KR102411461B1 - Formaldehyde Sensitive Functional Cotton Fiber - Google Patents

Abstract

The present invention provides a functional fiber and a functional cotton fiber capable of detecting formaldehyde to which a formaldehyde detection molecule including a pH indicator that is discolored at pH 7 or less is attached to the fiber. It provides the effect of resolving the problem of reduced sensitivity and economic problems, and provides a cotton fiber formaldehyde sensor that reacts sensitively to formaldehyde and can be easily identified with the naked eye, so that it can be used in places where it is likely to be exposed to formaldehyde. It relates to a cloth used where possible and to provide an effect that is usefully used as a patch using the same.

Description

Formaldehyde Sensitive Functional Cotton Fiber

The present invention relates to formaldehyde-sensitive functional cotton fibers. Specifically, it relates to a functional fiber having a formaldehyde detection molecule including a pH indicator that changes color at a pH of 7 or less on the fiber attached thereto.

Formaldehyde is a chemical compound used industrially in a variety of ways. Formaldehyde is used in the manufacture of plastics, as an adhesive in plywood board and chip board in the processing of wood, as an insulating material in the building industry, for spindle processing and easy-care processing in the textile industry. And it is used as a preservative in agriculture and food industry. Formaldehyde is used as a disinfectant and is further contained in cosmetics, body and oral care products, as well as in some cases paints, varnishes and carpets. Moreover, formaldehyde arises from incomplete combustion processes. For example, such processes are found in the combustion engines of automobiles, in foundries, in the production of plastic products or in the incineration of wood in small combustion plants. In the same way, formaldehyde also occurs during smoking and contributes to air pollution. Formaldehyde is a gaseous substance that can cause health problems such as eye irritation or mucosal irritation. Short-term exposure causes eye and respiratory irritation even at low concentrations: from 0.01 ppm to eye irritation, from 0.08 ppm to eye and nose irritation, and from 0.5 ppm to throat irritation. Concentrated vapors in excess of 10 ppm can cause severe irritation of the mucous membranes, including tearing, coughing, and burning of the nose and throat. Concentrations in excess of 30 ppm cause life-threatening toxic edema and pneumonia of the lungs. The chronic effects of formaldehyde cause problems such as insomnia, lethargy, loss of appetite, loss of appetite or irritability, eye irritation and conjunctivitis, skin irritation, chronic cough, colds and bronchitis, headache, depression, and chic building syndrome. Furthermore, formaldehyde can also cause hypersensitivity and has been suspected for some time to cause cancer or act mutagenic or teratogenic in humans. For this reason, the German Health Authority has introduced a maximum workplace concentration (Maximum Allowable Concentration (MAC)) of 0.3 ppm (0.375 mg/m ³ ). The indoor reference value is even lower at 0.1 ppm (0.125 mg). /m ³ ), because continuous exposure is expected in this case, and in underground stations, railway stations, airport facilities, etc., it is less than 100㎍/㎥, and in medical institutions, elderly care facilities, and daycare centers, the lower standard is 80㎍. /m3 For this reason, effective and rapid detection and measurement of formaldehyde in the air is of great importance.

Several methods for detecting formaldehyde in air are known from the prior art. There is a formaldehyde sensor in the form of nanoparticles that can detect fine formaldehyde, but since these sensors are in the form of particles, it is difficult to fix when directly applied to paper or fabric, so another binder is needed for fixation. , this may reduce the sensitivity of the sensor detection.

Under this background, the present inventors manufactured cloth and patches using the same for a place where formaldehyde is used or exposed to formaldehyde, etc. As a result of earnest efforts to do this, by developing a functional cotton fiber capable of detecting formaldehyde, the present invention was completed.

Republic of Korea Patent Publication 10-2018-0032401 (published date: 2018.03.30)

One object of the present invention is to provide a functional fiber having a formaldehyde detection molecule including a pH indicator that changes color at pH 7 or less on the fiber attached thereto.

Another object of the present invention is to provide a formaldehyde detection compound represented by the following formula (1).

[Formula 1]

In Formula 1,

X is a pH indicator,

n is an integer selected from 0 to 40;

This will be described in detail as follows. Meanwhile, each description and embodiment disclosed in the present invention may be applied to each other description and embodiment. That is, all combinations of the various elements disclosed herein fall within the scope of the present invention. In addition, it cannot be considered that the scope of the present invention is limited by the specific descriptions described below.

One aspect of the present invention for achieving the above object provides a functional fiber to which a formaldehyde detection molecule including a pH indicator that changes color at a pH of 7 or less is attached to the fiber.

Another aspect of the present invention for achieving the above object provides a formaldehyde detection compound represented by the following formula (1).

[Formula 1]

In Formula 1,

X is a pH indicator,

n is an integer selected from 0 to 40;

Specifically, the functional cotton fiber capable of detecting formaldehyde provides an effect of solving the problem that the sensor material is not fixed to the conventional fiber, the problem of reduced sensitivity due to the need for other binders, and the economic problem, and is sensitive to formaldehyde By providing a cotton fiber formaldehyde sensor that reacts and can be easily identified with the naked eye, it can provide an effect that can be usefully used as a cloth and a patch using the cloth used in places that can be exposed to formaldehyde, etc. .

As used herein, the term "formaldehyde" is a naturally occurring organic compound having the formula CH ₂ O(H-CHO) and is one of the simplest aldehydes. Formaldehyde is an important precursor used in the synthesis of many other substances and compounds. As of 1996, the production capacity of formaldehyde was estimated at 8.7 million tonnes per year. It is mainly used in the production of industrial resins such as particle boards and coatings. However, formaldehyde can pose serious risks to humans due to its widespread use, toxicity, and volatility, and in 2011 the U.S. National Toxicology Program declared it a “known to be a human carcinogen”. human carcinogen).

As used herein, the term "cotton fiber" means a fiber including a hydroxyl group, which is a functional group capable of a coupling reaction with the silane group of the compound represented by Formula 1 above.

Accordingly, the functional fiber to which the formaldehyde detection molecule according to the present invention is attached may be covalently attached to the functional fiber through a silane group of the molecule of the compound represented by Formula 1, and an amine group The pH can be changed to 7 or less by forming an amine compound through a Mannich reaction with formaldehyde through It is possible to provide functional fibers that can be visually confirmed by inducing changes. In addition, n in Formula 1 may be an integer selected from 0 to 5.

As used herein, the term “Mannich reaction” refers to a reaction in which active methylene is reacted with formaldehyde and an amine for aminomethylation. An experiment conducted by B. Lance in 1903 was generalized by C. Mannich in 1912. For example, when acetophenone is reacted with formaldehyde and dimethylamine hydrochloride, β-dimethylaminopropiophenone is formed. Since this reaction proceeds under extremely mild conditions, it can be said to be one of various reactions not only as a general organic reaction but also in the biosynthesis of alkaloids that proceed in vivo.

The pH indicator may include methyl red (MR: Methyl red), bromocresol purple, alizarin, or 4-nitrophenol, however, it is combined with GPTMS and reacts with formaldehyde and APTES to show a color change. As long as it is an indicator that can be used, it can be used without limitation.

The formaldehyde detection molecule may include, but is not limited to, glycidoxypropyltrimethoxysilane (GPTMS) and 3-aminopropyltriethoxysilane (APTES: 3-Aminopropyltriethoxysilane).

The GPTMS including the silane group may be chemically bonded to the fiber through a silane group, and the chemical bonding may be a covalent bond. It is possible to solve the problem that the sensitivity of detecting formaldehyde is lowered because the material for detecting formaldehyde is not fixed to the conventional fiber and a different binder is required.

APTES including the amine group can change the pH to 7 or less by forming an amine compound through a Mahini reaction with formaldehyde in the amine group in the molecule.

The formaldehyde detection molecule may include the glycidoxypropyltrimethoxysilane and the APTES in a molar ratio of 1:1 to 5.

The APTES (3-Aminopropyltriethoxysilane) may be included in a molar ratio of 1 to 5 to 1 to 1 of the glycidoxypropyltriethoxysilane, preferably 1:3.

Specifically, when the molar ratio of APTES is less than 1, detection may be impossible because the amine group contained in APTES cannot react with formaldehyde in an effective number. Therefore, it may not be possible to detect formaldehyde because the color change of the pH indicator material does not occur.

In addition, in a specific embodiment, it was confirmed that as the molar ratio of APTES increased within the aforementioned molar ratio range, the width of the color change rate increased and the detection intensity increased due to the increase of amine groups.

The pH indicator may be included in a molar ratio of 0.01 to 1 compared to 1 of the glycidoxypropyltrimethoxysilane.

Specifically, when the molar ratio of the pH indicator is less than 0.0.1, the sensing effect may be lowered due to low visibility, and if it exceeds 1, it may not be combined with GPTMS and thus may be unnecessary.

The formaldehyde detection molecule may be covalently attached to the fiber, but is not limited thereto.

Specifically, due to the GPTMS containing the silane group, the silane group and the fiber may be covalently bonded and attached to the fiber, and the material for detecting formaldehyde on the conventional fiber cannot be fixed and a different binder is required. Falling problems can be solved.

The compound may be represented by the following Chemical Formula 2, but is not limited thereto.

[Formula 2]

In a specific embodiment, in the formaldehyde-sensing functional fiber of the present invention, as the APTES content increases, the amine group increases, and the amine group reacts with the formaldehyde to increase the intensity of the red color. And it was confirmed that it can be usefully used as a patch using the same, and the formaldehyde detection molecule is fixed to the fiber without other binders to provide a functional fiber with high sensitivity.

The formaldehyde-sensing functional cotton fiber of the present invention provides an effect of solving the problem that the conventional sensor material cannot be fixed to the fiber, the problem of reduced sensitivity due to the need for other binders, and the high cost problem caused by the increase in manufacturing cost, By providing a cotton fiber formaldehyde sensor that reacts sensitively to formaldehyde and can be easily identified with the naked eye, it can be usefully used as a cloth and a patch using the same in a place that can be exposed to formaldehyde, etc.

1 is a photograph showing the color change before and after exposure to formaldehyde of the functional fiber of the present invention.
Figure 2 is a schematic diagram showing the manufacturing and comparison process of the functional fiber of the present invention.
3 is an FT-IR analysis graph showing whether or not a reaction to a solution containing the formaldehyde detection compound of the present invention is confirmed.
Figure 4 is a UV-vis graph showing the color intensity analysis of the acid and base of a solution containing the formaldehyde detection compound of the present invention.
5 is a graph showing the analysis of UV-vis change in the discoloration range of the solution containing the formaldehyde detection compound of the present invention.
6 is a photograph analyzing the color change according to the formaldehyde concentration and APTES ratio of the functional fiber of the present invention.
7 is a graph showing the analysis of the color change rate according to the addition ratio of APTES contained in the solution containing the formaldehyde detection compound of the present invention.
8 is an EA graph and SEM photograph showing the analysis of the material remaining after the fastness test of the functional fiber of the present invention.
9 is an EA graph and an SEM photograph of a functional fiber fiber with only MR added without APTES when manufacturing the functional fiber of the present invention.
10 is an EA graph and SEM photograph of a functional fiber fiber containing APTES and GPTMS 1:1 when manufacturing the functional fiber of the present invention.
11 is an EA graph and an SEM photograph of a functional fiber fiber containing APTES and GPTMS in a ratio of 1.5:1 when manufacturing the functional fiber of the present invention.
12 is an EA graph and SEM photograph of a functional fiber containing APTES and GPTMS in a ratio of 4:1 when manufacturing the functional fiber of the present invention.

Hereinafter, the present invention will be described in more detail through examples. These Examples are for explaining the present invention in more detail, and the scope of the present invention is not limited by these Examples.

Preparation Example 1: Preparation of formaldehyde-sensing functional fiber

A solution containing the formaldehyde detection compound was prepared and attached to the fiber to prepare a formaldehyde detection functional fiber.

Specifically, 60 g of ethanol was put into a 250 ml three-necked flask, and Glycidoxypropyltrimethoxysilane (GPTMS, purity grade 97%, sigma-aldrich) and Methyl red (sigma-aldrich, MR) were added at a molar ratio of 1:1 to prepare a first mixture did Acetic acid was added as an acid catalyst to the first mixture and stirred at 70° C. at 250 rpm for 6 hours to prepare a second mixture. 40 g of purified water was included in the second mixture, and aminopropyltriethoxysilane (APTES) was added at a ratio of 1 to 5 compared to GPTMS, and stirred at 250 rpm at 70° C. for 12 hours to prepare a solution containing a formaldehyde detection compound.

After the solution containing the prepared formaldehyde detection compound was dropped and attached to a cotton fabric, it was dried in a dry oven at 80° C. for 12 hours.

The color change was observed after exposure to formaldehyde gas using the prepared functional fiber.

As shown in FIGS. 1 and 2 , the functional fiber of the present invention can confirm the color change before and after exposure to formaldehyde, and it can be confirmed that the color intensity increases according to the amount of APTES added.

Test Example 1: Analysis of the reaction between the silane agent and methyl red

For the solution containing the formaldehyde detection compound prepared in Preparation Example 1, MR, GPTMS, APTES and a solution containing the formaldehyde detection compound were FR in order to determine whether a chemical bonding reaction between GPTMS APTES and the pH indicator actually occurred. -IR analysis.

As shown in Figure 3, through the ring-opening reaction, carboxyl acid (1724 peak) of MR and epoxide (1252, 909 peak) of GPTMS decreased, and amine (3400 peak) was found. could Through this, it was confirmed that the solution containing the formaldehyde detection compound had a desired chemical reaction.

Test Example 2: Analysis of color intensity change according to the ratio of acid and base APTES

The color intensity change according to the addition ratio of APTES was analyzed. Specifically, the solution containing the formaldehyde detection compound prepared in Preparation Example 1 was subjected to UV-vis analysis to analyze the color intensity change according to the addition ratio of APTES to the acid and base.

As shown in FIG. 4 , it was confirmed that the base pH 9 had a yellow color with a wavelength of 434 nm, and the acid pH 3 had a pink color with a wavelength of 525 nm.

In addition, it was found that the color intensity increased as the amount of APTES added increased. In addition, it was found that when trimethoxysilane was reacted with GPTMS in a mole ratio of 1:1, it was the same as the strength obtained by reacting APTES with GPTMS in a ratio of 4:1. From these results, it was confirmed that as the amount of APTES increased, the width of the color change rate increased, and as the amine group included in APTES increased, the color intensity increased.

Test Example 3: UV-vis change analysis of solutions containing MR and formaldehyde detection compounds

Analysis was performed to determine the effect of color change due to the reaction between GPTMS and MR. Specifically, the UV-vis change in the discoloration range was analyzed for the conventional MR and the solution containing the formaldehyde detection compound prepared in Preparation Example 1.

As shown in Figure 5, there was no significant change in the maximum color change at 525 nm in the acid, but the original MR showed the maximum color change at the wavelength of 442 nm in the base, and the solution containing the formaldehyde detection compound was finely directed toward the base. It can be confirmed that the shift (shift) by 3 nm. The shift of 3 nm from the base is thought to be due to the decrease in the pKa value through the reaction with Silane in the pH range of the solution containing the formaldehyde detection compound. In addition, it is considered that this is because the carboxylic acid is changed to an epoxide by forming a covalent bond during the reaction of MR and GPTMS. However, this change did not have a significant effect on the color change, and a large color change could not be detected even with the naked eye. From this, it can be seen that the reaction between GPTMS and MR forms a group that can be combined with cotton fabric without significantly affecting color change, so it can be easily and conveniently applied to cotton fabric.

Test Example 4: Analysis of color change of functional fibers according to the ratio of APTES and the concentration of the solution containing the formaldehyde detection compound

The color change of functional fibers according to the ratio of APTES and the concentration of the solution containing the formaldehyde detection compound was analyzed. Specifically, the APTES ratio of the MR-dyed fiber (None) and the solution containing the formaldehyde detection compound (MR+GPTMS+APTES) was prepared at a ratio of 1 to 4 compared to GPTMS, and functional fibers dyed with trimethoxysilane instead of APTES (trimethoxy silane) is added at a ratio of 1:4 to prepare a dyed fiber containing a formaldehyde detection compound, and to analyze the color change by exposing the formaldehyde concentration on the functional fiber to a concentration of 1 to 30% did

As shown in FIG. 6 , it was confirmed that the MR-only dyed fibers did not change color when exposed to saturated steam regardless of the formaldehyde concentration. The reason for this was determined that the amine group (-NH ₂ ) group did not exist on the fiber and did not react with the aldehyde group of formaldehyde. In addition, it was confirmed that as the concentration of formaldehyde increased, it changed closer to red.

Test Example 5: Color change rate according to the ratio of formaldehyde solution concentration and APTES

The color change rate according to the concentration of the formaldehyde solution and the addition ratio of APTES included in the solution including the formaldehyde detection compound was analyzed. Specifically, APTES was prepared in a solution containing a formaldehyde detection compound at 1:1, 1:1.5, 1:2 and 1:4 compared to GPTMS, and trimethoxysilane was added in a 1:4 ratio instead of APTES. The color change rate of the solution was analyzed.

As shown in FIG. 7 , it can be seen that as the APTES ratio increases, the color becomes closer to red, and the change is expressed as a ΔRGB value, which is shown in FIG. 12 . As a result of graphing the color change rate, APTES compared to GPTMS 1:1, 1:1.5, 1:2, 1:4 and when trimethoxysilane was used, the color of APTES in trimethoxysilane with more amine groups (-NH ₂ ) It can be seen that the change is larger. In addition, it can be seen that the color change rate increases only when the amount of APTES is increased. The reason for this can be presumed to be that, as the amount of APTES added increases, amine groups capable of reacting with formaldehyde increase relatively.

Test Example 6: Analysis of Si and N Changes According to APTES Ratio

After the fastness test (KS K ISO 105-C10: Washing fastness to soap and soda), EDS analysis was performed with an SEM image to confirm the remaining silane and methyl red (MR). Specifically, when manufacturing the functional fiber in Preparation Example 1, functional fiber containing only MR without APTES, and functional fiber containing APTES and GPTMS in 1:1, 1.5:1 and 4:1 when manufacturing the functional fiber prepared and subjected to EDS analysis with SEM images.

sample name Element (%) C O Si N Control 32.49 67.51 - - APTES 0 32.36 67.64 - - APTES 1 33.8 65.04 - - APTES 1.5 33.57 63.88 2.55 - APTES 4 28.39 59.32 2.83 8.96

[Scheme 1]

As shown in Table 1, Scheme 1, and FIGS. 8 to 12, it was found that the dye methyl red N part and the si part of silane were not found in the untreated control as in Table 1 and Scheme 1. In addition, it was found that the si peak was relatively increased as the amount of APTES added increased, and the N part of methyl red was confirmed in the sample of APTES 4 .

Combining the results of Test Examples 1 to 6 of the present invention, in the functional fiber capable of detecting formaldehyde of the present invention, the amine group increases as the APTES content increases, and the amine group reacts with the formaldehyde to increase the intensity of the red color, It was confirmed that the reaction between GPTMS and MR did not affect the color change. In addition, it is confirmed that the color intensity increases as the concentration of formaldehyde increases, so that it can be usefully used as a cloth used in places where it is likely to be exposed to formaldehyde and a patch using the same, and a solution containing a formaldehyde detection compound is used without other binders. It can be confirmed that it is fixed to the fiber to provide a functional fiber with high sensitivity.

From the above description, those skilled in the art to which the present invention pertains will understand that the present invention may be embodied in other specific forms without changing the technical spirit or essential characteristics thereof. In this regard, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention, rather than the above detailed description, all changes or modifications derived from the meaning and scope of the claims to be described later and their equivalents.

Claims (9)

As a functional fiber, a formaldehyde detection molecule including a pH indicator that changes color at pH 7 or less is attached to the fiber,
The formaldehyde detection molecule contains glycidoxypropyltrimethoxysilane (GPTMS: Glycidoxypropyltrimethoxysilane) and 3-aminopropyl triethoxysilane (APTES: 3-Aminopropyltriethoxysilane) in a molar ratio of 1: 1 to 5, characterized in that it contains , functional fibers.
The method of claim 1,
The pH indicator is selected from the group consisting of methyl red (MR: Methyl red), bromocresol purple, alizarin and 4-nitrophenol, functional fiber.
3. The method of claim 1 or 2,
Wherein the pH indicator is included in a molar ratio of 0.01 to 1 compared to 1 of the glycidoxypropyltrimethoxysilane, functional fiber.
The method of claim 1,
The formaldehyde detection molecule is covalently attached to the fiber, the functional fiber.
delete delete delete A composition for detecting formaldehyde in functional fibers comprising a formaldehyde detecting molecule including a pH indicator that discolors at pH 7 or less,
The formaldehyde detection molecule contains glycidoxypropyltrimethoxysilane (GPTMS: Glycidoxypropyltrimethoxysilane) and 3-aminopropyl triethoxysilane (APTES: 3-Aminopropyltriethoxysilane) in a molar ratio of 1: 1 to 5, characterized in that it contains , composition.
A method for detecting formaldehyde, comprising: contacting a functional fiber to which a formaldehyde detection molecule including a pH indicator that changes color at pH 7 or less is attached with a sample containing formaldehyde;
The formaldehyde detection molecule contains glycidoxypropyltrimethoxysilane (GPTMS: Glycidoxypropyltrimethoxysilane) and 3-aminopropyl triethoxysilane (APTES: 3-Aminopropyltriethoxysilane) in a molar ratio of 1: 1 to 5, characterized in that it contains , a method for detecting formaldehyde.

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