According to one embodiment of the present invention, it is possible to provide an adhesive pad having strong adhesion to the surface of an organic material such as an ex vivo tissue, an in vivo tissue, or a cut tissue.

In addition, it is possible to provide a biocompatible polymer adhesive pad.

In addition, it is possible to provide an adhesive pad capable of maintaining adhesive strength even from uneven external pressure in the direction of the adhesive polymer film layer and maintaining adhesive strength even from strong external pressure in the direction of the second elastic polymer film layer.

In addition, including the first viscoelastic polymer film layer and the second elastic polymer film layer including a hydrogen bond, even if the elasticity is temporarily changed by external pressure, it is possible to provide an adhesive pad that is self-healing over time. .

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the detailed description of the present invention or the configuration of the invention described in the claims.

1 is a schematic diagram of the entire layer structure of an adhesive pad attached to the surface of an organic material according to an embodiment of the present invention.
Figure 2 is an explanatory diagram for external pressure in the direction of the adhesive polymer film layer of the adhesive pad attached to the surface of the organic material according to an embodiment of the present invention.
3 is an explanatory diagram for external pressure in the direction of the second elastic polymer film layer of the adhesive pad attached to the surface of the organic material according to an embodiment of the present invention.
Figure 4 shows the binding and severing of hydrogen bonds within the first viscoelastic polymer film layer in response to the action of external pressure in the direction of the adhesive polymer film layer of the adhesive pad attached to the surface of the organic material according to an embodiment of the present invention. It is an explanatory drawing for
5 is a graph showing experimental results of the mechanical properties (adhesiveness of each layer) of an adhesive pad having a three-layer structure of an adhesive pad attached to an organic material surface according to an embodiment of the present invention.
6 is a diagram showing experimental results of mechanical properties (tensile strength of each layer) of an adhesive pad having a three-layer structure of an adhesive pad attached to an organic surface according to an embodiment of the present invention.
7 is a diagram showing a comparison of adhesive strength between a conventional commercially available adhesive and an adhesive pad attached to an organic surface according to an embodiment of the present invention.
8 is a view of an experimental example of an adhesive pad attached to an organic material surface according to an embodiment of the present invention.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be embodied in many different forms and, therefore, is not limited to the embodiments described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the specification, when a part is said to be "connected (connected, contacted, combined)" with another part, this is not only "directly connected", but also "indirectly connected" with another member in between. "Including cases where In addition, when a part "includes" a certain component, it means that it may further include other components without excluding other components unless otherwise stated.

Terms used in this specification are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "include" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

The term "adhesive pad" used herein refers to an embodiment of an adhesive pad including an adhesive polymer film layer, a first viscoelastic polymer film layer, and a second elastic polymer film layer.

The term “polymer film layer” used in this specification is not limited to only a thin film layer, but includes all kinds of thin films, thick films, films, film layers, and the like including polymer materials.

The term "A/B/C multilayer structure" used herein refers to a structure in which a B layer and a C layer are sequentially positioned on an A layer.

As used herein, the term “number of hydrogen bonds” refers to the number of possible hydrogen bonds per functional group of a polymer included in each elastic polymer film layer or viscoelastic polymer film layer.

A multi-layered adhesive pad attached to the surface of an organic material including “multiple structure of adhesive polymer film layer/first viscoelastic polymer film layer/second elastic polymer film layer” according to an embodiment of the present invention will be described.

1 is a schematic diagram of the entire layer structure of a multi-layer adhesive pad attached to an organic material.

Referring to Figure 1, a multi-layer adhesive pad attached to the surface of an organic material will be described.

The multilayer adhesive pad attached to the surface of the organic material may include an adhesive polymer film layer 100, a first viscoelastic polymer film layer 200, and a second elastic polymer film layer 300.

The adhesive polymer film layer 100 is a film layer containing an adhesive polymer, and may provide an effect of adhering to the organic material surface when approaching the target organic material surface. The first viscoelastic polymer film layer 200 is a film layer containing a polymer having both viscosity and elasticity, and when a non-uniform or uniform external force is applied from the surface of the organic material, the external force is dispersed to form a second elastic polymer film layer (300 ) can provide an effect that prevents the external force from being transmitted. The second elastic polymer film layer 300 is a film layer containing a polymer having elasticity, and when an external force is applied from the outside of the entire adhesive pad, based on the elastic force of the polymer included in the second elastic polymer film layer , It is possible to provide the effect of imparting elasticity while maintaining the shape of the entire adhesive pad.

The adhesive polymer film layer 100 is an adhesive polymer film layer 100 containing a hydrogel precursor, and can provide an effect of maintaining adhesive ability even when moisture exists on the surface of a tissue. At this time, when the adhesive polymer film layer 100 is adhered to the adhesive target, the hydrogel precursor inside the adhesive polymer film layer 100 absorbs moisture of the adhesive target to form an adhesive hydrogel layer. It can be characterized in that it is adhered. .

In addition, the adhesive polymer film layer 100 may use an alginate boronic acid derivative extracted from seaweed or the like. Unlike materials such as cyanoacrylate, fibrin glue, and polyethylene glycol, which have conventional toxicity, it is possible to overcome biotoxicity. The adhesive polymer film layer containing the alginate boronic acid derivative is characterized in that a hydrogel precursor is used, and when the adhesive polymer film layer 100 is in contact with an adhesive target, the hydrogel inside the adhesive polymer film layer 100 As the precursor absorbs the moisture of the adhesive target and forms an adhesive hydrogel layer, it can provide an adhesive effect. Since the hydrogel precursor is used, the adhesive pad is not sticky until it is attached to the surface of the organic material, so that the user of the adhesive pad can more accurately adhere the adhesive pad to a desired location.

The first viscoelastic polymer film layer 200 may be positioned on the adhesive polymer film layer 100, and the second elastic polymer film layer 300 may be positioned on the first viscoelastic polymer film layer 200. can

2 and 3 are diagrams showing the non-uniform or uniform external force of the organic material in the adhesive film direction 300 and the external force in the direction of the second elastic film layer, respectively.

Effects of the first viscoelastic polymer film layer 200 and the second elastic polymer film layer 300 will be described in detail with reference to FIGS. 2 and 3 .

The first viscoelastic polymer film layer 200 may include a viscoelastic polymer. 2, when external stress (external force 1 or external force 2) in the horizontal direction of the adhesive polymer film layer is applied to the adhesive polymer film layer 100 in the direction of the adhesive polymer film layer 100, the property of viscosity The first viscoelastic polymer film layer 200 having both properties of elasticity and elasticity can provide an effect of maintaining the adhesive strength of the adhesive pad by dispersing these external pressures.

Conversely, as shown in FIG. 3, the second elastic polymer film layer 300, even if an external force acts from the outside in the direction of the second elastic polymer film layer, based on the elastic force of the polymer included in the second elastic polymer film layer, the entire It is possible to provide an effect in which the adhesive force of the adhesive pad is not reduced. That is, the second elastic polymer film layer 300 does not have viscosity unlike the first viscoelastic polymer film layer 200, but is subject to continuous external stress (external force 3 or external force 4) generated in the organic tissue in the horizontal direction of the entire adhesive pad. ) can also provide an effect that can be countered. Accordingly, the adhesive force of the entire adhesive pad can be maintained.

At this time, the Young's modulus of the polymer included in the first viscoelastic polymer film layer 200 may be smaller than the Young's modulus of the polymer included in the second elastic polymer film layer 300. Since the Young's modulus of the polymer included in the first viscoelastic polymer film layer 200 is smaller than the Young's modulus of the polymer included in the second elastic polymer film layer 300, the first viscoelastic polymer film layer 200 is applied from the lower surface An external pressure may provide an effect in which the force is dispersed within the first viscoelastic polymer film layer 200 and not transmitted to the second elastic polymer film layer 300 . Conversely, the second elastic polymer film layer 300 is characterized in that it contains a polymer having a greater Young's modulus than the first viscoelastic polymer film layer 200, so that external pressure in the direction of the adhesive polymer film layer 100 is applied Thus, even if the pressure is transmitted, the effect of maintaining the entire structure of the adhesive pad can be provided.

That is, when the Young's modulus of the second elastic polymer film layer 300 is similar to or smaller than the Young's modulus of the first viscoelastic polymer film layer 200, adhesion by external pressure applied in the direction of the second elastic polymer film layer 300 The adhesive force of the pad can easily decrease, and on the contrary, when the uneven pressure presented from the tissue side in the direction of the adhesive polymer film layer 100 is strong, the second elastic polymer film layer 300 cannot counter the force and the adhesive pad adhesion can be easily reduced. Therefore, the effect of maintaining the adhesive force is achieved by including a polymer composition such that the Young's modulus of the polymer included in the second elastic polymer film layer 300 is greater than the Young's modulus of the polymer included in the first viscoelastic polymer film layer 200. can provide

In addition, in the polymer included in the first viscoelastic polymer film layer 200, the number of possible hydrogen bonds per functional group of the polymer included in the first viscoelastic polymer film layer 200 is the second elastic polymer film layer 300 It can be characterized in that it is smaller than the number of possible hydrogen bonds per functional group of the polymer it contains.

FIG. 4 is a view showing that the elasticity of the first viscoelastic polymer film layer 200 is changed by a non-uniform external force and then recovered over time. Referring to FIG. 4, a method for maintaining the viscoelasticity of the first viscoelastic polymer film layer 200 by hydrogen bonding will be described.

Hydrogen bonds are bonds between molecules, and bonding and cleavage proceed through a reversible process. When the difference in Young's modulus is made using hydrogen bonding, even if the elasticity inside the polymer temporarily changes, as shown in FIG. can do.

In addition, as a specific embodiment, the first viscoelastic polymer film layer 200 includes isophorone diisocyanate, and the second elastic polymer film layer 300 includes a polymer having a Young's modulus greater than the Young's modulus of the polymer containing isophorone diisocyanate. Conversely, the second elastic polymer film layer 300 includes Isophorone Diisocyanate or 4,4'-Methylenebis (Phenyl isocyanate), and the first viscoelastic polymer film layer 200 includes a second elastic polymer film. It may be a multi-layer adhesive pad attached to the surface of an organic material, characterized in that the layer 300 includes a polymer having a Young's modulus smaller than the Young's modulus of the polymer included.

The adhesive pad including the "multiple structure of the adhesive polymer film layer/first viscoelastic polymer film layer/second elastic polymer film layer" may be characterized as an adhesive pad composed of three layers.

According to an embodiment of the present invention, a method for manufacturing an adhesive pad including “multiple structure of adhesive polymer film layer/first viscoelastic polymer film layer/second elastic polymer film layer” will be described.

In the adhesive pad manufacturing method, the step of preparing the first viscoelastic polymer film layer 200 and the second elastic polymer film layer 300, the second elastic polymer film layer on the upper surface of the first viscoelastic polymer film layer 200 ( 300) and forming an adhesive polymer film layer on the lower surface of the first viscoelastic polymer film layer 200.

In addition, in the step of preparing the first viscoelastic polymer film layer 200 and the second elastic polymer film layer 300, the Young's modulus of the viscoelastic polymer included in the first viscoelastic polymer film layer 200 is the second elastic polymer film. It may be characterized in that it is smaller than the Young's modulus of the elastic polymer included in the layer 300.

In addition, the step of forming the adhesive polymer film layer 100 on the lower surface of the first viscoelastic polymer film layer 200 is a step of modifying the lower surface of the first viscoelastic polymer film layer 200 to be hydrophilic by treating the lower surface with oxygen plasma. and forming the adhesive polymer film layer 100 by applying an adhesive polymer solution to the lower surface of the first viscoelastic polymer film layer 200 modified to be hydrophilic.

In addition, the first viscoelastic polymer film layer 200 may include Isophorone Diisocyanate, and the second elastic polymer film layer 300 may include a polymer having a Young's modulus greater than that of Isophorone Diisocyanate. .

In addition, the second elastic polymer film layer 300 includes Isophorone Diisocyanate or 4,4'-Methylenebis (Phenyl isocyanate), and the first viscoelastic polymer film layer 200 includes a second elastic polymer film layer, It may be characterized in that it includes a polymer having a Young's modulus smaller than the Young's modulus of a polymer having a Young's modulus.

In addition, the reforming step may include a step of oxygen plasma treatment for 3 to 5 minutes at a power of 50 W to 150 W on the surface (the first viscoelastic polymer film layer 200) having a low Young's modulus.

In addition, the adhesive polymer film layer 100 may be characterized in that it includes an alginate boronic acid polymer compound.

In a specific embodiment, the adhesive polymer film layer 100 includes an alginate boronic acid polymer, the first viscoelastic polymer film layer 200 includes isophorone diisocyanate, and the second elastic polymer film layer 300 may be a method for manufacturing a multi-layer adhesive pad attached to an organic surface, characterized in that it contains Isophorone Diisocyanate or 4,4'-Methylenebis (Phenyl isocyanate).

Hereinafter, experimental examples, examples, and manufacturing examples of the present invention will be described in detail with reference to the accompanying drawings.

manufacturing example

This manufacturing example consists of three steps.

The first step is composed of a step of manufacturing an adhesive polymer film layer, a polymer 100 layer, a first viscoelastic polymer film layer 200, and a second elastic polymer film layer 300.

The second step is a lamination step, the first lamination step of laminating the first viscoelastic polymer film layer 200 and the second elastic polymer film layer 300, surface modification of the first viscoelastic polymer film 200 by oxygen plasma treatment. step, a second lamination step of laminating the adhesive polymer film layer and the polymer layer 100 on the modified surface.

The third step consists of a drying step of drying the adhesive polymer film layer and the polymer layer.

Hereinafter, the above processes are described along with specific reaction conditions.

One. Manufacturing step of polymer film layer

(One) Manufacturing step of adhesive polymer film layer 100

1) Dissolving 1g of alginate polymer in 250mL of 0.1M MES buffer (pH 5.0)

2) Dissolving 700 mg of 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 100 mg of N-hydroxysuccinimide in 10 mL of tertiary distilled water, and then adding 1 mL per minute to the solution in which the alginate polymer was dissolved. A first addition step

3) 300 mg of 3-Aminoheylboronic acid hydro-chloride was dissolved in 10 mL of tertiary distilled water, added to the solution after the first addition step, and reacted for 12 hours

4) Dialysis step of removing unreacted boronic acid through a 3-day dialysis process

5) Freeze-drying step of producing dried polymer through freeze-drying process

made through

(2) First viscoelastic polymer film layer 200 manufacturing step

1) Step of creating a nitrogen environment by adding 100 g of Aminopropyl terminated polydimethyl siloxane and 400 mL of Chloroform, installing an ice bath, and flowing nitrogen

2) 10 mL of triethylamine was added 1 hour after the nitrogen environment creation step 1st addition step of manufacturing the 1st viscoelastic polymer film layer

3) 1 hour after the first addition step of preparing the first viscoelastic polymer film layer, the second addition step of preparing the first viscoelastic polymer film layer by dissolving 4.45 g of Isophorone Diisocyanate in Chloroform

4) 1 hour after the second addition step of preparing the first viscoelastic polymer film layer, stop supplying the ice bath and nitrogen, gradually increase the reaction temperature to room temperature, and react for 4 days

5) 4 days after the reaction step, 15 mL of methanol was added to terminate the reaction and remove residual active molecules.

6) After the reaction termination step, a first concentration step of concentrating the reaction solution in half using a rotary evaporator

7) A first filtration step of removing 60 mL of methanol into the reaction solution concentrated by the concentration step, leaving it aside for 30 minutes, and removing the white material and the clear solution in the upper layer.

8) After the filtration step, 100 mL of chloroform was added, the solution was thoroughly mixed, 60 mL of methanol was added again, and after 30 minutes, the step of removing the white matter and the clear solution in the upper layer was repeated three more times. Second filtration step

9) A second concentration step of removing the solvent from the solution after the second filtration step using a rotary evaporator

10) After the second concentration step, the polymer production step is to prepare a polymer with a low Young's modulus by pouring it into a Teflon dish and drying for about 3 days to remove the solvent.

11) Polymer film layer production step of dissolving 1 g of the prepared polymer in chloroform, pouring it into a Teflon dish with a diameter of 10 cm, and drying for more than 1 day to produce a polymer film layer with a low Young's modulus

is produced through

(3) Second elastic polymer film layer 300 manufacturing step

1) Step of creating a nitrogen environment by adding 100 g of Aminopropyl terminated polydimethyl siloxane and 400 mL of Chloroform, installing an ice bath, and flowing nitrogen

2) 10 mL of triethylamine was added 1 hour after the nitrogen environment creation step 1st addition step of manufacturing the 2nd elastic polymer film layer

3) 1 hour after the first addition step of preparing the second elastic polymer film layer, the second addition step of preparing the second elastic polymer film layer by dissolving 2.7 g of isophorone diiso cyanate and 2 g of phenyl isocyanate in chloroform

4) 1 hour after the second addition step of preparing the second elastic polymer film layer, stop the ice bath and nitrogen supply, gradually increase the reaction temperature to room temperature, and react for 4 days

5) 4 days after the reaction step, 15 mL of methanol was added to terminate the reaction and remove residual active molecules.

6) After the reaction termination step, a first concentration step of concentrating the reaction solution in half using a rotary evaporator

7) A first filtration step of removing 60 mL of methanol into the reaction solution concentrated by the concentration step, leaving it aside for 30 minutes, and removing the white material and the clear solution in the upper layer.

8) After the filtration step, 100mL of chloroform was added, the solution was thoroughly mixed, 60mL of methanol was added again, and after 30 minutes, the step of removing the white matter and the clear solution in the upper layer was repeated three more times. Second filtration step

9) A second concentration step of removing the solvent from the solution after the second filtration step using a rotary evaporator

10) After the second concentration step, the polymer production step is to prepare a polymer with a high Young's modulus by pouring it into a Teflon dish and drying for about 3 days to remove the solvent.

11) Polymer film layer production step of dissolving 1 g of the prepared polymer in chloroform, pouring it into a Teflon dish with a diameter of 10 cm, and drying for more than 1 day to produce a polymer film layer with a high Young's modulus

is produced through

2. Lamination step

(1) vertically stacking the first viscoelastic polymer film layer 200 and the second elastic polymer film layer 300 having different Young's moduli

(2) A modification step of modifying the surface of the first viscoelastic polymer film layer to be hydrophilic by treating the surface (first viscoelastic polymer film layer) having a low Young's modulus with oxygen plasma for 3 minutes at a power of 100 W.

(3) applying an alginate boronic acid polymer solution on the surface of the first viscoelastic polymer film layer modified to be hydrophilic

is produced through

3. drying step

This is a step in which an alginate boronic acid polymer solution is applied to the surface of the first viscoelastic polymer film layer modified to be hydrophilic, and then the polymer film layer is dried to form a thin layer.

The multilayer adhesive pad formed through the polymer film manufacturing step, polymer film lamination step, and polymer film drying step of the above preparation example includes the adhesive polymer film layer 100 containing alginate boronic acid and the first viscoelastic polymer film containing isophorone diisocyanate. It is a multi-layered adhesive pad attached to the surface of an organic material including a layer 200 and a second elastic polymer film layer 300 containing isophorone diisocyanate and phenyl isocyanate.

In the adhesive pad manufactured according to the above preparation example, the Young's modulus of the first viscoelastic polymer film layer was 0.12 MPa and the Young's modulus of the second elastic polymer film layer was 0.62 MPa. That is, the Young's modulus of the first viscoelastic polymer film layer and the second elastic polymer film layer showed a difference of about 5 times.

Using the multi-layer adhesive pad attached to the surface of the organic material prepared in the above preparation example, several experiments were conducted to prove the increased adhesive strength. In the following experimental example, the experimental example will be described with reference to the drawings.

Experimental Example 1

5 is a diagram explaining mechanical properties of an adhesive pad having a triple layer structure.

The high adhesive force of the adhesive pad composed of “a multi-layered structure of adhesive polymer film layer / first viscoelastic polymer film layer / second elastic polymer film layer” is explained. In order to confirm that the adhesive strength is improved by the triple-layer structure, classification and experiments were carried out by dividing into a total of four groups, and the results, Figure 5, are summarized in Table 1 below.

Table 1 below relates to the mechanical properties (adhesive strength of each layer) of the three-layered adhesive pad.

entry Adhesive polymer film layer Viscoelastic polymer film layer Elastic polymer film layer PDMS Effect (kPa) One O O O X 22~23 2 O X X O 2-3 3 O X O X 16-18 4 O O X X 22~23

In these experiments, skin tissue of mice and the like was used, and it was prepared in 0.5 cm * 1 cm. Thereafter, a polyester (PET) film was attached to the back side and tissue without adhesive polymer, and the tissue and adhesive pad were attached and measured using a universal test machine. Using a 10N load cell, the adhesion was confirmed by stretching at least three specimens from each group at a rate of 20 mm per minute upwards.

The entry 1 is an adhesive pad composed of an adhesive polymer film layer, a viscoelastic polymer film layer, and an elastic polymer film layer, the entry 2 is an adhesive pad composed of an adhesive polymer film layer and PDMS, and the entry 3 is an adhesive pad composed of an adhesive polymer film layer and an elastic polymer film layer. An adhesive pad composed of a film layer, entry 4 is an adhesive pad composed of an adhesive polymer film layer and a viscoelastic polymer film layer.

When the adhesive polymer film layer and the viscoelastic polymer film layer of the entry 1 and entry 4 are adjacent to each other, the most excellent effect was obtained with an adhesive force of 22 kPa to 23 kPa. On the other hand, when only the PDMS of entry 2 was deposited and tested, the adhesive strength was the lowest, and the difference in adhesive strength between the two was 7 to 11 times.

When only the elastic polymer film layer of entry 3 was used, the effect was relatively better than that of the case of using PDMS of entry 2, but the effect was higher than when the viscoelastic polymer film layer and the adhesive polymer film layer of entry 1 and entry 4 were placed adjacently. came out low As a result, when the adhesive polymer film layer and the viscoelastic polymer film layer are adjacent to each other, the adhesive force of the adhesive pad is maximized.

Experimental Example 2

The tensile strength of each triple layer was measured.

6 is a view explaining the mechanical properties of the three-layered adhesive pad.

To measure the tensile strength of each layer, it was stretched 5 times the original length through a universal testing machine and then stretched again after 10 minutes to measure the tensile strength after recovery. The entries used in the experiment are as summarized in Table 2 below.

Table 2 below is a table of the mechanical properties (tensile strength of each layer) of the three-layered adhesive pad.

entry Types of polymer film layers a Elastic polymer film layer b Viscoelastic polymer film layer c Elastic polymer film layer + viscoelastic polymer film layer

In addition, to measure the tensile strength of each layer, the tensile strength after recovery was measured by stretching it 5 times the original length through a universal testing machine and then stretching it again after 10 minutes.

Entry a is an elastic polymer film layer, entry b is a viscoelastic polymer film layer, and entry c is a film layer composed of an elastic polymer film layer and a viscoelastic polymer film layer.

As can be seen in FIG. 6, in the case of entry a using only the elastic polymer film layer, the degree of stretching and recovery of the adhesive pad was 20% lower than that of entry c. This indicates that the viscoelastic layer behind the elastic layer can stably support the load again. Therefore, it is possible to utilize a triple layer adhesive pad utilizing the principle of dispersing force so that it can be stably attached.

Experimental Example 3

Experiments were also conducted to compare the adhesive strength of this commercially available adhesive pad with existing commercial adhesives. Conventional commercially available adhesives are summarized in Table 3 below, and the results of this experiment can be seen in FIG. 8.

Table 3 below is a table showing the results of an experiment comparing adhesive strength with commercially available adhesives.

entry test subject Adhesion (kPa) One Triple layer adhesive pad (invention of this application) 22 to 23 2 Kwik-Cast around 0.4 3 Kwik-Sil around 0.3 4 Greenplast Q around 0.5 5 Tisseel around 0.2

The commercial adhesive adhered to the curing time suggested in the user manual, and was measured using a 10N load cell at a speed of 20mm/min by applying a polyester film to the back side without tissue and adhesive surface.

Entry 1 is a triple layer adhesive pad, and entries 2 to 5 are Kwik-Cast, Kwik-Sil, Greenplast Q, and Tisseel products that have already been commercialized, respectively.

As can be seen from Figure 4, it can be seen that the adhesive force of the triple layer adhesive pad is 40 times higher than that of commercial adhesives.

Experimental Example 4

In addition, to confirm the versatility of this adhesive pad, an experiment was conducted to see if it could be applied to various tissues.

For this experiment, the film was attached to the heart, small intestine, and liver of the rat, and then lifted with tweezers to confirm.

As can be seen through FIG. 5, when the adhered film is lifted using tweezers, it can be seen that the adhered tissue maintains an adhered state and has strong adhesive strength enough to be lifted together.

Finally, the invention of the present application uses a hydrogel precursor as an adhesive, rather than simply using a hydrogel adhesive, so that the adhesive force occurs when contacting a tissue. In the case of conventional adhesives, since the adhesive force is expressed before attaching the adhesive to the tissue, a sticky adhesive pad must be used. there was a point However, in the case of the present application, the hydrogel precursor is also included, and the adhesive force is expressed only after attaching to the tissue, so that the user of the product can overcome the inconvenience previously felt in the process of attaching the adhesive pad.

The above description of the present invention is for illustrative purposes, and those skilled in the art can understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present invention. will be. Therefore, the embodiments described above should be understood as illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present invention is indicated by the following claims, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts should be interpreted as being included in the scope of the present invention.

100: adhesive polymer film layer
200: first viscoelastic polymer film layer
300: second elastic polymer film layer

Claims (18)

an adhesive polymer film layer;
a first viscoelastic polymer film layer positioned on the adhesive polymer film layer; and
A second elastic polymer film layer positioned on the first viscoelastic polymer film layer,
Characterized in that the number of hydrogen bonds possible per functional group of the first viscoelastic polymer film layer contained in the first viscoelastic polymer film layer is smaller than the number of hydrogen bonds possible per functional group of the elastic polymer contained in the second elastic polymer film layer. A multi-layer adhesive pad that attaches to organic surfaces. According to claim 1,
The multi-layer adhesive pad attached to the surface of the organic material, characterized in that the adhesive polymer film layer comprises a hydrogel precursor. According to claim 2,
When the adhesive polymer film layer adheres to the adhesive target, the hydrogel precursor inside the adhesive polymer film layer absorbs moisture of the adhesive target to form an adhesive hydrogel layer and adheres to the organic material surface. pad. According to claim 2,
The hydrogel precursor is characterized in that it comprises an alginate boronic acid polymer, a multi-layer adhesive pad attached to the surface of the organic material. According to claim 1,
A multilayer adhesive pad attached to an organic surface, characterized in that the Young's modulus of the viscoelastic polymer contained in the first viscoelastic polymer film layer is smaller than the Young's modulus of the elastic polymer contained in the second elastic polymer film layer. According to claim 1,
The Young's modulus of the viscoelastic polymer included in the first viscoelastic polymer film layer is smaller than the Young's modulus of the elastic polymer included in the second elastic polymer film layer, so that the external pressure applied from the lower surface direction of the adhesive polymer film layer is A multi-layer adhesive pad attached to the surface of an organic material, characterized in that the force is dispersed within the 1-viscoelastic polymer film layer so that no external pressure is transmitted to the second elastic polymer film layer. delete According to claim 1,
The first viscoelastic polymer film layer includes isophorone diisocyanate, and the second elastic polymer film layer includes an elastic polymer having a Young's modulus greater than the Young's modulus of the viscoelastic polymer of the first viscoelastic polymer film layer. Characterized in that, a multi-layer adhesive pad attached to an organic surface. According to claim 1,
The second elastic polymer film layer includes isophorone diisocyanate, and the first viscoelastic polymer film layer includes a viscoelastic polymer having a Young's modulus smaller than the Young's modulus of the elastic polymer of the second elastic polymer film layer. Characterized in that, a multi-layer adhesive pad attached to an organic surface. According to claim 1,
The second elastic polymer film layer includes phenyl isocyanate (4,4'-Methylenebis (Phenyl Isocyanate)), and the first viscoelastic polymer film layer has a Young's modulus smaller than the Young's modulus of the elastic polymer of the second elastic polymer film layer. A multi-layer adhesive pad attached to an organic surface, comprising a viscoelastic polymer. Preparing a first viscoelastic polymer film layer and a second elastic polymer film layer;
forming a second elastic polymer film layer on an upper surface of the first viscoelastic polymer film layer; and
It characterized in that it comprises the step of forming an adhesive polymer film layer on the lower surface of the first viscoelastic polymer film layer,
Characterized in that the number of hydrogen bonds possible per functional group of the first viscoelastic polymer film layer contained in the first viscoelastic polymer film layer is smaller than the number of hydrogen bonds possible per functional group of the elastic polymer contained in the second elastic polymer film layer. A method for manufacturing a multi-layer adhesive pad attached to an organic surface. According to claim 11,
The step of preparing the first viscoelastic polymer film layer and the second elastic polymer film layer,
Method for manufacturing a multilayer adhesive pad attached to an organic surface, characterized in that the Young's modulus of the viscoelastic polymer included in the first viscoelastic polymer film layer is smaller than the Young's modulus of the elastic polymer included in the second elastic polymer film layer. . According to claim 11,
The step of forming an adhesive polymer film layer on the lower surface of the first viscoelastic polymer film layer,
modifying the lower surface of the first viscoelastic polymer film layer to be hydrophilic by treating with oxygen plasma; and
Forming an adhesive polymer film layer by applying an adhesive polymer solution to the lower surface of the first viscoelastic polymer film layer modified to be hydrophilic. According to claim 11,
The first viscoelastic polymer film layer includes isophorone diisocyanate, and the second elastic polymer film layer includes an elastic polymer having a Young's modulus greater than the Young's modulus of the viscoelastic polymer of the first viscoelastic polymer film layer. Characterized in that, a method for manufacturing a multi-layer adhesive pad attached to an organic surface. According to claim 11,
The second elastic polymer film layer includes isophorone diisocyanate, and the first viscoelastic polymer film layer includes a viscoelastic polymer having a Young's modulus smaller than the Young's modulus of the elastic polymer of the second elastic polymer film layer. Characterized in that, a method for manufacturing a multi-layer adhesive pad attached to an organic surface. According to claim 11,
The second elastic polymer film layer includes phenyl isocyanate (4,4'-Methylenebis (Phenyl Isocyanate)), and the first viscoelastic polymer film layer has a Young's modulus smaller than the Young's modulus of the elastic polymer of the second elastic polymer film layer. A method for manufacturing a multi-layer adhesive pad attached to an organic surface, characterized in that it comprises a viscoelastic polymer. According to claim 11,
The method of manufacturing a multi-layer adhesive pad attached to an organic surface, characterized in that the adhesive polymer film layer comprises an alginate boronic acid polymer. According to claim 11,
The adhesive polymer film layer includes an alginate boronic acid polymer, the first viscoelastic polymer film layer includes isophorone diisocyanate, and the second elastic polymer film layer includes isophorone diisocyanate. Diisocyanate) or phenyl isocyanate (4,4'-Methylenebis (Phenyl Isocyanate)), characterized in that it comprises a multi-layer adhesive pad attached to the surface of the organic material manufacturing method.

Images