KR102180459B1 - Covering materials for wound capable of pH detection, and method for manufacturing the same - Google Patents

Abstract

Wound covering material; And a non-woven fabric substrate positioned on one side of the wound covering material and having nanofibers; including, wherein the nanofibers include a fiber-forming polymer and a pH-sensitive dye, and a pH sensitive wound covering material, and a method of manufacturing the same.

Description

TECHNICAL FIELD [Covering materials for wound capable of pH detection, and method for manufacturing the same}

The present invention relates to a pH-sensable wound coating material, and a method of manufacturing the same, and more specifically, without a separate electrical device, a pH-sensable wound coating material capable of quickly detecting a change in pH of a wound site, and a method of manufacturing the same It is about.

Skin protects the human body from various harmful environments such as external microorganisms, ultraviolet rays, and chemicals, as well as preventing dehydration and regulating body temperature by inhibiting water evaporation, an important organ that occupies the largest surface area in our body. to be.

On the other hand, as the industrial society develops, the possibility of skin damage due to various causes such as severe burns, trauma, wounds, bedsores and skin diseases is increasing, and at this time, wounds that cannot be primary sutured are severe defects that require skin transplantation. It also leaves.

Therefore, repair of damaged skin tissue is a very important problem, and in order to promptly heal the wound and minimize various secondary side effects, wound treatment using an appropriate wound covering material is essential.

On the other hand, the pH of normal skin has a function of preventing bacterial invasion by having a weak acidity of about pH 4.8 to 6.0, but the body fluid is neutral. When the wound is normally healed during the wound healing process, the pH changes from weak base to neutral and then weakly acidic, but in the case of poorly healed wounds, it remains basic for a longer time. For example, if the pH of the exudate extracted from the wound of a chronic patient is 6 to 7.5, it can be determined that the wound is healing well, and if the pH of the exudate extracted from the wound is 7.5 to 8, the inflammatory reaction continues and additional treatment is required. It can be judged as necessary.

Therefore, in the wound treatment management field, in the case of a severe or chronic patient with a severe degree of skin trauma, the pH of the wound site can serve as an index to confirm the healing state of the wound, so it is very important to quickly check the pH change. In the wound site, various reactions occur during the natural healing process, and in the case of oxygen release, angiogenesis, proteolytic activity, and bacterial toxicity, the condition of the wound site can be estimated because it causes a pH change.

Conventionally, in order to check the pH of the wound area, a method of combining a pH-sensitive dye using a dyeing method of a wound covering material or a method of receiving an electrical signal from the wound covering material has been used.

In this case, when using the “dyeing method”, the manufacturing process is complicated and applicable materials may be limited because a separate dyeing process is required. When using the dip dyeing method, there is a limit to increasing the amount of dye used as an indicator. In the case of using a printing method, a separate binder is added, so that the ability to detect pH compared to the amount of dye used is likely to decrease, and when a high content is loaded, it is easy to block the flow of exudate or decrease the flexibility. In addition, when a fabric or non-woven material having a fiber diameter of several tens of micrometers is used as a substrate, the flexibility is likely to be significantly lower than that of nanofibers, and when dye is added in a dip dyeing method, the response rate is likely to drop. When a film is used as a substrate, the flexibility is liable to be inferior, complexing with other substrates is limited, and the flow of exudate is easily hindered.

In the case of using a method of receiving an electrical signal from the wound covering, a separate display device or power supply device that displays the electrical signal and collected data by mounting a sensor on the wound covering may be inconvenient and expensive to use.

Therefore, there is still a need to develop a wound coating material having excellent pH sensing performance and flexibility.

The problem to be solved by the present invention is to provide a wound covering material capable of rapidly detecting a pH change of a wound site and having excellent flexibility, and a method of manufacturing the same without a separate electrical device.

In order to solve this problem, according to an aspect of the present invention,

Wound covering material; And located on one side of the wound covering, a non-woven base material having nanofibers; including,

The nanofiber is provided with a pH-sensing wound covering material comprising a fiber-forming polymer and a pH-sensitive dye.

The wound coating material may include a hygroscopic wound coating material, a protective wound coating material, or a mixture of two or more of them.

It may further include an additional wound coating material on one side of the non-woven fabric substrate that does not face the wound coating material.

The pH-sensible wound coating material is formed by stacking the first wound coating material, the nonwoven fabric substrate, and the second wound coating material in this order, and the first wound coating material is a hygroscopic wound coating material, and the second wound coating material is a protective wound coating material. have.

The nonwoven base material may be located on the entire surface of the wound covering material, or may be located only in part.

The non-woven base material is located only on a part of one side of the wound covering material, and may be a square, circular, dot type, mesh type, oblique type, cross shape, letter display type, irregular type, or a mixture of two or more of them.

The pH sensing range of the pH-sensitive dye may be a pH of 4 to 10.

The pH-sensitive dyes are anthocyanin, methyl orange, methyl yellow, metanil yellow, Congo red, chlorophenol red, bromocresol Green (Bromocresol Green), Bromothymol blue (Bromothymol blue), Bromocresol purple (Bromocresol purple), Bromophenol blue (bromophenol blue), Methyl red (Methly red), o-cresolphthalein (o-cresolphthalein) , Phenolphthalein, Alizarine yellow R, Thymolphthalein, Thymol blue, Methylene blue, Sorbitol, Methyl Ethyl Ketone, Cresol red (Cresol red), or a mixture of two or more thereof may be included.

The melting point of the fiber-forming polymer may be 50 to 200°C.

The fiber-forming polymer is polycaprolactone, polyvinyl alchohol, polylactic acid, poly m-aramid, polyurethane, polyurethane, polylactic acid-glycolic acid ( Poly lactide-co-glycolide), polyvinylidene fluoride, polyaniline, polyamide, polyimide, polyamide-imide, polysulfone, Polymethyl methacrylate, or a mixture of two or more of them may be included.

The pH-sensitive dye may be 0.5 to 25 parts by weight based on 100 parts by weight of the fiber-forming polymer.

The specific surface area of the nonwoven substrate may be 3 to 350 m ² /g.

The porosity of the nonwoven fabric substrate may be 70 to 99%.

The average diameter of the nanofibers may be 10 to 1,000 nm.

The thickness of the nonwoven substrate may be 50 to 500 μm.

A standard pattern capable of confirming a pH value detected according to a color change of the nonwoven fabric substrate may be further included on one side of the pH-sensable wound covering material.

According to another aspect of the invention,

Preparing a polymer solution by dissolving a fiber-forming polymer in a solvent;

Preparing a mixed solution by mixing a pH-sensitive dye with the prepared polymer solution;

Electrospinning the mixed solution to prepare a nonwoven fabric having nanofibers; And

There is provided a method of manufacturing a pH-sensing wound covering material comprising; bonding the wound covering material to one surface of the nonwoven fabric substrate.

Distilled water, acetone, ethanol, dimethylacetamide (DMAc), tetrahydrofuran (THF), dimethylformamide (DMF), acetic acid (Acetic acid), chloroform (Chloroform), methylpyrroly Don (N-Methyl-2-pyrrolidone), dimethyl sulfoxide (DMSO), dichloromethane (Dichloromethane), or a mixture of two or more thereof may be included.

The step of bonding the wound covering material to one side of the nonwoven substrate may be performed by a thermal fusion method, an adhesive method, an ultrasonic bonding method, a high frequency bonding method, or a mixing method of two or more of them.

It may further include the step of bonding an additional wound coating material on one side of the non-woven fabric substrate that does not face the wound coating material.

According to the present invention, it is possible to provide a wound covering material capable of detecting pH including a nanofiber nonwoven fabric having excellent pH sensing performance and excellent flexibility due to its large specific surface area and porosity.

Specifically, the pH sensitive wound covering material of the present invention uses a nanofiber nonwoven fabric characterized in that the color changes according to the pH change of the wound site, so that the color change is observed visually rather than measuring the pH through a separate electric device. It is easy to use and cheap. In addition, by manufacturing a nonwoven fabric having a nanometer-level diameter through electrospinning a polymer mixed with a dye capable of detecting pH, the specific surface area is large, the response speed is fast, and the flexibility is excellent, so that it adheres to the curved area. The treatment is easy even when combined with a dressing, and it has porosity, so it does not interfere with the flow of liquids such as exudates discharged from the wound area. Furthermore, it is easy to manufacture by using a blending method with a polymer, and has a high content. It is easy to mix the dyes of, and various polymers can be used as a substrate.

In addition, the pH-sensing wound covering material of the present invention is particularly applicable to chronic wounds, and can be used for the purpose of observing changes in the pH of the medium when culturing cells for the purpose of tissue engineering.

The following drawings attached to the present specification illustrate preferred embodiments of the present invention, and serve to further understand the technical spirit of the present invention together with the detailed description of the present invention to be described later. It is limited only to and should not be interpreted.
1 is a schematic cross-sectional view of a wound covering material capable of detecting pH according to an embodiment of the present invention.
2 is a schematic cross-sectional view of a wound covering material capable of detecting pH according to an embodiment of the present invention.
3 is a schematic cross-sectional view of a wound covering material capable of detecting pH according to an embodiment of the present invention.
4A, 4B, and 4C are views schematically showing various patterns of a nonwoven fabric with nanofibers including a pH-sensitive dye in the wound covering material capable of detecting pH according to an embodiment of the present invention.
5A and 5B schematically illustrate an example in which a standard pattern capable of confirming a pH value detected according to a color change of a nonwoven fabric substrate is further included on one side of the wound covering material capable of detecting pH according to an embodiment of the present invention. It is a drawing.
6 is an optical photograph of the wound coating material capable of detecting pH prepared in Example 1.
7 and 8 are optical photographs observing the color change according to the pH change of the pH-sensable wound covering material prepared from Examples 1 and 3, respectively.
9A and 9B are optical photographs observing the color change according to pH change and the pH-sensable wound covering material prepared from Example 3, respectively.
10 is an optical photograph of a color change according to a pH change of a pH-sensable wound covering prepared from Example 2 and Comparative Example 1

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Prior to this, terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventors appropriately explain the concept of terms in order to explain their own invention in the best way. Based on the principle that it can be defined, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.

Accordingly, the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiment of the present invention, and do not represent all the technical spirit of the present invention, and thus various alternatives that can be substituted for them at the time of application It should be understood that there may be equivalents and variations.

A pH-sensing wound covering material according to an aspect of the present invention includes: a wound covering material; And a nonwoven fabric substrate positioned on one side of the wound covering material and having nanofibers, wherein the nanofibers include a fiber-forming polymer and a pH-sensitive dye.

The wound covering material refers to a medical substrate capable of effectively absorbing blood or exudates generated from wounds such as wounds or burns or maintaining a moist environment while effectively protecting the wound area. Therefore, the wound covering material should be excellent in biocompatibility, so that there should be no rejection reaction to the wound area, and should have functions such as wound protection, contamination prevention, exudate absorption, bleeding or loss of body fluid.

In addition, the characteristics required to be equipped as the above wound covering are “to be able to remove exudate and toxic elements”, “to be able to maintain a moist environment on the wound surface”, “to be easy to exchange gas”, “secondary Some examples include protecting the wound from infection” and “can be removed without further trauma”.

The wound covering material according to an embodiment of the present invention may have various forms such as a nonwoven fabric type, a film type, and a foam type, and the raw material may be formed of various materials such as synthetic polymers, natural polymers, and bio-derived materials.

These wound coverings can be divided into hygroscopic wound coverings and protective wound coverings according to their required performance.

The hygroscopic wound covering material should have a moisture permeability capable of maintaining high moisture permeability in order to directly face the wound area to prevent invasion of normal skin around the wound, and to remove exudate and toxic elements. Non-woven fabric type, foam type, and the like can be applied as the hygroscopic wound covering material, and the non-woven fabric type includes a carboxymethyl cellulose non-woven fabric, alginate non-woven fabric, cellulose non-woven fabric, and chitosan non-woven fabric, etc., which are excellent in biocompatibility, and the like.

The protective wound covering material serves to protect the wound from secondary infection, such as waterproofing and preventing bacteria penetration, and is a polymer film type (for example, a polyurethane film, etc.), a polymer sheet type (for example, Hydrogel sheet, etc.).

The wound coating material according to an embodiment of the present invention may include a hygroscopic wound coating material, a protective wound coating material, or a mixture of two or more of them.

1 to 3 are schematic cross-sectional views of a wound covering material capable of detecting pH according to an embodiment of the present invention.

Referring to Figure 1, the pH-sensing wound coating material according to an embodiment of the present invention is a wound coating material (1), and a non-woven fabric having nanofibers including a pH-sensitive dye located on one side of the wound coating material (1). It includes a base material (2).

Referring to Figure 2, the pH-sensing wound covering material according to an embodiment of the present invention is a wound covering material 3, and a non-woven fabric having nanofibers including a pH-sensitive dye located on one side of the wound covering material 3 It includes a base material (2). Comparing FIGS. 1 and 2, in FIG. 1, the nonwoven fabric substrate 2 having nanofibers including the pH-sensitive dye is located on the upper surface of the wound covering material 1, and in FIG. 2, the pH-sensitive dye is included. The nonwoven base material 2 having nanofibers is located on the lower surface of the wound covering material 3. At this time, when the lower side of the wound covering material 1 in FIG. 1 is the wound area, the wound covering material 1 is directly facing the wound area, and a hygroscopic wound covering material may be applied among the types of the wound covering material described above. In addition, when the lower side of the nonwoven fabric base material 2 having the nanofibers including the pH-sensitive dye in FIG. 2 is the wound area, the wound covering material 3 does not directly face the wound area, and the aforementioned wound Of the types of cladding, protective wound cladding may be applied.

According to FIG. 3, the pH-sensable wound coating material according to an embodiment of the present invention includes a first wound coating material (1), a non-woven fabric base material having nanofibers containing a pH-sensitive dye (2), and a second wound coating material ( It can be formed by stacking in the order of 3). In this case, the first wound covering material may be a hygroscopic wound covering material positioned directly facing the wound area, and the second wound covering material may be a protective wound covering material. The non-woven fabric substrate (2) having nanofibers containing the pH-sensitive dye is a hygroscopic wound covering (1) that serves to absorb exudate by directly facing the wound site, and a protective wound that prevents secondary infection from outside It is interposed between the covering materials 3. The hygroscopic wound covering material 1 absorbs and contains exudate, and after a certain period of time, the impregnated exudate and the like are provided with nanofibers containing the pH-sensitive dye located on the upper surface of the hygroscopic wound covering material 1 It comes into contact with the non-woven base material 2. At this time, as a result of contact with the exudate liquid, the nanofibers including the pH-sensitive dye constituting the nonwoven substrate 2 cause a predetermined color change depending on the pH of the exudate. At this time, by looking at the color change, it is possible to determine the exudate pH condition, specifically, the actual condition of the wound area.

The nonwoven base material may be located on the entire surface of the wound covering material, or may be located only in part. At this time, when the non-woven base material is located on the entire surface of the wound covering material, the response speed may be increased and visibility may be improved. When the non-woven base material is located only on a part of one side of the wound coating material, transparency can be prevented from deteriorating when it is combined with a wound coating material that has excellent transparency and is advantageous for observation of the wound area.

The non-woven base material is located only on a part of one side of the wound covering material, and may be introduced in various forms. Non-limiting examples of the shape may be a triangle, a square, a circle, a dot type, a mesh type, an oblique line, a cross shape, a letter display type, an irregular shape, or a mixture of two or more of them. In this case, the character display type may further emphasize visibility by making the character “caution” stand out, for example.

4A, 4B, and 4C are views schematically showing various patterns of a nonwoven fabric with nanofibers including a pH-sensitive dye in the wound covering material capable of detecting pH according to an embodiment of the present invention. Referring to FIGS. 4A, 4B, and 4C, the nonwoven fabric base material having nanofibers containing a pH-sensitive dye does not cover all of the upper surface of the wound covering material, but is located only in part, and its shape is also a square, It has a cross shape and a mesh shape, respectively.

In addition, according to an embodiment of the present invention, the pH detection range of the pH-sensitive dye may be a pH of 4 to 10, or a pH of 5 to 10, or a pH of 6 to 9. At least one pH-sensitive dye may be mixed with the nanofiber, and two or more pH-sensitive dyes may be mixed and used depending on the pH detection range of the dye. At this time, since a pH-sensitive dye having a wide pH detection range, such as anthocyanin, can detect both acidity and basicity, it may be more advantageous in the application of the present invention.

The pH-sensitive dyes include anthocyanin, methyl orange, methyl yellow, metanil yellow, Congo Red, chlorophenol red, bromo Cresol Green, Bromothymol Blue, Bromocresol Purple, Bromophenol Blue, Methyl Red, o-Cresolphthalein ), Phenolphthalein, Alizarine Yellow R, Thymolphthalein, Thymol Blue, Methylene Blue, Sorbitol, Methyl Ethyl Ketone , Cresol Red, or a mixture of two or more of them may be included. In particular, anthocyanin extracted from natural vegetables may be used as the pH-sensitive dye.

According to the manufacturing method described later, a pH-sensitive dye may be mixed with a polymer solution to form nanofibers through electrospinning. In this case, for some pH-sensitive dyes, a method of bonding with a polymer through chemical modification may be applied.

The melting point of the fiber-forming polymer may be 50 to 300°C, or 50 to 150°C. When the melting point of the fiber-forming polymer has such a range, it is easy to attach a nanofiber nonwoven fabric containing a pH-sensitive dye with other components of a wound covering material such as a urethane film by a simple process such as thermal fusion or ultrasonic bonding. can do.

The fiber-forming polymer is not limited as long as it is a material capable of electrospinning into nanofibers, including pH-sensitive dyes, examples of which are polycaprolactone, polyvinyl alchohol, and polylactic acid. , Poly m-aramid, Polyurethane, Poly lactide-co-glycolide, Polyvinylidene fluoride, Polyaniline, Polyamide ), polyimide, polyamide-imide, polysulfone, polymethyl methacrylate, or a mixture of two or more of them.

The content of the pH-sensitive dye may be 0.5 to 25 parts by weight, 5 to 20 parts by weight, or 5 to 15 parts by weight based on 100 parts by weight of the fiber-forming polymer. When the content of the pH-sensitive dye satisfies this range, pH-sensitivity may be ensured, and manufacturing processability of the nanofiber nonwoven fabric may be improved during the electrospinning process.

The specific surface area of the nonwoven substrate may be 3 to 350 m ² /g, or 4 to 35 m ² /g, or 7 to 30 m ² /g. When the specific surface area of the non-woven fabric base material satisfies this range, the pH sensitivity is improved, and a problem in which the manufacturing processability of the nano-fiber non-woven fabric becomes too thin during the electrospinning process can be prevented.

The porosity of the nonwoven substrate may be 70 to 99%, or 80 to 95%. When the porosity of the non-woven fabric base material satisfies this range, the flow of fluid such as exudate from the wound portion of the human body is not disturbed, and the shape of the non-woven fabric base material is maintained, thereby improving the processability of manufacturing the wound covering material.

The thickness of the non-woven substrate may be 50 to 500 µm, more preferably 100 to 300 µm. When the thickness of the nonwoven substrate satisfies this range, visibility may be improved, handling may be facilitated in a process, and flexibility may be improved.

The average diameter of the nanofibers may be 10 to 1,000 nm, or 100 to 800 nm, or 120 to 450 nm. When the average diameter of the nanofibers satisfies this range, the electrospinning process is easy and the pH response speed can be improved.

A standard pattern capable of confirming a pH value detected according to a color change of the nonwoven fabric substrate may be further included on one side of the pH-sensable wound covering material. As such a standard pattern, referring to FIG. 5A, different pH values corresponding to the continuous color change are described, and referring to FIG. 5B, standard colors corresponding to a specific pH value are presented.

A method of manufacturing a pH sensitive wound covering according to an aspect of the present invention,

Preparing a polymer solution by dissolving a fiber-forming polymer in a solvent;

Preparing a mixed solution by mixing a pH-sensitive dye with the prepared polymer solution;

Electrospinning the mixed solution to prepare a nonwoven fabric having nanofibers; And

It includes; bonding the wound covering material to one surface of the nonwoven fabric substrate.

Hereinafter, we will look at each step.

First, an electrospinning method is used to prepare the nonwoven substrate of the present invention. A polymer solution is prepared by dissolving the fiber-forming polymer in a solvent. The fiber-forming polymer is as described above.

The solvent used for preparing the polymer solution is not particularly limited, but as non-limiting examples, distilled water, acetone, ethanol, dimethylacetamide (Dimethylacetamide, DMAc), tetrahydrofuran (THF), dimethylformamide, DMF), acetic acid, chloroform, methyl pyrrolidone (N-Methyl-2-pyrrolidone), dimethyl sulfoxide (DMSO), dichloromethane, or two or more of these It may contain mixtures.

In this case, the content of the polymer in the polymer solution may be adjusted to 5 to 20% by weight, or 8 to 15% by weight of the total polymer solution. When the weight% is adjusted in this way, it is possible to obtain an electrospinning solution that is uniformly dissolved and has an appropriate viscosity and is easy to handle, resulting in improved spinning properties and a uniform diameter distribution of the prepared fibers.

Next, a mixed solution is prepared by mixing a pH-sensitive dye with the prepared polymer solution. The pH-sensitive dye may be 0.5 to 25 parts by weight, 5 to 20 parts by weight, or 5 to 15 parts by weight based on 100 parts by weight of the fiber-forming polymer. When the content of the pH-sensitive dye satisfies this range, pH-sensitivity may be ensured, and manufacturing processability of the nanofiber nonwoven fabric may be improved during the electrospinning process. The kind of the pH-sensitive dye is as described above.

According to an embodiment of the present invention, a fiber-forming polymer is completely dissolved in a solvent without impurities, a pH-sensitive dye is mixed therein, and stirred at room temperature for about 12 hours, and then a mixed solution for electrospinning can be prepared. .

Next, the mixed solution is electrospun to prepare a nonwoven fabric including nanofibers.

According to a conventional electrospinning system and theory, the electrospinning process must be performed under high voltage, and the air condition inside the chamber is also very important due to the characteristics of electrospinning. In the case of manufacturing fibers by such a general process, due to the electrostatic process characteristics sensitive to the environment (temperature, humidity) of the spinning chamber, minute changes in the shape of the fibers occur, and it is difficult to make a reproducible material.

According to an embodiment of the present invention, the electrospinning device includes one or more syringes in which 18G to 24G nozzles made of stainless steel are inserted into an integrally configured (+) charge high voltage generator, an integrated drum, and a quantitative discharge pump, or It may be equipped with two or more. In the present invention, after manufacturing each fiber nonwoven fabric according to the concentration of the solution, applied voltage, spinning distance, fluid velocity, rotation speed of the current collector plate, etc., which have an important influence on the fiber shape among various process factors, the structure and shape are analyzed and the reproducibility is the most. Good electrospinning conditions were obtained and applied.

Electrospinning according to an embodiment of the present invention, the applied voltage 5 to 100 kV, the spinning speed of the solution (fluid speed) 0.1 to 10 ul/min, the spinning distance 3 to 50 cm, the rotation speed of the current collector plate 10 to 1,000 rpm It is carried out under the electrospinning conditions of.

The nanofiber web obtained as a result of the electrospinning can be applied as a nonwoven substrate as it is, or the residual solvent is removed from the nanofiber web obtained as a result of the electrospinning, and finally, a nonwoven substrate having nanofibers containing a pH-sensitive dye is prepared. can do. At this time, a vacuum oven or the like may be used to remove the residual solvent.

Thereafter, the wound covering material is bonded to one side of the nonwoven fabric substrate.

The step of bonding the wound covering material to one side of the non-woven substrate may be performed by a heat fusion method, an adhesive method using an adhesive, an ultrasonic adhesion method, a high frequency adhesion method, or the like.

According to an embodiment of the present invention, it may further include the step of bonding an additional wound coating material on one side of the non-woven base material that does not face the wound coating material.

Hereinafter, examples will be described in detail to aid understanding of the present invention. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the following examples. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

Example One

(1) Preparation of non-woven base material

A polymer solution was prepared by dissolving polycaprolactone (PCL) to 14% by weight in a mixed solvent (weight ratio = 45/45/10) of tetrahydrofuran (THF)/dimethylformamide (DMF)/acetic acid. Anthocyanin-based dye (CAS#11029-12-2, Xian Baichuan Biotech) was added to the polymer solution to 15 parts by weight based on 100 parts by weight of polycaprolactone, and stirred at 60° C. for 2 hours to prepare a mixed solution. At this time, the pH detection range of the anthocyanin-based dye was pH 0 to 14.

Thereafter, 3 mL of the mixed solution was spun onto a rotating drum current collector plate using an electrospinning device, and a nanofiber web was formed. At this time, the applied voltage was 15 kV and the spinning distance (between the syringe tip and the current collector plate) during electrospinning. Distance) was 15 cm, the spinning speed (fluid speed) was 25 ul/min, the rotation speed of the drum-type current collector was adjusted to 300 rpm, and the temperature and humidity during electrospinning were 30°C and 50% RH, respectively. Then, the formed nanofiber web was dried under reduced pressure at room temperature for 24 hours using a vacuum oven, and the residual solvent was removed to prepare a nonwoven fabric substrate having nanofibers mixed with a pH-sensitive dye. At this time, the specific surface area of the nonwoven substrate was 15 m ² /g, the porosity was 87%, the thickness was 70 μm, the elongation was 300%, and the average diameter of the nanofibers was 230 nm.

At this time, the method of measuring the properties of the nonwoven fabric substrate was as follows, and the same was applied hereinafter.

1) Specific surface area of the nonwoven base material

The specific surface area of the nonwoven fabric substrate was measured using a liquid nitrogen physical adsorption method of BET equipment (ASAP2010, Micromeritics, USA).

2) Porosity of the nonwoven base material

The porosity of the nonwoven substrate was measured by a Mercury porosimeter (Autopore IV 9500 V1.07, Micromeritics Instrument Corporation, Norcross, GA).

3) Thickness of the non-woven base material

The thickness of the non-woven substrate was measured using a thickness gauge (Mitutoyo).

4) Elongation of the nonwoven base material

The elongation of the nonwoven base material was measured by using a tensile strength measuring device, with a sample width of 10 mm, a gripping distance of 20 mm, and a tensile speed of 20 mm/min.

5) Average diameter of nanofibers of nonwoven fabric base

It was measured using a scanning electron microscope (SEM), and at this time, the fiber diameter was measured 10 times and the average value was described.

(2) Manufacturing of wound covering material capable of detecting pH

The prepared nonwoven fabric base material (nanofiber nonwoven fabric base material mixed with pH sensitive dye) having nanofibers mixed with the prepared pH sensitive dye was cut into a size of 1.5cm×1.5cm. The cut-off pH-sensitive dye-incorporated nanofiber nonwoven fabric substrate was placed on the upper surface of a hygroscopic carboxymethylcellulose nonwoven fabric (AQUACEL™, ConvaTec) as a wound covering material to prepare a pH sensitive wound covering material. Fig. 6 shows an optical picture of the prepared pH sensitive wound covering. Referring to Figure 6, the prepared pH-sensitive wound covering material is a carboxymethyl cellulose non-woven fabric (10, wound covering material), a non-woven fabric substrate 11 having nanofibers mixed with a pH-sensitive dye is positioned on the upper surface.

Example 2

(1) Preparation of non-woven base material

A non-woven fabric substrate having polycaprolactone nanofibers mixed with a pH-sensitive dye was prepared in the same manner as in Example 1, except that 5 parts by weight of an anthocyanin-based dye, which is a pH-sensitive dye, was used based on 100 parts by weight of polycaprolactone. .

At this time, the specific surface area of the nonwoven substrate was 13 m ² /g, the porosity was 86%, the thickness was 68 μm, the elongation was 280%, and the average diameter of the nanofibers was 250 nm.

(2) Manufacturing of wound covering material capable of detecting pH

In the same manner as in Example 1 (2), except that the non-woven fabric base material prepared in Example 3 (1) was used instead of the non-woven fabric base material prepared in Example 1 (1), Was prepared.

Example 3

(1) Preparation of non-woven base material

In the same manner as in Example 2 (1), a non-woven fabric substrate having polycaprolactone nanofibers mixed with a pH-sensitive dye was prepared.

(2) Manufacturing of wound covering material capable of detecting pH

The prepared nonwoven fabric substrate (nanofiber nonwoven fabric substrate mixed with pH sensitive dye) having nanofibers mixed with the prepared pH-sensitive dye was cut into a size of 1 cm×1 cm. Place the cut pH-sensitive dye-incorporated nanofiber nonwoven fabric substrate as the first wound covering material on the upper surface of the hygroscopic carboxymethylcellulose nonwoven fabric (AQUACEL™, ConvaTec), and the pH-sensitive dye-mixed nanofiber nonwoven fabric substrate second A protective substrate, a polyurethane film (MED 5500SI, Vancive) with an adhesive, was attached as a wound covering material. As a result, a pH sensitive wound covering material was prepared in which a non-woven fabric substrate with nanofibers containing a pH-sensitive dye was located between the carboxymethylcellulose non-woven fabric and the polyurethane film.

Comparative example One

To prepare a solution used for printing, first, as a binder, 2 g of ethyl cellulose and 3 g of triethyl citrate as a plasticizer were mixed with methanol as a solvent, followed by stirring for about 6 hours. , 0.5% by weight of anthocyanin dye was added to the solution, and then stirred for 1 hour to prepare a printing solution. This solution was transferred to each polyester fabric (ISO 105-F04 polyester standard white cloth) and dried at 80°C for 5 minutes. At this time, the content of the anthocyanin dye was about 5% by weight compared to the polyester fabric.

Experimental example One; Measurement of color change according to pH

Solutions of pH 4 to 10 were each prepared using a buffer solution.

The prepared buffer solution for each pH was added dropwise in an amount of 0.5 mL to each of the separate Petri dishes, and the pH-sensing wound prepared from Examples 1 to 3 and Comparative Example 1 so that the carboxymethylcellulose nonwoven fabric as a wound covering material touched the buffer solution The cladding was placed. As a result, it was confirmed that the carboxymethylcellulose nonwoven fabric was first sufficiently wetted in a buffer solution, and then the buffer solution penetrated into the nanofiber nonwoven fabric substrate containing a pH-sensitive dye located on the upper surface of the wound covering material to express color.

7 and 8 are optical photographs observing the color change according to the pH change of the pH-sensable wound covering material prepared from Examples 1 and 2, respectively.

Referring to FIGS. 7 and 8, it was confirmed that colors were distinguished well enough to be visually identifiable according to pH. It was confirmed that the color was pink in acidic conditions and blue in basic conditions. In the case of Example 1 (FIG. 7) having a large content of the pH-sensitive dye, it was possible to visually confirm a more vivid color change than that of Example 2 (FIG. 8).

9A and 9B are optical photographs observing the color change according to pH change and the pH-sensable wound covering material prepared from Example 3, respectively.

Referring to FIG. 9A, between the pH-sensitive dye-incorporated nanofiber nonwoven fabric base 22 is a hygroscopic carboxymethylcellulose nonwoven fabric 21 as a first wound covering material and a polyurethane film 23 as a protective substrate as a second wound covering material. It is located in.

Referring to FIG. 9B, it was confirmed that colors were well distinguished so that they could be identified with the naked eye according to pH. In acidic conditions, it was confirmed that the pink color decreased and gradually became blue as it went from neutral to basic.

10 is an optical photograph of a color change according to a pH change of a pH-sensable wound covering prepared from Example 2 and Comparative Example 1

Referring to FIG. 10, the pH-sensable wound covering material of Example 2 had a distinct color change than that of Comparative Example 1.

Claims (20)

Wound covering material; And located on one side of the wound covering, a non-woven base material having nanofibers; including,
The nanofibers contain a fiber-forming polymer and a pH-sensitive dye,
The fiber-forming polymer is polycaprolactone, polylactic acid, poly m-aramid, polyurethane, poly lactide-co-glycolide, Polyvinylidene fluoride, polyaniline, polyamide, polyimide, polyamide-imide, polysulfone, polymethyl methacrylate ), or a pH-sensing wound covering consisting of a mixture of two or more of them. The method of claim 1,
The wound coating material is a hygroscopic wound coating material, a protective wound coating material, or a pH-sensing wound coating material comprising a mixture of two or more of them. The method of claim 1,
A pH-sensable wound coating material further comprising an additional wound coating material on one side of the nonwoven base material that does not face the wound coating material. The method of claim 1,
The pH-sensable wound coating material is formed by stacking the first wound coating material, the nonwoven fabric base material, and the second wound coating material in this order, and the first wound coating material is a hygroscopic wound coating material, and the second wound coating material is a protective wound coating material. Detectable wound covering. The method of claim 1,
The non-woven base material is located on the entire surface of the wound coating material, or is located only in part of the wound coating material capable of detecting pH. The method of claim 5,
The non-woven base material is located only on a part of one side of the wound coating material, a square, circular, dot type, mesh type, oblique type, cross shape, letter display type, irregular shape, or a combination of two or more of them, pH sensing possible wound coating material. The method of claim 1,
The pH detection range of the pH-sensitive dye is a pH-sensing wound covering material of 4 to 10. The method of claim 1,
The pH-sensitive dyes are anthocyanin, methyl orange, methyl yellow, metanil yellow, Congo red, chlorophenol red, bromocresol Green (Bromocresol Green), Bromothymol blue (Bromothymol blue), Bromocresol purple (Bromocresol purple), Bromophenol blue (bromophenol blue), Methyl red (Methly red), o-cresolphthalein (o-cresolphthalein) , Phenolphthalein, Alizarine yellow R, Thymolphthalein, Thymol blue, Methylene blue, Sorbitol, Methyl Ethyl Ketone, Cresol red (Cresol red), or a pH-sensitive wound covering comprising a mixture of two or more thereof. delete delete The method of claim 1,
The pH-sensitive dye is 0.5 to 25 parts by weight based on 100 parts by weight of the fiber-forming polymer. The method of claim 1,
A pH sensitive wound covering material having a specific surface area of 3 to 350 m ² /g of the nonwoven substrate. The method of claim 1,
A pH-sensing wound covering material having a porosity of 70 to 99% of the nonwoven fabric substrate. The method of claim 1,
The average diameter of the nanofibers is 10 to 1,000nm pH detection possible wound covering. The method of claim 1,
The thickness of the non-woven fabric substrate is 50 to 500 ㎛ pH detection possible wound covering. Wound covering material; And located on one side of the wound covering, a non-woven base material having nanofibers; including,
As a pH-sensing wound covering material, wherein the nanofibers include a fiber-forming polymer and a pH-sensitive dye,
A pH-sensable wound coating further includes a standard pattern capable of confirming a pH value detected according to a color change of the nonwoven fabric on one side of the pH-sensable wound coating material. A polymer solution is prepared by dissolving a fiber-forming polymer in a solvent, and the fiber-forming polymer is polycaprolactone, polylactic acid, poly m-aramid, polyurethane, Poly lactide-co-glycolide, polyvinylidene fluoride, polyaniline, polyamide, polyimide, polyamide-imide, Polysulfone (Polysulfone), polymethyl methacrylate (Polymethyl Methacrylate), or a step consisting of a mixture of two or more thereof;
Preparing a mixed solution by mixing a pH-sensitive dye with the prepared polymer solution;
Electrospinning the mixed solution to prepare a nonwoven base material including nanofibers; And
The method of manufacturing a wound covering material capable of detecting the pH of claim 1 comprising; bonding the wound covering material to one surface of the nonwoven fabric substrate. The method of claim 17,
The solvent is acetone, ethanol, dimethylacetamide (DMAc), tetrahydrofuran (THF), dimethylformamide (DMF), acetic acid, chloroform (Chloroform), methylpyrrolidone ( N-Methyl-2-pyrrolidone), dimethyl sulfoxide (DMSO), dichloromethane (Dichloromethane), or a method for producing a pH-sensing wound covering material comprising a mixture of two or more thereof. The method of claim 17,
The step of bonding the wound coating material to one side of the non-woven fabric substrate is a method of manufacturing a pH-sensing wound coating material that is performed by a heat fusion method, an adhesive method, an ultrasonic bonding method, a high frequency bonding method, or a mixing method of two or more of them. The method of claim 17,
The method of manufacturing a pH-sensing wound covering material further comprising the step of combining an additional wound covering material on one side of the nonwoven fabric base material that does not face the wound covering material.

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