KR20230050008A - pH sensing membrane with improved leaching resistance of indicator and manufacturing method thereof - Google Patents
pH sensing membrane with improved leaching resistance of indicator and manufacturing method thereof Download PDFInfo
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- 238000001139 pH measurement Methods 0.000 title claims abstract description 52
- 238000002386 leaching Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000012528 membrane Substances 0.000 title abstract description 21
- 229920002678 cellulose Polymers 0.000 claims abstract description 60
- 239000001913 cellulose Substances 0.000 claims abstract description 60
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 25
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 25
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 19
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 15
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims abstract description 13
- 230000008859 change Effects 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 11
- 229960000800 cetrimonium bromide Drugs 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- KHLVKKOJDHCJMG-QDBORUFSSA-L indigo carmine Chemical compound [Na+].[Na+].N/1C2=CC=C(S([O-])(=O)=O)C=C2C(=O)C\1=C1/NC2=CC=C(S(=O)(=O)[O-])C=C2C1=O KHLVKKOJDHCJMG-QDBORUFSSA-L 0.000 claims description 8
- 229960003988 indigo carmine Drugs 0.000 claims description 8
- 235000012738 indigotine Nutrition 0.000 claims description 8
- 239000004179 indigotine Substances 0.000 claims description 8
- PRZSXZWFJHEZBJ-UHFFFAOYSA-N thymol blue Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C PRZSXZWFJHEZBJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000004043 dyeing Methods 0.000 claims description 5
- 230000008961 swelling Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000004043 responsiveness Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 1
- 239000012670 alkaline solution Substances 0.000 abstract 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical group Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 abstract 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 20
- 239000007853 buffer solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical group C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229960003431 cetrimonium Drugs 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 238000000985 reflectance spectrum Methods 0.000 description 1
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- 239000011800 void material Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
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- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N21/80—Indicating pH value
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- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
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Abstract
Description
본 발명은 양극성화된 셀룰로오스 및 폴리디메틸실록산를 활용하여 지시약의 침출저항성을 개선시킬 수 있는 pH 감지막의 제조방법 및 상기 방법으로 제조된 pH 감지막에 관한 것이다.The present invention relates to a method for manufacturing a pH sensing film capable of improving the leaching resistance of an indicator by utilizing anodized cellulose and polydimethylsiloxane, and to a pH sensing film manufactured by the method.
광학 pH 센서(Optical pH sensor)를 제조하는 방법은 지시약을 고정화(immobilization)하는 기술에 따라 크게 두 가지 방법으로 구분된다.A method of manufacturing an optical pH sensor is largely divided into two methods depending on a technique for immobilizing an indicator.
첫 번째 방법은 지시약(indicator)을 기질(substrate)에 공유 결합하는 방법으로써, 지시약의 화학적 구속에 의해 지시약의 침출이 적고 센서의 장기수명을 보장할 수 있는 이점을 가진다. 그러나, 이 방법은 제조공정이 복잡하며, 다양한 지시약을 공유결합 할 수 없으므로 센서의 pH 계측 범위가 제한적인 문제점이 있다.The first method is a method of covalently binding an indicator to a substrate, and has an advantage of ensuring a long lifespan of the sensor with less leaching of the indicator due to chemical confinement of the indicator. However, this method has a problem in that the manufacturing process is complicated and the pH measurement range of the sensor is limited because various indicators cannot be covalently bonded.
두 번째 방법은, 졸-겔(Sol-gel)법을 활용하여 지시약을 기질에 물리적으로 구속하는 방법으로써, 센서의 제조방법이 간단하며, 다양한 지시약을 혼합하여 센서를 제조할 수 있으므로, 넓은 pH범위를 계측할 수 있는 센서를 제조하는데 용이한 이점을 갖는다. 그러나, 상기 방법은 지시약의 구속력이 약하여 시간 경과에 따른 지시약의 침출이 문제가 되고 있다.The second method is a method of physically confining the indicator to the substrate using the sol-gel method. The manufacturing method of the sensor is simple, and since the sensor can be manufactured by mixing various indicators, a wide range of pH It has the advantage of being easy to manufacture a sensor capable of measuring range. However, since the binding force of the indicator is weak in the above method, leaching of the indicator over time is a problem.
이러한 배경 하에, 본 발명자는 졸-겔(Sol-gel)법을 활용한 pH 센서의 침출저항성능을 개선하고자, 물리적 구속과 더불어 정전기적 인력을 통해 지시약을 구속할 수 있는 센서 소재를 개발하고자 하였다. 그 결과 셀룰로오스 및 폴리디메틸실록산에 양극성을 부여함으로써 음극성을 갖는 지식약을 정전기적 인력으로 구속시키고, 동시에 폴리디메틸실록산이 셀룰로오스의 표면에 형성되어 셀룰로오스의 풀림(Swelling)을 보호함으로써 지시약을 물리적으로 구속시킬 수 있음을 확인함으로써 본 발명을 완성하였다. Under this background, the present inventors tried to develop a sensor material capable of binding an indicator through electrostatic attraction in addition to physical restraint in order to improve the leaching resistance performance of a pH sensor using a sol-gel method. . As a result, by imparting positive polarity to cellulose and polydimethylsiloxane, the negative polarity is constrained by electrostatic attraction, and at the same time, polydimethylsiloxane is formed on the surface of cellulose to protect the swelling of cellulose, thereby physically The present invention was completed by confirming that it could be restrained.
따라서 본 발명의 목적은 지시약(염료)의 침출저항성을 효과적으로 개선시킬 수 있는 pH 감지막의 제조방법을 제공하는 것이다.Accordingly, an object of the present invention is to provide a method for manufacturing a pH sensing film capable of effectively improving the leaching resistance of an indicator (dye).
본 발명의 다른 목적은, 상기 방법으로 제조된 지시약(염료)의 침출저항성이 개선된 pH 감지막을 제공하는 것이다.Another object of the present invention is to provide a pH sensing film with improved leaching resistance of the indicator (dye) prepared by the above method.
본 발명의 또 다른 목적은, 상기 pH 감지막을 포함하는 pH 센서를 제공하는 것이다.Another object of the present invention is to provide a pH sensor including the pH sensing film.
상기와 같은 본 발명의 목적을 달성하기 위해서, In order to achieve the object of the present invention as described above,
본 발명은 a) 폴리디알릴디메틸 암모늄클로라이드(Poly diallyldimethylammonium chloride) 수용액에 셀룰로오스를 넣고 50~60℃에서 1~2시간 동안 반응시켜 셀룰로오스를 양이온화시키는 단계; b) 양이온화된 셀룰로오스에 지시약을 포함하는 용액을 처리하여 셀룰로오스를 염색시키는 단계; c) 염색된 셀룰로오스를 설탕 용액에 침지한 후 50~60℃에서 건조시키는 단계; 및 d) 설탕 용액으로 코팅된 셀룰로오스를 폴리디메틸실록산 및 세트리모늄 브로마이드를 포함하는 혼합용액에 침지시킨 후 건조시키는 단계를 포함하는, pH 변화에 따라 색상이 변화하는 pH 감지막의 제조방법을 제공한다.The present invention comprises the steps of a) adding cellulose to an aqueous solution of poly diallyldimethylammonium chloride and reacting at 50 to 60 ° C. for 1 to 2 hours to cationize cellulose; b) dyeing cellulose by treating cationized cellulose with a solution containing an indicator; c) immersing the dyed cellulose in a sugar solution and drying at 50-60 ° C; and d) immersing the cellulose coated with the sugar solution in a mixed solution containing polydimethylsiloxane and cetrimonium bromide, followed by drying. .
본 발명의 일실시예에 있어서, 상기 지시약은 티몰 블루(Thymol blue) 및 인디고 카마인(Indigo carmine)일 수 있다.In one embodiment of the present invention, the indicator may be thymol blue and indigo carmine.
본 발명의 일실시예에 있어서, 상기 설탕 용액은 50%(w/v) 농도를 가질 수 있다.In one embodiment of the present invention, the sugar solution may have a concentration of 50% (w / v).
본 발명의 일실시예에 있어서, 상기 혼합용액은 세트리모늄 브로마이드를 3%(w/v) 농도로 포함할 수 있다.In one embodiment of the present invention, the mixed solution may include cetrimonium bromide at a concentration of 3% (w/v).
또한, 본 발명은 상기 방법으로 제조된 pH 변화에 따라 색상이 변화하는 pH 감지막을 제공한다.In addition, the present invention provides a pH sensing film prepared by the above method, the color of which changes according to the change in pH.
본 발명의 일실시예에 있어서, pH 감지막은 지시약의 침출저항성이 개선될 수 있다.In one embodiment of the present invention, the leaching resistance of the pH sensing film can be improved.
또한, 본 발명은 상기 pH 감지막을 포함하는 pH 센서를 제공한다.In addition, the present invention provides a pH sensor including the pH sensing film.
본 발명의 pH 감지막 제조방법은 셀룰로오스에 폴리디알릴디메틸 암모늄클로라이드(Poly diallyldimethylammonium chloride) 작용기를 도입하는 단계를 통해 셀룰로오스에 양극성을 부여함으로써 음극성을 갖는 지시약과 정전기적인 결합을 통해 지시약을 1차 구속시킬 수 있으며; 또한, 폴리디메틸실록산(Polydimethylsiloxane)에 세트리모늄 브로마이드 작용기를 도입하는 단계를 통해 폴리디메틸실록산에 양극성을 부여함으로써 음극성을 갖는 지시약과 정전기적인 결합을 통해 지시약을 2차 구속시킬 수 있다. 뿐만 아니라, 본 발명의 pH 감지막 제조방법은 폴리디메틸실록산이 셀룰로오스의 풀림(Swelling)을 보호함으로써 지시약을 물리적으로 구속시킬 수 있는바, 지시약의 침출저항성능이 개선되는 효과를 갖는다.The pH sensing film manufacturing method of the present invention provides a positive polarity to cellulose through the step of introducing a poly diallyldimethylammonium chloride functional group into cellulose, thereby first making the indicator through electrostatic bonding with an indicator having a negative polarity. can bind; In addition, by imparting a positive polarity to the polydimethylsiloxane through the step of introducing a cetrimonium bromide functional group into the polydimethylsiloxane, the indicator may be secondarily constrained through electrostatic bonding with the indicator having a negative polarity. In addition, the pH sensing film manufacturing method of the present invention has an effect of improving the leaching resistance of the indicator because the polydimethylsiloxane protects the swelling of the cellulose to physically restrain the indicator.
한편, 본 발명의 pH 감지막 제조방법은 셀룰로오스를 설탕 용액으로 코팅하는 단계를 통해, 폴리디메틸실록산-셀룰로오스 복합재료 사이에 인위적인 공극을 형성할 수 있는바, pH 감지막 내부로의 산 또는 염기성 용액의 침투가 원활하게 이루어짐으로써 pH 감지막의 응답성이 개선되는 이점을 갖는다.On the other hand, the pH sensing film manufacturing method of the present invention can form an artificial void between the polydimethylsiloxane-cellulose composite material through the step of coating cellulose with a sugar solution, so that an acid or basic solution into the pH sensing film It has the advantage that the responsiveness of the pH sensing film is improved by smooth permeation.
도 1은 본 발명의 pH 감지막 제조방법을 대략적으로 보여주는 모식도이다(cel: cellulose, PDDACI: Poly diallyldimethylammonium chloride, TB: Thymol blue, IC: Indigo carmine, PDMS: Poly dimethylsiloxane, CTAB: Cetrimonium bromide).
도 2는 본 발명에 있어서 양극성화된 셀룰로오스 및 폴리디메틸실록산이 음극성을 갖는 지시약(염료)과 정전기적 인력을 형성하는 기작을 보여주는 것이다.
도 3은 다양한 pH(pH 8 내지 pH 12)의 노출에 따른 본 발명의 pH 감지막의 색상 변화를 보여주는 사진이다.
도 4는 pH 8에서부터 pH 12에 이르기까지 본 발명의 pH 감지막의 반사스펙트럼 그래프이다.
도 5는 본 발명의 pH 감지막(실시예 1) 및 일반 염색종이(비교예 1)의 시간 경과에 따른 지시약 침출 정도를 측정한 그래프이다.1 is a schematic diagram schematically showing a method for manufacturing a pH sensing film of the present invention (cel: cellulose, PDDACI: Poly diallyldimethylammonium chloride, TB: Thymol blue, IC: Indigo carmine, PDMS: Poly dimethylsiloxane, CTAB: Cetrimonium bromide).
Figure 2 shows the mechanism of forming an electrostatic attraction with an indicator (dye) having an anodized cellulose and polydimethylsiloxane having a negative polarity in the present invention.
Figure 3 is a photograph showing the color change of the pH sensing film of the present invention according to exposure to various pH (
Figure 4 is a reflectance spectrum graph of the pH sensing film of the present invention from
5 is a graph measuring the degree of indicator leaching over time of the pH sensing film of the present invention (Example 1) and general dyed paper (Comparative Example 1).
본 발명은 pH 변화에 따라 색상이 변화하는 pH 감지막의 제조 방법으로서, 지시약의 침출저항성을 개선시키는 것을 목적으로 하며, a) 폴리디알릴디메틸 암모늄클로라이드(Poly diallyldimethylammonium chloride) 수용액에 셀룰로오스를 넣고 50~60℃에서 1~2시간 동안 반응시켜 셀룰로오스를 양이온화시키는 단계; b) 양이온화된 셀룰로오스에 지시약을 포함하는 용액을 처리하여 셀룰로오스를 염색시키는 단계; c) 염색된 셀룰로오스를 설탕 용액에 침지한 후 50~60℃에서 건조시키는 단계; 및 d) 설탕 용액으로 코팅된 셀룰로오스를 폴리디메틸실록산 및 세트리모늄 브로마이드를 포함하는 혼합용액에 침지시킨 후 건조시키는 단계를 포함할 수 있다.The present invention is a method for manufacturing a pH sensing film whose color changes with pH change, and aims to improve the leaching resistance of an indicator, a) adding cellulose to an aqueous solution of poly diallyldimethylammonium chloride and Cationizing cellulose by reacting at 60° C. for 1 to 2 hours; b) dyeing cellulose by treating cationized cellulose with a solution containing an indicator; c) immersing the dyed cellulose in a sugar solution and drying at 50-60 ° C; and d) immersing the cellulose coated with the sugar solution in a mixed solution containing polydimethylsiloxane and cetrimonium bromide and then drying.
본 발명의 a) 단계는 셀룰로오스를 양이온화시키는 단계로서, 자세하게는 3%(w/v) 농도의 폴리디알릴디메틸 암모늄클로라이드(Poly diallyldimethylammonium chloride) 수용액에 셀룰로오스를 넣은 후 50~60℃에서 1~2시간 동안 반응시킴으로써 셀룰로오스를 양이온화시키는 단계이다.Step a) of the present invention is a step of cationizing cellulose, and in detail, after putting cellulose in an aqueous solution of poly diallyldimethylammonium chloride at a concentration of 3% (w / v), 1 to 2 at 50 ~ 60 ℃ This is a step of cationizing cellulose by reacting for a period of time.
본 발명에서는 상기 a) 단계를 통해 셀룰로오스에 폴리디알릴디메틸 암모늄클로라이드(Poly diallyldimethylammonium chloride) 작용기를 도입함으로써 셀룰로오스에 양극성을 부여할 수 있는바, 음극성을 갖는 지시약(염료)을 정전기적인 결합을 통해 구속시킬 수 있다.In the present invention, a positive polarity can be imparted to cellulose by introducing a poly diallyldimethylammonium chloride functional group into cellulose through step a), and an indicator (dye) having a negative polarity can be electrostatically bonded to the cellulose. can be imprisoned.
본 발명의 b) 단계는 양이온화된 셀룰로오스를 염색시키는 단계로서, 자세하게는 상기 a) 단계를 통해 제조된 양이온화된 셀룰로오스를 지시약(염료)를 포함하는 용액에 넣고 50~60℃에서 1~2시간 동안 가열함으로써 셀룰로오스를 염색시키는 단계이다.Step b) of the present invention is a step of dyeing cationized cellulose, and in detail, the cationized cellulose prepared through step a) is put into a solution containing an indicator (dye) and 1 to 2 at 50 to 60 ° C. It is a step of dyeing cellulose by heating for a period of time.
상기 b) 단계에서 지시약은 음극성을 갖는 염료로서 티몰 블루(Thymol blue) 및 인디고 카마인(Indigo carmine)을 사용할 수 있으나, 음극성을 갖는 것이면 특별히 그 종류를 한정하지 않으며, 제조하고자 하는 목적에 맞게 종래 알려진 지시약으로 변경할 수 있다.In the step b), Thymol blue and Indigo carmine can be used as the indicator as a dye having a negative polarity, but the type is not particularly limited as long as it has a negative polarity, and it is suitable for the purpose to be manufactured. It can be changed to a conventionally known indicator.
본 발명의 c) 단계는 염색된 셀룰로오스를 설탕 용액으로 코팅하는 단계로서, 자세하게는 상기 b) 단계를 통해 제조된 염색된 셀룰로오스를 50%(w/v) 농도의 설탕 용액에 침지한 후 50~60℃에서 건조시키는 단계이다.Step c) of the present invention is a step of coating the dyed cellulose with a sugar solution, in detail, after immersing the dyed cellulose prepared through step b) in a sugar solution of 50% (w / v) concentration, It is a step of drying at 60 ° C.
본 발명에서는 상기 c) 단계를 통해 폴리디메틸실록산-셀룰로오스 복합재료 사이에 인위적인 공극을 형성할 수 있는바, pH 감지막 내부로의 산 또는 염기성 용액의 침투가 원활하게 이루어짐으로써 pH 감지막의 응답성이 개선시킬 수 있다.In the present invention, artificial voids can be formed between the polydimethylsiloxane-cellulose composite material through the step c), so that the acid or basic solution penetrates smoothly into the pH sensing film, thereby improving the responsiveness of the pH sensing film. can be improved
본 발명의 d) 단계는 설탕 용액으로 코팅된 셀룰로오스에 양이온화된 폴리디메틸실록산을 형성시키는 단계로서, 자세하게는 상기 c) 단계를 통해 제조된 설탕 용액으로 코팅된 셀룰로오스를 폴리디메틸실록산 및 세트리모늄 브로마이드를 포함하는 혼합용액에 침지시킨 후 건조시키는 단계이다.Step d) of the present invention is a step of forming cationized polydimethylsiloxane on the cellulose coated with the sugar solution, and in detail, the cellulose coated with the sugar solution prepared through step c) is treated with polydimethylsiloxane and cetrimonium This is a step of immersing in a mixed solution containing bromide and then drying.
상기 d) 단계에서 혼합용액은 세트리모늄 브로마이드를 3%(w/v) 농도로 포함할 수 있다.In step d), the mixed solution may contain cetrimonium bromide at a concentration of 3% (w/v).
본 발명에서는 상기 c) 단계를 통해 폴리디메틸실록산에 세트리모늄 브로마이드 작용기를 도입함으로써 폴리디메틸실록산에 양극성을 부여할 수 있는바, 음극성을 갖는 지시약을 정전기적인 결합을 통해 구속시킬 수 있을 뿐 아니라, 폴리디메틸실록산이 셀룰로오스의 풀림(Swelling)을 보호함으로써 지시약을 물리적으로 구속시킬 수 있다.In the present invention, by introducing a cetrimonium bromide functional group into the polydimethylsiloxane through step c), it is possible to impart a positive polarity to the polydimethylsiloxane, so that an indicator having a negative polarity can be constrained through electrostatic bonding. , Polydimethylsiloxane can physically restrain the indicator by protecting the swelling of cellulose.
본 발명은 또한, 상기 방법으로 제조된 pH 변화에 따라 색상이 변화하는 pH 감지막을 제공한다.The present invention also provides a pH sensing film prepared by the above method, the color of which changes according to the change in pH.
본 발명의 상기 a) 단계 내지 d) 단계를 포함하는 과정을 통해 제조된 pH 감지막은 정전기적인 인력 및 물리적 구속을 통해 지시약의 침출저항성을 효과적으로 개선시킬 수 있다.The pH sensing film prepared through the process including steps a) to d) of the present invention can effectively improve the leaching resistance of the indicator through electrostatic attraction and physical restraint.
본 발명에 있어서, ‘침출저항성’이라 함은 지시약이 침출되지 않도록 하는 침출에 대해 견디는 힘을 의미한다.In the present invention, 'leaching resistance' means the ability to withstand leaching that prevents the indicator from leaching.
본 발명은 또한, 상기 pH 감지막을 포함하는 pH 센서를 제공한다.The present invention also provides a pH sensor including the pH sensing film.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명하고자 한다. 이들 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. These examples are intended to explain the present invention in more detail, and the scope of the present invention is not limited to these examples.
<실시예><Example>
재료 준비material preparation
폴리디알릴디메틸 암모늄클로라이드(Poly diallyldimethylammonium chloride, PDDACI)는 시그마 알드리치에서 구입하였으며, 셀룰로오스 멤브레인은 현대 마이크로(NO.100)에서 구입하였고, 티몰 블루(Thymol blue) 및 인디고 카마인(Indigo carmine)은 대정에서 구입하였다. 폴리디메틸실록산(Poly dimethylsiloxane, PDMS)는 다우코닝(Sylgard 184)에서 구입하였으며, 세트리모늄 브로마이드(Cetrimonium bromide, CTAB)는 대정에서 구입하였으고, 아세트산은 삼양산업에서 구매하였다. pH 감지막의 색상 변화를 관찰하기 위해 활용된 pH 완충용액은 대정에서 구매하였다.Poly diallyldimethylammonium chloride (PDDACI) was purchased from Sigma Aldrich, cellulose membrane was purchased from Hyundai Micro (NO.100), and Thymol blue and Indigo carmine were purchased from Daejeong. Purchased. Polydimethylsiloxane (PDMS) was purchased from Dow Corning (Sylgard 184), Cetrimonium bromide (CTAB) was purchased from Daejeong, and acetic acid was purchased from Samyang Industry. The pH buffer solution used to observe the color change of the pH sensing film was purchased from Daejeong.
<실시예 1><Example 1>
본 발명의 pH 감지막 제조Preparation of the pH sensing membrane of the present invention
셀룰로오스 멤브레인 5g을 폴리디알릴디메틸 암모늄클로라이드(Poly diallyldimethylammonium chloride, PDDACI) 3%(w/v) 수용액에 투입한 후 60℃에서 1시간 동안 반응시켜 셀룰로오스 멤브레인을 양이온화시켰다. 이후, 티몰 블루(Thymol blue) 및 인디고 카마인(Indigo carmine) 포화용액을 1:4 비율(부피비)로 제조한 뒤, 상기 혼합용액에 양이온화된 셀룰로오스 멤브레인을 넣고 60℃에서 1시간 동안 가열하여 셀룰로오스 멤브레인을 염색하였다. 염색된 셀룰로오스 멤브레인을 핀셋으로 집어 50%(w/v) 설탕 용액에 1초간 짧게 침지한 후, 60℃에서 4시간 동안 건조하였다. 폴리디메틸실록산(Poly dimethylsiloxane, PDMS) 1L에 세트리모늄 브로마이드(Cetrimonium bromide, CTAB) 3g을 녹여 3%(w/v) 혼합용액을 제조하였다. 상기 제조된 혼합용액에 설탕 코팅이 완료된 셀룰로오스 멤브레인을 핀셋으로 집어 1초 동안 짧게 침지시킨 후 실온에서 72 시간 건조시키는 과정을 거쳐 셀룰로오스 멤브레인 상부 및 하부에 상기 혼합용액이 형성되도록 하였다.5 g of the cellulose membrane was added to a 3% (w/v) aqueous solution of poly diallyldimethylammonium chloride (PDDACI), and then reacted at 60° C. for 1 hour to cationize the cellulose membrane. Thereafter, a saturated solution of Thymol blue and Indigo carmine was prepared in a 1:4 ratio (volume ratio), and then a cationized cellulose membrane was added to the mixed solution and heated at 60 ° C. for 1 hour to obtain cellulose The membrane was stained. The dyed cellulose membrane was picked up with tweezers and briefly immersed in a 50% (w/v) sugar solution for 1 second, and then dried at 60° C. for 4 hours. A 3% (w/v) mixed solution was prepared by dissolving 3 g of cetrimonium bromide (CTAB) in 1 L of polydimethylsiloxane (PDMS). Pick up the sugar-coated cellulose membrane in the prepared mixed solution with tweezers, briefly immerse it for 1 second, and then dry at room temperature for 72 hours to form the mixed solution on the upper and lower portions of the cellulose membrane.
<비교예 1><Comparative Example 1>
일반 염색종이 제조Manufacture of plain dyed paper
티몰 블루(Thymol blue) 및 인디고 카마인(Indigo carmine) 포화용액을 1:4 비율(부피비)로 제조한 뒤, 상기 혼합용액에 셀룰로오스 멤브레인을 넣고 60℃에서 1시간 동안 가열하여 셀룰로오스 멤브레인을 염색하였다.After preparing a saturated solution of Thymol blue and Indigo carmine at a ratio of 1:4 (volume ratio), a cellulose membrane was added to the mixture and heated at 60° C. for 1 hour to dye the cellulose membrane.
<실험예 1><Experimental Example 1>
본 발명의 pH 감지막을 이용한 pH 변화에 따른 색변화 및 반사 스펙트럼Color change and reflection spectrum according to pH change using the pH sensing film of the present invention
본 발명의 pH 감지막을 이용한 pH 변화에 따른 색변화 및 반사 스펙트럼을 측정하기 위하여, 분광측색계(CM 2500d, Konica Minolta)를 사용하였다. pH 감지막의 색상 변화를 유도하기 위해, pH 완충용액 3ml를 pH 감지막 위에 떨어뜨린 뒤, 약 3분 후 pH 완충 용액을 제거하고 감지막의 색변화 및 반사 스펙트럼을 관찰하였다. 이때, 반사 스펙트럼의 가시광선 범위는 360nm에서 740nm 이었다.In order to measure color change and reflection spectrum according to pH change using the pH sensing film of the present invention, a spectrophotometer (CM 2500d, Konica Minolta) was used. In order to induce a color change of the pH sensing film, 3 ml of the pH buffer solution was dropped on the pH sensing film, and after about 3 minutes, the pH buffer solution was removed, and the color change and reflection spectrum of the sensing film were observed. At this time, the visible light range of the reflection spectrum was 360 nm to 740 nm.
그 결과 pH 8에서 pH 12로 진행됨에 따라 녹색에서 파란색으로 색이 변화되는 것을 확인하였다(도 3 참조). 본 발명의 pH 감지막은 pH가 8에서 12로 증가할수록, 적색 영역대의 가시광선 반사율이 감소하였으며 청색 영역대의 가시광선 반사율은 증가하는 것을 확인할 수 있었다(도 4 참조).As a result, it was confirmed that the color changed from green to blue as the pH changed from
<실험예 2><Experimental Example 2>
본 발명의 pH 감지막의 침출저항성능 개선 효과Leach resistance improvement effect of the pH sensing membrane of the present invention
본 발명의 pH 감지막의 침출저항성능 개선 효과를 확인하기 위하여, pH 12 완충용액에 <실시예 1>을 통해 제조된 본 발명의 pH 감지막 및 <비교예 1>에서 제조된 염색 종이를 침지시켜 반사율 변화를 관측하였다. 침출저항성능 검증실험은 최대 900초까지 수행되었으며, 반사율 변화는 600nm에서 관측되었다.In order to confirm the effect of improving the leaching resistance of the pH sensing film of the present invention, the pH sensing film of the present invention prepared in <Example 1> and the dyed paper prepared in <Comparative Example 1> were immersed in a
그 결과 도 5에서 나타낸 바와 같이, <비교예 1>은 지시약의 침출이 급격히 일어나 400초까지 반사율이 급격히 증가하는 반면, <실시예 1>을 통해 제조된 본 발명의 pH 감지막의 경우 900초까지 침출이 거의 나타나지 않았으며, 0초 에서와 유사한 반사율을 나타내었다.As a result, as shown in FIG. 5, in <Comparative Example 1>, the reflectance rapidly increases up to 400 seconds due to rapid leaching of the indicator, whereas in the case of the pH sensing film of the present invention prepared through <Example 1>, up to 900 seconds Almost no leaching was observed, and the reflectance was similar to that at 0 sec.
상기와 같은 결과를 통해, 본 발명의 pH 감지막의 경우 침출저항성능이 효과적으로 개선된 것을 확인할 수 있었다.Through the above results, it was confirmed that the leaching resistance performance was effectively improved in the case of the pH sensing membrane of the present invention.
이제까지 본 발명에 대하여 그 바람직한 실시예들을 중심으로 살펴보았다. 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자는 본 발명이 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 변형된 형태로 구현될 수 있음을 이해할 수 있을 것이다. 그러므로 개시된 실시예들은 한정적인 관점이 아니라 설명적인 관점에서 고려되어야 한다. 본 발명의 범위는 전술한 설명이 아니라 특허청구범위에 나타나 있으며, 그와 동등한 범위 내에 있는 모든 차이점은 본 발명에 포함된 것으로 해석되어야 할 것이다.So far, the present invention has been looked at with respect to its preferred embodiments. Those skilled in the art to which the present invention pertains will be able to understand that the present invention can be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative rather than a limiting point of view. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the equivalent scope will be construed as being included in the present invention.
Claims (7)
b) 양이온화된 셀룰로오스에 지시약을 포함하는 용액을 처리하여 셀룰로오스를 염색시키는 단계;
c) 염색된 셀룰로오스를 설탕 용액에 침지한 후 50~60℃에서 건조시키는 단계; 및
d) 설탕 용액으로 코팅된 셀룰로오스를 폴리디메틸실록산 및 세트리모늄 브로마이드를 포함하는 혼합용액에 침지시킨 후 건조시키는 단계를 포함하는, pH 변화에 따라 색상이 변화하는 pH 감지막의 제조방법.a) cationizing cellulose by adding cellulose to an aqueous solution of poly diallyldimethylammonium chloride and reacting at 50 to 60° C. for 1 to 2 hours;
b) dyeing cellulose by treating cationized cellulose with a solution containing an indicator;
c) immersing the dyed cellulose in a sugar solution and drying at 50-60 ° C; and
d) A method for producing a pH sensing film whose color changes according to pH change, comprising the steps of immersing cellulose coated with a sugar solution in a mixed solution containing polydimethylsiloxane and cetrimonium bromide and drying it.
상기 지시약은 티몰 블루(Thymol blue) 및 인디고 카마인(Indigo carmine)인 것을 특징으로 하는, pH 변화에 따라 색상이 변화하는 pH 감지막의 제조방법.According to claim 1,
The indicator is characterized in that thymol blue (Thymol blue) and indigo carmine (Indigo carmine), a method for producing a pH sensing film whose color changes according to pH change.
상기 설탕 용액은 50%(w/v) 농도를 갖는 것을 특징으로 하는, pH 변화에 따라 색상이 변화하는 pH 감지막의 제조방법.According to claim 1,
The sugar solution is characterized in that it has a concentration of 50% (w / v), a method for producing a pH sensing film whose color changes according to pH change.
상기 혼합용액은 세트리모늄 브로마이드를 3%(w/v) 농도로 포함하는 것을 특징으로 하는, pH 변화에 따라 색상이 변화하는 pH 감지막의 제조방법.According to claim 1,
The mixed solution is characterized in that it contains cetrimonium bromide at a concentration of 3% (w / v), a method for producing a pH sensing film whose color changes with pH change.
상기 pH 감지막은 지시약의 침출저항성이 개선된 것을 특징으로 하는, pH 변화에 따라 색상이 변화하는 pH 감지막.According to claim 5,
The pH sensing film is characterized in that the leaching resistance of the indicator is improved, a pH sensing film whose color changes according to pH change.
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| KR101772322B1 (en) * | 2016-04-11 | 2017-08-29 | 한양대학교 에리카산학협력단 | Colorimetric sensing film, and method for manufacturing colorimetric gas sensor using same |
| KR20190111250A (en) * | 2018-03-22 | 2019-10-02 | 서울시립대학교 산학협력단 | Methods for surface-enhanced Raman scattering using three-dimensional porous nanoplasmonic network |
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| KR101772322B1 (en) * | 2016-04-11 | 2017-08-29 | 한양대학교 에리카산학협력단 | Colorimetric sensing film, and method for manufacturing colorimetric gas sensor using same |
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