KR20190112935A - pH DETECTING MICRO-STRUCTURED STICKER AND THE MANUFACTURING METHOD THEREOF - Google Patents

Abstract

Disclosed are a pH detecting micro-structured sticker capable of measuring a pH level of a sample solution of several microliters (μL), and a manufacturing method thereof. The pH detecting micro-structured sticker of the present invention comprises: a substrate; an adhesive layer formed on one surface of the substrate; and a pH detecting microstructure formed on the other surface of the substrate. The pH detecting microstructure includes a polymer matrix and a pH discoloration detecting pigment dispersed in the polymer matrix, and is configured to change color thereof in an acidity range by contact with an acidic solution, a neutral solution or a basic solution. The pH detecting micro-structured sticker of the present invention can be used by arbitrarily selecting and arranging microstructures for detecting the acidic solution, neutral solution and an acidic and basic solution according to a usage. In addition, the pH detecting micro-structured sticker of the present invention can be manufactured by a simple manufacturing process with inexpensive raw materials, thereby being quickly manufactured in large quantities.

Description

pH sensing micro structure sticker and its manufacturing method {pH DETECTING MICRO-STRUCTURED STICKER AND THE MANUFACTURING METHOD THEREOF}

The present invention relates to a structure capable of sensing the pH of a trace amount of a sample solution and a method of manufacturing the same.

Recently, the development of a lab-on-a-chip in vitro diagnostic device for diagnosing diseases using blood, urine or saliva is rapidly developing. It is important to measure the acidity pH of a solution for the examination of human health or for the measurement of environmental fields and analytical measurements of life science biosamples. In particular, by measuring the acidity of the biochemical sample solution, it is possible to check whether it is harmful to the human body or the state of the sample solution is normal. In addition, pH measurement is important in water quality analysis and measurement of general chemical sample solutions. Under these circumstances, sensors for measuring pH by electrochemical methods have been developed in the last decades.

However, although it is important to measure the pH of the trace amount of the sample solution contained in the microchannel or microchamber of the lab-on-a-chip device, which is rapidly developing in recent years, it is difficult to measure.

Recently, a sensor for measuring pH by an optical method has been developed, but a sensor for measuring a short wavelength fluorescence signal, and using quantum dots by protonation or deprotonation of an organic dye. In the vicinity of the pKa value, the unit measures the pH by swelling or aggregating in response to pH to indicate the change in intensity of luminescence. However, the sensor manufactured by this method has a low signal-to-noise ratio, and non-specific interference by other materials of the sensor may occur, which is a limited method for practical use.

The existing pH meter tester is unable to measure the pH of very small sample solution of several microliters (μL) due to the large amount of sample solution needed to measure pH. However, among sample solutions in the medical and biotechnology fields, the sample solution may have a very small volume or a very small amount. In such a case, pH measurement is practically difficult. It is necessary to overcome the limitations of the existing pH measuring device and to develop a technology for measuring the pH of a very small sample solution (a few μL).

Korean Patent Publication No. 10-2016-0026593 (Published: 2016.03.09) Korea Patent Registration No. 10-1174360 (Registration Date: 2012.08.09) Japanese Patent Publication No. 2013-019804 (Published: 2013.01.31)

The present invention has been made to solve the above-mentioned conventional problems, an object of the present invention is to provide a microstructure having a pH detection function capable of measuring the pH of the sample solution (a few μL) and a manufacturing method thereof. .

PH sensing microstructure sticker according to the present invention,

Board; An adhesive layer or an adhesive layer formed on one surface of the substrate to support the pH sensing microstructure to be described later, and to easily attach and use the surface of various objects; And a pH sensing microstructure formed on the other surface of the substrate.

The pH sensing microstructure is characterized in that it comprises a polymer matrix and pH discoloration detection dye dispersed in the polymer matrix.

Preferably, the polymer matrix is characterized in that it has a porosity.

Preferably, it characterized in that it comprises a plurality of pH sensing microstructures spaced apart on the substrate.

Preferably, at least one of the plurality of pH-sensing microstructures may include a pH discoloration dye which is different from the pH discoloration detection dye contained in the remaining structure, thereby for an acidic solution, a neutral solution, or a basic solution. One sticker made of a combination of microstructures containing different pH discoloration detection dyes on one sticker in accordance with an acidity range, such as a solvent, or a microstructure for the acidic solution, the neutral solution, or the basic solution. One sticker can be implemented.

Preferably, the pH sensing microstructures comprise one or more pH discoloration sensing dyes such that one pH sensing microstructure can simultaneously detect acidity and basicity to exhibit color change.

Furthermore, the present invention is a method of manufacturing the pH-sensitive microstructure sticker,

(a) mixing and dispersing a pH fading detection dye having a different color according to the acidity of the contacting solution in a polymer solution; (b) applying a polymer solution including the pH discoloration sensing dye to the other surface of the substrate to which an adhesive or an adhesive is applied to one surface; (c) adding heat or ultraviolet rays to advance the curing reaction of the polymer solution containing the pH fading detection dye; provides a method for producing a pH-sensitive microstructure sticker comprising a.

Preferably, in the step (c), the polymer solution is characterized in that the curing reaction is carried out by the addition of heat or ultraviolet rays to increase the molecular weight to form a polymer matrix of the solid or semi-solid form.

Preferably, in step (c), the polymer solution subjected to the curing reaction by heat is injected into the mold and then heated to prepare a microstructure, or the photomask on top of the polymer solution undergoing the curing reaction by ultraviolet light. After the arrangement is characterized in that the microstructure is produced by irradiating with ultraviolet light.

Preferably, the pH sensing microstructure may be prepared to have a polymer matrix with or without pores therein depending on the intended use.

In order to prepare a pH sensing microstructure having a polymer matrix having internal pores, the polymer solution further includes a blowing agent, and after completing step (c), the cured microstructure is heated to decompose the blowing agent. And removing to form a porous polymer matrix in the microstructure.

In addition, in order to produce a pH-sensing microstructure having a polymer matrix having the internal pores, the polymer solution further comprises a water-soluble polymer powder, and after completing step (c), the polymer solution contained in the cured microstructure Dissolving and removing the water-soluble polymer powder with water may further include forming a porous polymer matrix in the microstructure.

The present invention can be easily attached and detached to the object to be used as a pH-sensitive micro-structured sticker that can measure the acidity of the trace sample solution, so the pH measurement solution and the range of application is wide.

In general, the pH meter measuring instrument used for pH measurement has a large amount of sample solution required for pH measurement because the probe tube for measuring pH is thick. However, since the pH-sensitive microstructure sticker of the present invention detects the pH of the microstructures of several tens to hundreds of micrometers (μm), the pH measurement can be performed with only a few microliters (μL) of sample solution such as the volume of a drop of water. As a result, the types and range of applications of the sample solutions available are very wide.

The pH sensing microstructure sticker of the present invention is capable of measuring pH for an acidic, neutral or basic solution, and arbitrarily arranges a single or a plurality of acidic solution sensing microstructures, neutral solution sensing microstructures or basic solution sensing microstructures. It is easy to use and has great utility because it can be manufactured.

The pH-sensing microstructured sticker of the present invention is simple in the manufacturing process, the material is inexpensive and the sensitivity is high, it is possible to mass production quickly at an affordable price.

1 is a diagram illustrating a pH sensing microstructure sticker according to the present invention.
2 is a view showing a pH-sensitive porous microstructured sticker of the present invention.
3 is a diagram illustrating a pH sensing microstructured sticker comprising a plurality of dyes according to the present invention.
Figure 4 is a view showing the type of pH-sensitive micro-structured stickers that discolor in the acid, neutral, basic range in the present invention.
Figure 5 is a photograph of the pH-sensing microstructure sticker prepared according to the present invention.
Figure 6 is a photograph of the color change when the pH range of the acid-sensitive and neutral pH-sensitive micro-structured sticker and acid solution in the present invention.
Figure 7 is a photograph of the color change when the pH range of the pH-sensitive micro-structured sticker and a basic solution in the basic discoloration range in the present invention.
8 is a photograph of the color change when the acidic solution and the basic solution are respectively injected into the pH sensing microstructure sticker prepared to have both the acid and basic dye discoloration range in the present invention.
Figure 9 is a photograph taken by manufacturing a pH-sensitive porous micro-structured sticker having a dye range of acid and basic discoloration in the present invention.
FIG. 10 is a photograph of color change by injecting a basic solution into a pH-sensitive porous microstructured sticker having a basic dye discoloration range in the present invention.

In describing the present invention, when it is determined that detailed descriptions of related known functions or configurations may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

Embodiments according to the concept of the present invention can be variously modified and can have various forms, and specific embodiments will be illustrated in the drawings and described in detail in the present specification or application. However, this is not intended to limit the embodiments in accordance with the concept of the present invention to a particular disclosed form, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise" or "having" are intended to indicate that there is a feature, number, step, action, component, part, or combination thereof that is described, and that one or more other features or numbers are present. It should be understood that it does not exclude in advance the possibility of the presence or addition of steps, actions, components, parts or combinations thereof.

Hereinafter, with reference to the accompanying drawings a preferred embodiment of a porous biocompatible polymer structure and a method for producing the same according to the present invention. The terms to be described below are terms defined in consideration of the functions of the present invention, and may be changed according to conventional conventions or the intention of a user. Therefore, the definition of each term should be made by reviewing the contents throughout the present specification.

Hereinafter, with reference to the accompanying drawings, a preferred embodiment of the pH-sensing microstructured sticker and a method of manufacturing the same according to the present invention will be described in detail.

Example 1 Preparation of pH Sensitive Microstructured Sticker

The overall form and components of the pH sensing microstructured sticker according to the present invention are shown in FIG. 1. And a photograph taken of the pH-sensing microstructure sticker actually prepared according to the present invention is shown in FIG.

As shown in FIG. 1, the pH-sensing microstructure sticker 100 according to the present invention includes a polymer matrix including a pH discoloration sensing dye 105 on an upper surface of the substrate 110 on which an adhesive 120 is applied. Made of 101. The pH sensing microstructures according to the invention can be prepared and used in single or in plurality. In addition, the shape of the pH-sensing microstructure according to the present invention can be manufactured in various forms, such as hexagonal or polygonal or circular or hemispherical. In addition, the pH-sensing microstructure according to the present invention may be manufactured to a large size of several millimeters (mm) or more, and may be manufactured to a microstructure having a size of several tens to hundreds of micrometers (μm).

The result of actually preparing the pH sensing microstructured sticker according to the present invention is shown in FIG. 5. 5 (a) is a photograph of the pH-sensing microstructure sticker prepared according to the present invention, Figure 5 (b) is a photograph of the state attached to the pH-sensing microstructure sticker prepared according to the present invention. The pH sensing microstructured sticker according to the invention shown in Figure 5 was prepared using the following materials.

Methyl red was used as the pH change detection dye, and PEG (ME) polyethylene glycol (Methyl ether acrylate) was used as the polymer matrix. In order to proceed with the curing reaction by UV irradiation, 3% by weight of 2-Hydroxy-2-methylpropiophenone was added to PEGMEA (Poly (ethylene glycol) methyl ether acrylate) solution to prepare a mixed solution. And 2% by weight of methyl red was added to the mixed solution and dispersed. A photomask in the form of a micro structure pattern having a diameter of 700 micrometers (μm) was used to prepare the micro structure. The mixed solution in which the methyl red was dispersed was applied to a portion of the transparent tape on which an adhesive was applied on one side, and the photomask was disposed thereon, and irradiated with ultraviolet rays for 10 seconds. After removing the uncured unreacted mixed solution, a pH sensing microstructured sticker was obtained. The resulting photograph is shown in FIG. 5.

Example 2 pH Sensing Performance Test of pH Sensitive Microstructured Sticker

Figure 6 is a photograph of the color change when the pH range of the acid-sensitive and neutral pH-sensitive micro-structured sticker and acid solution in the present invention. Figure 6 (a) to (c) is a photograph of a microstructure including a pH change detection dye showing a color change when the acidic solution is contacted, Figure 6 (d) is a contact when the neutral solution The microstructure including the pH fading detection dye showing a color change in the photograph. More specifically, Figure 6 (a) is a photograph of a pH-sensitive micro-structured sticker containing 2% by weight of basic fuchsin as a pH fading detection dye, Figure 6 (a) in 1 is Figure 6 is a photograph of the pH-sensitive micro-structured sticker prepared in Figure 2 (a) is a photograph after the acidic solution (pH 2.5) injection. And (b) of Figure 6 is a photo of manufacturing a pH sensing microstructure sticker containing 2% by weight methyl orange (methyl orange) as a pH change detection dye, in Figure 6 (b) 1 is the pH sensing microstructure 6 is a photograph of a sticker, and 2 in FIG. 6B is a photograph after injecting an acidic solution (pH 2.5). And (C) of Figure 6 is a photo of manufacturing a pH sensing microstructure sticker containing 2% by weight methyl red (methyl red) as a pH fading detection dye, in Figure 6 (C) 1 is the pH sensing microstructure 6 is a photograph of a sticker, and 2 in FIG. 6 (c) is a photograph after injection of an acid solution (pH 2.5). And (D) of Figure 6 is a photograph of the pH-sensitive microstructure sticker comprising a 2% by weight neutral red (neutral red) as a pH fading detection dye, in Figure 6 (D) 1 is the pH-sensing microstructure 6 is a photograph of a sticker, and 2 in (d) is a photograph after the acidic solution (pH 2.5) is injected.

Figure 7 is a photograph of the color change when the pH range of the pH-sensitive micro-structured sticker and a basic solution in the basic discoloration range in the present invention. Figure 7 (a) is a photo of manufacturing a pH sensing microstructure sticker containing 2 wt% phenolphthalein (phenolphthalein) as a pH change detection dye, in Figure 7 (a) 1 is to prepare the pH sensing microstructure sticker In Figure 7 (a), 2 is a photograph after injecting a basic solution (pH 13.0). And (b) of Figure 7 is a photo of manufacturing a pH sensing microstructure sticker containing 2% by weight of thymolphthalein (thymolphthalein) as a pH change detection dye, in Figure 7 (b) 1 is the pH sensing microstructure. A sticker is a photograph prepared, and FIG. 7 (b) is a photograph after injecting a basic solution (pH 13.0). And (C) of Figure 7 is a photo of manufacturing a pH sensing microstructure sticker containing 2% by weight indigo carmine (indigo carmine) as a pH change detection dye, in Figure 7 (C) 1 is the pH sensing microstructure A sticker is photographed, and 2 in FIG. 7 (c) is a photograph after injection of a basic solution (pH 13.0).

Example 3 Preparation of pH Sensitive Microstructured Sticker Containing a plurality of Dyes and pH Sensitive Performance Test

The pH sensing microstructures of the present invention can be prepared to include a single or a plurality of pH fading detection dyes. In FIG. 3, a pH sensing microstructure sticker 300 including a plurality of dyes including pH discoloration sensing dye 1 105 and pH discoloration sensing dye 2 106 in the polymer matrix 101 is illustrated. 8 shows a photo of actually manufacturing a pH sensing microstructure sticker including a plurality of fillers according to the present invention. The manufacturing process of the pH sensing microstructure shown in Figure 8 is as shown in Example 1. However, in FIG. 8, 2 wt% methyl orange was used as the pH fading detection dye 1 and 2 wt% indigo carmine was included in one microstructure as the pH fading detection dye 2. As a result, the photograph is shown as 1 in FIG. 8 (a) and 1 in FIG. 8 (b). Figure 8 (a) is a photograph showing the process and results of discoloration when the acid solution (pH 2.5) is injected, 1 in Figure 8 (a) is a state before injecting the acid solution, Figure 8 (a) In Figure 2 is a photo showing a state in which some of the microstructures disposed below the color change in contact with the acidic solution, Figure 3 (a) in Figure 3 is a photo showing the state in which all of the microstructures discolored in contact with the acidic solution. to be. And (b) of Figure 8 is a photo showing the process and results of discoloration when the basic solution (pH 13.0) is injected, in Figure 1 (b) of Figure 8 before the injection of the basic solution, Figure 8 ( B) in Figure 2 is a picture showing a state in which some of the microstructures disposed on one side discolored in contact with the basic solution, Figure 3 (b) of Figure 8 shows the state in which all of the microstructures discolored in contact with the basic solution. It is photograph to show.

As shown in (a) to (b) of FIG. 8, it can be observed that the color changes immediately upon contact with an acidic solution or a basic solution, through which the function of the pH sensing microstructure of the present invention can be seen to be excellent. .

Example 4 Preparation of pH Sensitive Microstructured Stickers Having Single or Multiple pH Sensitive Microstructures

The pH sensing microstructure sticker of the present invention can be prepared by combining a single or multiple pH, sensing microstructures. Figure 4 is a view showing the type of pH-sensitive micro-structured stickers that discolor in the acid, neutral, basic range in the present invention. As an example, as shown in 1, 2, and 3 of FIG. 4, a plurality of microstructures including pH discoloration detection dyes exhibiting color change upon contact with an acidic solution may be prepared in a single or on a single substrate. It is possible to manufacture and use a plurality. Herein, for example, microstructures including pH discoloration detection dyes such as basic fuchsin, methyl orange, methyl red, etc., which exhibit color change upon contact with an acidic solution, may be used. It can manufacture and use. And as shown in (b) of Figure 4 it is possible to manufacture a microstructure containing a pH discoloration detection dye showing a color change when the neutral solution is contacted, it is possible to manufacture and use a single or multiple on one substrate . Here, for example, a microstructure including a pH fading detection dye, such as neutral red, which exhibits a color change upon contact with a neutral solution, may be prepared and used. And as shown in 1, 2, 3 in Figure 4 (c) to produce a plurality of microstructures containing a pH change detection dye showing a color change when the basic solution in contact with a single or multiple on a substrate It is possible to manufacture and use. Here, for example, a microstructure including a pH discoloration sensing dye such as phenolphthalein, thymolphthalein, indigo carmine, etc., which exhibits color change upon contact with a basic solution may be prepared and used. Can be.

Example 5 Preparation of pH Sensitive Porous Microstructured Stickers and pH Sensing Performance Test

In the process of manufacturing a pH-sensitive microstructure sticker according to the present invention can be used to prepare a pH-sensitive porous microstructures.

2 is a view showing a pH-sensitive porous microstructured sticker 200 according to the present invention. Prepared to have pores 210 inside the polymer matrix 101 including pH discoloration sensing dye 105, the formation of the pores 210 is prepared by using a blowing agent or by mixing a water-soluble polymer powder in the water tank A method of dipping and dissolving can be used. 9 shows a photograph of a pH-sensitive porous microstructured sticker prepared according to the present invention. In the preparation of the pH-sensitive porous microstructured sticker, PEGMEA (Poly (ethylene glycol) methyl ether acrylate) is used as the organic polymer, and 3 wt% 2-Hydroxy-2-methylpropiophenone as an initiator for curing reaction by UV irradiation. Was used, 2% by weight pH discoloration detection dye was mixed, 30% by weight polyvinylpyrrolidone (PVP) powder was used as the water-soluble polymer powder.

In the manufacturing process of the pH-sensitive porous microstructured sticker, a PEGMEA mixed solution containing 3 wt% 2-Hydroxy-2-methylpropiophenone and 30 wt% PVP is applied on one side of an adhesive-coated substrate and UV is applied for 10 seconds. Investigate. The porous structure was prepared by dissolving and removing the water-soluble polymer PVP powder by immersing the cured structure on the substrate in a water bath for 30 minutes. After drying the porous structure was injected 5% by weight pH discoloration detection dye solution to be absorbed in the porous structure. Thereafter, the porous substrate was placed in a heating oven, and the pH-sensitive porous microstructured sticker was prepared by drying at 70 ° C. for 20 minutes. The result prepared as above is shown in FIG. 9 (a) to (b) are photographs of a porous structure including a pH discoloration detection dye that changes color upon contact with an acidic solution, and FIGS. 9 (a) and (d) are contacted with a basic solution. It is a photograph of a porous structure including a pH discoloration detection dye which is discolored at the time. Figure 9 (a) is a structure containing a basic fuchsin (basic fuchsin) as a pH fading detection dye, Figure 9 (b) is a structure containing methyl red as a pH fading detection dye, 9 (c) is a structure containing phenolphthalein as a pH change detection dye, Figure 9 (d) is a structure containing thymolphthalein as a pH change detection dye.

FIG. 10 is a photograph of color change by injecting a basic solution into a pH-sensitive porous microstructured sticker having a basic dye discoloration range in the present invention. 10 (a) is a photo before contacting the basic solution as a porous structure containing 2% by weight thymolphthalein, Figure 10 (b) is a basic solution (pH 13.0) is in contact with the porous structure At the same time is a picture showing a color change, Figure 10 (c) is a photo showing a color change color by contacting the basic solution (pH 13.0) to the porous structure.

When manufacturing in the form of a porous structure as described above there is a pore inside the sample solution is more free access and the surface area of the porous structure is greatly increased, the contact area with the sample solution is greatly increased so that the discoloration rate is faster.

Hereinbefore, the present invention has been illustrated and described with respect to specific embodiments, but the present invention is not limited thereto, and the following claims are not limited to the scope of the present invention without departing from the spirit and scope of the present invention. It can be easily modified and modified by those skilled in the art.

100: pH Sensing Micro Structure Sticker
101: polymer matrix
105: pH discoloration detection dye or pH discoloration detection dye 1
106: pH discoloration detection dye 2
110: substrate
120: adhesive
200: pH Sensitive Porous Microstructured Stickers
210: pore
300: pH sensing microstructure sticker comprising a plurality of dyes

Claims (11)

Board;
An adhesive layer or an adhesive layer formed on one surface of the substrate; And
It includes; pH sensing microstructure formed on the other side of the substrate,
The pH-sensing microstructure, pH sensing microstructure sticker comprising a polymer matrix and pH discoloration detection dye dispersed in the polymer matrix. The method of claim 1,
PH-sensitive micro structure sticker, characterized in that the polymer matrix has a porosity. The method of claim 1,
And a plurality of pH sensing microstructures spaced apart on said substrate. The method of claim 3, wherein
One or more of the plurality of pH-sensing microstructures, pH fading microstructures sticker, characterized in that it comprises a pH discoloration detection dye and other pH discoloration detection dye contained in the remaining structure. The method of claim 1,
pH-sensing microstructures stickers pH sensing microstructures, characterized in that it comprises one or more pH discoloration detection dye. The method of claim 1,
The pH discoloration detection dyes include basic fuchsin, methyl orange, methyl red, methyl red, neutral red, phenolphthalein, thymolphthalein, indigo carmine ( indigo carmine, safranin O, crystal violet, methyl violet, metanil yellow, bromocresol green, sultone form , 4-nitrophenol, tropaolin, α-naphtholbenzein, methyl blue and orange II sodium salt PH sensing micro structure sticker. (a) mixing and dispersing a pH fading detection dye having a different color according to the acidity of the contacting solution in a polymer solution;
(b) applying a polymer solution including the pH discoloration sensing dye to the other surface of the substrate to which an adhesive or an adhesive is applied to one surface;
(c) adding heat or ultraviolet rays to advance the curing reaction of the polymer solution containing the pH fading detection dye. The method of claim 7, wherein
In the step (c), the polymer solution is a method for producing a pH-sensitive microstructure sticker, characterized in that the curing reaction proceeds by the addition of heat or ultraviolet rays to increase the molecular weight to form a polymer matrix of a solid or semi-solid form. The method of claim 7, wherein
In step (c),
After injecting a polymer solution that undergoes a curing reaction by heat into a mold, heat is applied to prepare a microstructure,
A method of manufacturing a pH sensing microstructure sticker, wherein the microstructure is prepared by irradiating ultraviolet rays after disposing a photomask on top of a polymer solution in which a curing reaction is performed by ultraviolet rays. The method of claim 7, wherein
The polymer solution further comprises a blowing agent,
After completing the step (c), the method for producing a pH-sensitive microstructure sticker further comprises the step of heating the cured microstructure to decompose and remove the blowing agent to form a porous polymer matrix in the microstructure. . The method of claim 7, wherein
The polymer solution further comprises a water-soluble polymer powder,
After completing step (c), further comprising the step of dissolving and removing the water-soluble polymer powder contained in the cured microstructure with water to form a porous polymer matrix in the microstructure, characterized in that it further comprises Method for producing a structure sticker.

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