KR20100117256A - Poisonous substance-absorbing additives for fiber and textiles fabricated using the same - Google Patents

Abstract

PURPOSE: Fiber processing chemicals for removing poisonous substances and a fiber with a function of removing poisonous substances added to a cellulosic fiber system by the same are provided to permanently remove poisonous substances. CONSTITUTION: Fiber processing chemicals for removing poisonous substances include a β-cyclodextrin derivative. The fiber processing chemicals are coupled with a cellulosic fiber system fiber. The β-cyclodextrin derivative is made of at least one of β-cyclodextrin with a cyanuric chloride substituent, β-cyclodextrin with epichlorohydrin substituent, or a β-cyclodextrin derivative with a citric acid substituent.

Description

Textile processing agent for removing harmful substances and fibers having a harmful substance removal function added to the cellulose-based fiber processing agent {POISONOUS SUBSTANCE-ABSORBING ADDITIVES FOR FIBER AND TEXTILES FABRICATED USING THE SAME}

The present invention relates to a fiber processing agent for removing harmful substances and a fiber having a function of removing harmful substances added to cellulose fibers such as cotton and rayon. More particularly, the present invention relates to a fiber processing agent for removing harmful substances including β-cyclodextrin derivatives and capable of durable bonding to cellulose fibers, and a fiber having a function of removing harmful substances added to cellulose fibers.

Cyclohepta amylose (cycloheptaamylose) β- cyclodextrin (β-cyclodextrin) is also referred to as D ^<+> - as glucopyranose (D ^<+> -glucopyranose) unit is connected to the structure 7, form the overall shape of a donut shape. 1 is a diagram showing the molecular structure of β-cyclodextrin. In Fig. 1, the structure of β-cyclodextrin takes an arrangement in which secondary hydroxy groups attached to the C-2 and C-3 atoms on the glucose unit are located on one side of the ring and primary hydroxyl groups are located on the opposite side. At this time, the diameter of the internal cavity is reduced due to the free rotation of the primary hydroxyl groups, so that β-cyclodextrin has a trapezoidal cylindrical shape in which the secondary hydroxyl groups are located slightly wider. In this cylindrical structure, the outer part is hydrophilic and the inner part contains only CH and glucoside oxygen. Hydrophobicity (ML Bender and M. Komiyama, "Cyclodextrin Chemistry", Springer-Verlag, New York, 1978, pp. 3-9).

The cavity of β-cyclodextrin forms an inclusion complex with a compound of the appropriate size, with an inner diameter and depth of 7.0 mm (see J. Am. Chem. Soc., 1974 , 96 , 3630-3639). This phenomenon is greatly influenced by geometrical factors as well as chemical factors. Upon inclusion, the hydrophobic portion of the guest molecule is oriented for maximum contact with the nonpolar cavity, while the hydrophilic portion is located externally and is arranged to maximize contact between the solvent and the hydroxyl group of β-cyclodextrin. In other words, due to the polarity and hydrophilicity of the outer surface and the hydrophobicity of the cavities, β-cyclodextrin may have a hydrophobic compound in the hydrophilic mediator, and the formation of the complex is affected by the polarity of the guest molecule on the premise of size suitability.

In general, the inclusion of β-cyclodextrin is composed of substitution of water molecules in the cavity with a less polar guest molecule by using water as a medium. The interaction between a relatively nonpolar molecule and an incompletely hydrated hydrophobic cavity Proceed. Therefore, hydrophilic or strongly hydrated or ionized groups are difficult to form complexes, and the stability of the clathrate is proportional to the hydrophobicity of the guest molecule, so that the stability increases when the guest molecule containing methyl or ethyl substituent in the appropriate position is included. The driving force for the formation of the complex is not clear, but the cavitation and the water present therein, the water and guest molecules and the substitution occurring between the guest molecule and the cavity, β-cyclodextrin during complex formation It is known to depend on a number of factors, including mitigation of ring strain and Van der Waals interactions between host and guest (see JM Lehn (Ed), "Comprehensive Supramolecular Chemistry", Vol. 3, Cyclodextrins, Pergamon, New York, 1996, pp. 190-191; J. Appl. Polym. Sci. , 2000 , 78 , 1986-1991).

Formation of the complex is a kind of encapsulation function. Unlike microcapsules that have already been put to practical use, this is a molecular encapsulation function. The microcapsules contain 10 ¹⁰ to 10 ¹³ molecules and are sensitive to external friction or physical stimuli, whereas the inclusion complexes have 1 or 2 guest molecules. Only part of the guest molecule can be entrapped and sensitive to chemical stimuli such as substitution reactions by nonpolar solvents rather than physical stimuli.

Such inclusion properties of β-cyclodextrin are expected to be widely used in the textile industry in the form of clathrates such as surfactant removal or substitute of surfactants, fiber processing agents, perfumes, insecticides, antimicrobial agents, etc. ( See Starch / Starke , 2003 , 55 , 191-196). Looking at the papers applying β-cyclodextrin to textile products, Lee et al. described the binding of vinyl-based monomers to β-cyclodextrin and grafting it onto cotton fibers and the antimicrobial and aromatic properties of the textile products using them. (See J. Appl. Polym. Sci. , 2000 , 78 , 1986-1991; J. Appl. Polym. Sci. , 2001 , 80 , 438-446). The delay and leveling effect of β-cyclodextrin has been published (see J. Appl. Polym. Sci. , 2006 , 100 , 208-218). Recently, Cumbasa et al. The bactericidal effect of cyclodextrins was published ( J. Appl. Polym. Sci. , 2007 , 103 , 2660-2668). In fact, β-cyclodextrin has been applied to the deodorizing, fragrance, antibacterial and wastewater treatment filters of textile products since the late 1980s. However, since there is not much research on applying β-cyclodextrin to textile products, the need for development thereof is emerging.

SUMMARY OF THE INVENTION An object of the present invention is to provide a fiber processing agent for removing harmful substances including β-cyclodextrin derivatives, which can be durably bonded to cellulose fibers.

Another object of the present invention is to provide a fiber having a harmful substance removal function, the fiber processing agent is bonded to cellulose fibers.

To this end, the fiber processing agent for removing harmful substances of the present invention has introduced a reactive functional group capable of binding to cellulose fibers in β-cyclodextrin derivatives. Cyanuric chloride (CC '), epichlorohydrin, or citric acid may be used as the reactive functional group for this purpose. Hazardous substances that can be removed by the fiber processing agent for removing harmful substances of the present invention include hydrophobic substances having a benzene ring, such as benzene, toluene, phenol and nicotine.

On the other hand, the fiber having a harmful substance removal function of the present invention is the fiber processing agent is durable bonded to the cellulose fiber using a reactive functional group.

It was confirmed that the fiber processing agent according to the present invention can bind and entrap harmful substances such as benzene and toluene in the pupil formed by the β-cyclodextrin derivative. In particular, β-cyclodextrin derivatives include reactive substituents in the form of monochlorotriazines, which can react with cellulose fibers to obtain durable fibers for removing harmful substances. It became possible to block Since the fiber having the function of removing harmful substances of the present invention is bound to β-cyclodextrin derivatives and cellulose-based fibers via a reactive substituent, the removal of harmful substances is almost permanent. Furthermore, the entrapment of harmful substances may also be easily removed by general water washing including a surfactant.

The fiber processing agent for removing harmful substances of the present invention has introduced a reactive substituent capable of binding to cellulose fibers in β-cyclodextrin derivatives. Cyanuric chloride (CC '), epichlorohydrin, or citric acid may be used as the reactive functional group for this purpose.

Β-cyclodextrin derivatives in the form of monochlorotriazine are bound to the primary and secondary OH functional groups of cellulose. Nucleophilic substitution occurs during the reaction. As the reactive group in the form of dichlorotriazine is substituted for H ⁺ of the hydrated cellulose fiber, durable covalent bonds are formed. In addition, an alkali catalyst is generally used to advantageously ionize the cellulosic fibers for the reaction, and the alkali catalyst serves to neutralize the acid, which is a reaction residue. As described above, the bond between the β-cyclodextrin derivative and the cellulosic fiber via the reactive substituent forms a covalent bond between the processing agent and the fiber, so that the effect of removing the harmful substances is almost permanent.

Toxic substances which can be removed by the fiber processing agent for removing harmful substances of the present invention include a substance having a benzene ring, such as benzene, toluene, phenol and nicotine.

On the other hand, the fiber for removing harmful substances of the present invention is the fiber processing agent is durable bonded to the cellulose fiber. At this time, as the cellulose fibers, cotton, kapok, flax, ramie, hemp, jute, bovine fiber, manila hemp, sisal hemp, New Zealand hemp, coconut fiber, coir, pulp, rayon, viscose rayon or cellulose acetate alone or these It can be used in a mixture of two or more of them.

Hereinafter, the present invention will be described in detail with reference to Examples. These examples are only presented by way of example only to more specifically describe the present invention, the scope of the present invention is not limited by these examples.

Example  One. Monochloro Triazine system Cyclodextrin  Preparation of Derivatives

   1-1. Synthesis of β-cyclodextrin-CC

β-cyclodextrin is a product of Nippon Food Corporation, without purification, cyanuric chloride is a product of Aldrich Chemical Co. (99% purity), Emulsifier was purchased as a product (DMS-371, purity 95%) of Doa Petrochemical Co., Ltd. without being purified. Other reagents were also used without purification of commercial grade 1 or higher. Toluene (Ducksan 99.5%) and benzene (DC Chemical, 99.5%) were used as the targets of inclusion.

Cyanuric chloride is widely used as a raw material for synthesizing reactive dyes.In alkaline conditions, the first Cl group in cyanuric chloride reacts at 0 ~ 5 ℃, and the second Cl group reacts only after raising the temperature to 20 ℃. The Cl group reacts only when it is 50 ℃ or higher. The specific synthesis method followed a known method (see J. Korean). Soc . of Textile Eng . Chem . , 1984 , 218-225).

First, 0.04 mol of cyanuric chloride was dissolved in 60 ml of acetone. Then, 100 ml of an aqueous solution of 0.042 mol NaOH was slowly added dropwise to the cyanuric chloride solution over about 1 hour while maintaining a temperature of 0 to 5 ° C. and a pH of 7 to 8. Stirred. After stirring for 1 hour while maintaining the temperature to prepare a water-soluble cyanuric chloride. 0.01 mol β-cyclodextrin was dispersed in 100 ml of distilled water, and the 0.012 mol water-soluble cyanuric chloride solution prepared above was stirred dropwise over about 1 hour while maintaining the temperature at 30 ° C. or below and pH 7-8. Thereafter, 100 ml of an aqueous solution of 0.02 mol NaOH was slowly added dropwise over about 1 hour while maintaining the temperature of 30 to 35 ° C, and the reaction was further stirred for 2 hours. The β-cyclodextrin (hereinafter, 'β-cyclodextrin-CC') derivative of the obtained monochlorotriazine form was precipitated in an excess of acetone and washed again with acetone 10 times.

   1-2. Chlorine and Nitrogen Content Analysis

Determine the chlorine content of β-cyclodextrin-CC synthesized by the combustion flask method (J. Shugar and JT Ballinger, "Chemical Technicians' Ready Reference Handbook", McGraw-Hill Inc., NY, 1990, p. 299). The nitrogen content was determined using an elemental analyzer (EA 1110). 2 shows the chlorine and nitrogen contents of β-cyclodextrin-CC. In Fig. 2, (■) is a theoretical numerical value, and (▒) is a value obtained in an experiment. The presence of a reactor of β-cyclodextrin-CC synthesized by quantitative chlorination using a numerical combustion flask method was confirmed. The quantitative data of Cl group and the quantitative data of N obtained through elemental analysis were compared with the reaction theory and β The reaction ratio of cyclodextrin and cyanuric chloride could be confirmed. When β-cyclodextrin and cyanuric chloride are reacted 1: 1, the synthesized derivative has a theoretical nitrogen content of 3.26% and a chlorine content of 2.76%. Since the chlorine content and nitrogen content of the synthesized monochlorotriazine type β-cyclodextrin derivatives have almost similar values, it was confirmed that β-cyclodextrin and cyanuric chloride reacted normally 1: 1.

Example  2. β- Cyclodextrin - CC To Cellulose Fibers

   2-1. Application of processing agent to cellulose fiber

KS K 0905 standard cotton cloth was used as the cellulose fiber. The process was carried out in a pad-dry-pad-heat treatment-washing process. 100% pick-up was padded to a solution made of β-cyclodextrin-CC 20 g / l prepared in Example 1 and 200 g / l urea and dried at 80 ° C. for 5 minutes. Then, 100% pick-up was added to 20g / l sodium carbonate and 20g / l sodium chloride mixture to pad the cotton fabric, followed by heat treatment at 110 ° C. for 4 minutes, thereby processing β-cyclodextrin-CC to the cotton fabric.

   2-2. Spectroscopic analysis

Figure 3 shows the combination of the processing agent treated fabric and untreated fabric using FT-IR (Prospect FT-IR, Midac Co.). At 900 cm ^-1 , a peak that does not appear in the untreated cotton fabric appears, which was analyzed by a COC stretching vibration peak combining a secondary hydroxyl group reactor of cellulose and a reactor of β-cyclodextrin-CC. In addition, as shown in FIG. 3, since the COC stretching vibration peak did not change even after five washings, it was confirmed that the processing agent was bonded to the cellulose fibers with durability.

Example 3 Hazardous Substances of β-Cyclodextrin-CC Inclusion  effect

   3-1. Benzene Inclusion of β-cyclodextrin-CC

4 is a schematic diagram showing a process in which harmful substances are included in β-cyclodextrin. In FIG. 4, each (□) represents a hazardous substance and (○) represents a solvent molecule. As schematically shown in Fig. 4, the water molecules in the cavity are entrapped by a substitution reaction with a less polar guest molecule, and the hydrophobic cavity of β-cyclodextrin-CC in which the relatively nonpolar benzene is incompletely hydrated. The interaction of harmful substances proceeded.

5A, 5B and 5C are UV-Visible spectral absorbance graphs of β-cyclodextrin-CC, benzene and benzene inclusion β-cyclodextrin-CC, respectively. After preparing 0.02 mol of benzene, 0.01 mol of β-cyclodextrin-CC was added thereto, and the mixture was stirred for 48 hours at room temperature in a suspended state. After inclusion, UV-visible spectrophotometer (UNICAM 8700 series) was used to compare the absorbance of β-cyclodextrin-CC of 1 × 10 ^-4 M with β-cyclodextrin-CC in the benzene and benzene inclusion states. As a result of absorbance analysis of UV-visible spectrophotometer, it was confirmed that β-cyclodextrin-CC contained benzene, a harmful substance, to control direct contact between the harmful substance and skin.

   3-2. Toluene Inclusion of β-cyclodextrin-CC

Water molecules in the β-cyclodextrin-CC cavity are entrapped by substitutions with less polar guest molecules, which interact with the hydrophobic cavity of the relatively nonpolar toluene incompletely hydrated β-cyclodextrin-CC. The entrapment of harmful substances proceeded.

6A and 6B are UV-Visible spectral absorbance graphs of toluene and toluene inclusion β-cyclodextrin-CC, respectively. After preparing 0.02mol of toluene aqueous solution, β-cyclodextrin-CC 0.01mol was added thereto, and the mixture was stirred for 48 hours at room temperature in a suspended state to make inclusion. After inclusion, UV-visible spectrophotometer (UNICAM 8700 series) was used to analyze the absorbance of 1 × 10 ^-4 M of toluene and β-cyclodextrin-CC in the toluene inclusion state. As a result of absorbance analysis of UV-visible spectrophotometer, it was confirmed that the inside of β-cyclodextrin-CC contained toluene which is a harmful substance, and thus the harmful substance was removed in the hazardous environment.

The present invention described above is not limited to the above-described embodiments and the accompanying drawings, and various substitutions, modifications, and changes are possible within the scope without departing from the technical spirit of the present invention. It will be apparent to those who have knowledge.

1 is a diagram showing the molecular structure of β-cyclodextrin,

 Figure 2 is a diagram showing the chlorine, nitrogen content of β-cyclodextrin-CC,

 Figure 3 is a diagram showing the coupling and washing durability of β-cyclodextrin-CC treated fabric and untreated fabric,

Figure 4 is a schematic diagram showing the process of inclusion of the harmful substances in β-cyclodextrin,

5A, 5B and 5C are UV-Visible spectral absorbance graphs of β-cyclodextrin-CC, benzene and benzene inclusion β-cyclodextrin-CC, respectively,

6A and 6B are UV-Visible spectral absorbance graphs of toluene and toluene inclusion β-cyclodextrin-CC, respectively.

Claims (7)

A fiber processing agent for removing harmful substances including β-cyclodextrin derivatives and capable of durable bonding to cellulose fibers. The β-cyclodextrin derivative according to claim 1, wherein the β-cyclodextrin derivative is a β-cyclodextrin having a cyanuric chloride substituent, a β-cyclodextrin having an epichlorohydrin substituent, or a β-cyclodextrin derivative having a citric acid substituent. The fiber processing agent, characterized in that at least one selected from the group consisting of. The method of claim 1, wherein the harmful substance is a textile processing agent, characterized in that the material having a benzene ring. The method according to claim 1, wherein the harmful substance is at least one substance selected from the group consisting of benzene, toluene, phenol and nicotine. The cellulosic fibers to be bonded are cotton, kapok, flax, ramie, burlap, jute, chopped fiber, manila hemp, sisal, new zealand hemp, coconut fiber, coir, pulp, rayon, viscose rayon and cellulose. The textile processing agent, characterized in that at least one selected from the group consisting of acetate. Fiber having a function of removing the harmful substances added to the cellulose fiber is a fiber processing agent of claim 1 to 5. The method of claim 6, wherein the cellulose-based fibers are cotton, kapok, flax, ramie, burlap, jute, chopped fiber, manila hemp, sisal hemp, New Zealand hemp, coconut fiber, coir, pulp, rayon, viscose rayon and cellulose acetate Fibers with the harmful substance removal function, characterized in that at least one selected from the group consisting of.

Images