TW200946740A - Antiseptic and creaseproof reagent for cotton fabric - Google Patents

Abstract

An antiseptic and creaseproof reagent for cotton fabric comprises low molecular weight chitosan having a molecular weight between 3000 and 80000. The cotton fabric treated by the antiseptic and creaseproof reagent of this invention can further increase its creaseproof characteristic. In addition, since the low molecular weight chitosan is made by degradation of natural material, the health concern of the use of chemical reagent in the cotton fabric can be reduced. Moreover, because the low molecular weight chitosan is antiseptic per se, the cotton fabric treated by the antiseptic and creaseproof reagent of this invention can increase its antiseptic characteristic, thereby increasing the functionality of the cotton fabric.

Description

200946740 IX. Description of the invention: [Technical field of the invention] The present invention relates to a cotton fabric antibacterial anti-wrinkle agent, in particular to a cotton fabric antibacterial anti-wrinkle agent containing low molecular weight chitosan, which can be improved - cotton Antibacterial and anti-allergic effect of fabric. ° [Prior Art] Chitosan is a natural polymer compound. In general, chitin, which has a deacetylation degree of more than 55%, is called chitosan, and the degree of polymerization is 2 〇. The glycan is known as a chitosan or a low molecular weight chitosan (LWCS). Because the relative molecular weight of chitosan is large, it is usually in the hundreds of thousands or even millions, and due to the action of nitrogen bonds inside and outside the molecule, its chemical properties are stable, its solubility is very poor, and it can only be dissolved in a small amount of dilute acid solution. It is not directly soluble in water, so its application is limited. The low molecular weight chitinase is directly soluble in water, has strong permeability, and has many functions superior to chitosan macromolecules, such as antibacterial property, sorption of anionic dyes, inhibition of tumor growth, and lowering of cholesterol. And functions such as blood lipids are known, so low molecular weight chitosan is a fairly attractive direction in current research. Cotton fabrics are comfortable to wear because of their good breathability and hygroscopicity. However, cotton fabrics tend to wrinkle due to their poor elasticity, which often requires ironing and is inconvenient. At present, the method for improving the wrinkle resistance of cotton fabrics is usually to treat cotton fabrics with anti-wrinkle treatments. However, due to the importance of modern health concepts, how to use the more natural way to improve the cotton fabrics is the researcher and manufacturer of cotton fabrics. One of the directions of hard work. 5 200946740 [Summary of the Invention] In view of the fact that the existing cotton fabric anti-wrinkle agent has the disadvantage of improving the wrinkle resistance of the cotton fabric, the object of the present invention is to provide a cotton fabric containing a low molecular weight chitosan. Antibacterial anti-anti-agent, which uses more natural materials to improve the wrinkle of cotton fabrics. In order to achieve the above object, the cotton fabric antibacterial anti-wrinkle agent of the present invention contains a low molecular weight chitinase having a molecular weight of from 3,000 to 80,000. Preferably, the cotton fabric antibacterial anti-wrinkle agent of the present invention further contains dimethylol dihydroxyethylene (DMDHEU, Dimethy) ethylene urea. Preferably, the cotton fabric antibacterial anti-wrinkle agent of the present invention further comprises a softening agent. Preferably, the softening agent is a fourth level salting surfactant. Preferably, the cotton fabric antibacterial anti-wrinkle agent of the present invention further contains magnesium chloride. The specific efficacies that can be achieved by the present invention include: 1. The antibacterial anti-anti-agent of the present invention has a low molecular weight chitosan, so that the cotton fabric treated by the anti-wrinkle anti-wrinkle agent of the present invention can further improve the wrinkle resistance, and Because low molecular weight chitosan is degraded from natural materials, it can reduce the health concerns of chemical agents used in cotton fabrics. 2. The low molecular weight chitosan used in the present invention is itself resistant to bacteria. Therefore, the cotton fabric treated with the antibacterial anti-wrinkle agent of the present invention can increase the antibacterial property of the cotton fabric to improve the functionality of the cotton fabric. 6 200946740 [Embodiment] At present, the preparation methods of low molecular weight chitosan are generally acid degradation, degradation, oxidation degradation and other degradation methods, such as radiation method, microwave right ultrasonic method and the like. At present, the main methods for degradation in acidic solutions are the acid and sulfuric acid methods, etc. In the acidic solution, water will catalyze (4). Although the acid hydrolysis method is simple in engineering, the production and reading are low and the molecular weight of the product is difficult to control, and the contamination in the separation process is serious, so it is not suitable for industrial use. The enzyme degradation method is a biochemical method for preparing oligosaccharides by using chitosan degrading enzymes to degrade uranium. This method is to add no other agents during the process of introducing milder conditions. & no side reaction ^sheng' has less environmental pollution; in addition, the process of enzyme degradation and the distribution of product molecules are easier to control. However, the high cost and the immature technology are currently obstacles in application. Oxidative degradation & is a kind of μ which has been studied in recent years. This method has the advantages of rapid degradation, low cost, simple engineering and no residual toxicity. The commonly used reagents mainly include hydrogen peroxide and nitrite. universal. Therefore, the low molecular weight enthalpy of the preferred embodiment of the present invention is produced by an oxidative degradation process, and the manufacturing process is as follows: First, 2 g of chitosan is dissolved in hydrochloric acid (Η. !) ^Liquid. (4) 30 minutes, respectively, 5 different concentrations of peroxidized wind (5%, 7.5%, 10%, 125% and 15%), added to the above solution, and heated and stirred at 50 C for 4 hours' then Filtered by suction method. When filtering, the upper layer is washed with hydrazine water until neutral, then dried and weighed. The lower layer solution is added with three 200946740 times of ethanol and placed for 24 hours, then filtered, dried and weighed. A water-soluble low molecular weight chitosan is obtained, and the obtained products are represented by C5, C7.5, CIO, C12.5 and C15, respectively.

The prepared low molecular weight chitosan was subjected to various analysis to understand its properties. The determination of viscosity and molecular weight was carried out by the following methods: the dryness of each sample was determined by 〇·1Μ acetic acid and 〇_2M. The gasified sodium solution was used as a solvent, and the sample concentration was 1 g/L. The viscosity was measured by an Ubbelohde viscometer at 25 t, and the crude molecular weight of the sample was calculated according to the Mark-Houwink equation [π]=Κ[Μν] α. The alpha values were 1.81 χ 10·3 cm3/g and 0.93, respectively, and the results of elemental analysis, viscosity and molecular weight analysis of each sample are shown in Table 1. Table 1. Elemental Analysis, Viscosity and Molecular Weight Analysis of Low Molecular Weight Chitosan Sample Hydrogen Peroxide (%) Nitrogen Component (%) Hydrocarbon Oxygen-Viscosity (ml/g) Molecular Weight Primary Chitosan 7.40 39.06 6.22 47.32 293.474 240,500 C5 5.0 6.39 37.56 7.01 49.02 64.628 77,210 C7.5 7.5 6.36 36.95 6.98 49.71 34.944 40,100 C10 10.0 6.35 36.83 6.94 49.88 14.081 15,090 C12.5 12.5 6.33 36.93 6.90 49.94 8.455 8,720 C15 15.0 5.92 35.77 6.59 51.72 7.762 3,650 ❹ It can be found that after the degradation treatment of chitosan with hydrogen peroxide, its molecular weight and viscosity will decrease and decrease with the increase of the amount of hydrogen peroxide. This is the degradation of the chitosan molecular chain by hydrogen peroxide. Caused. As for the analysis of the content of each element, it is not directly related to the amount of hydrogen peroxide used. Functional analysis of low molecular weight chitosan is performed using Bio_Rad 8 200946740

For the analysis of Digilab FTS-200 Fourier spectrum analyzer, please refer to the first 4, where the A curve is the undegraded original chitosan analysis spectrum γ can be found at I574 cm" with c〇NH group The absorption peak, which is the relationship between the original chitosan and a little chitin. In the figure, B, 匚~乜原-line are the maps of C5, C10 and Cl5 respectively. It can be seen from the figure that the low molecular weight = glycan has a distinct peak near 1600-1630 cnr1, which is the absorption peak. It is a new side chain group of low molecular weight chitosan. Detection of Chemical Shift of iH_NMR Analysis of Low Molecular Weight Chitosan The lanthanide was detected by a liquid nuclear magnetic resonance apparatus of the BRUKER AMX-400 type. 1 Refer to the h_NMR spectrum of CI5 shown in the second figure, which has an absorption bee at 3.16ppm for H-2'. There are four absorption peaks between 3.57-3.80 ppm for H-3, H-4, H. -5 and H-6, and there is an absorption peak of H-7 at 1.91 ppm, and the absorption position of H-1 is at 4.75 ppm. The absorption spectrum data of the low molecular weight chitosan and the chitosan provided in the literature and the original undegraded chitosan were shown in Table 2. Table 2 1H-NMR chemical shift detection results (d20 solution) ❷____ ______H-1 H-2 H-3 H-4 H-5 H-6 H-7 Chitosan 34.87 3.18 3.78 3.83 3.74 3.87 2.07 Chitin Sugar 15 4.80 3.16 3.61 3.78 3.72 3.82 2.02 LWCS (C15) 4.75 3.16 3.57 3.66 3.71 3.80 1.91 a: The chitosan provided by the literature b: the original undegraded chitosan is known from the results of Table 2, chitin The absorption of various protons of sugar is not very different, and the structural formula of low molecular weight chitosan degraded by hydrogen peroxide is similar to that of the original chitosan. 9 200946740 Please refer to the third figure for the low molecular weight chitosan m, w ^ . A nine (X-ray) test;::, 2 two for the original undegraded chitosan detection knot - at 4 Η There is an absorption peak in the left and right, but the absorption peak of the low molecular weight chitosan condensed gradually disappears with the increase of the hydrogen peroxide concentration, as shown in the figure (10)), C(C1〇) and D(C15). In addition, the original undegraded chitosan has a distinct absorption peak at 2丨.2, but C15 is different. "It is also shifted to 22.5 〇 and 22^ ==. It is known that adding more hydrogen peroxide will change the crystal structure of chitosan. The following will actually test the anti-allergic properties of low-molecular-weight chitosan cotton fabrics. The following formulas are merely illustrative of the invention, and are not intended to limit the scope of the invention in any way, but are intended to indicate how to practice the materials and methods of the invention. First, different molecular weights of low molecular weight chitosan are obtained. (C5, cl〇 and C15) each 5g, 1g, 2g and 3g, pour the above low molecular weight chitin into 100ml of distilled water, stir for 15 minutes to dissolve all, then add 8 Dimethyl dihydroxyl ethylene urea (dmdHEU), 0.8 g of magnesium sulfide (MgCl2) and 3 ml of softener (such as a fourth-grade ammonium salt surfactant) were stirred for 15 minutes to form a process. Dip a 20 χ 24 cm white cotton cloth into the working fluid, apply a two-dip two-pressure method, and place it in a ultrasonic oscillator. The impregnated white cotton cloth is taken for pressure suction (Pick up = 80°/. )' and pre-event at 80 ° C for 5 minutes And heat treatment at different temperatures (130X:, 140 ° C, 150 ° C), then wash and dry to form a processing cloth, the processing cloth is loaded into the PE bag to be tested for its properties. The dry anti-wrinkle angle of the processed cloth according to ASTM D1 295-61 Monsanto type test 10 200946740. The test of the force type 丨 丨 以 is tested by the Alphaten 400 tensile tester according to ASTM 37G standard, and the softness and yellowness of the processed cloth are respectively INTECO softness test machine ( The water platform tilt angle is 45〇) and the 300A type color difference meter is used for detection. The test results are shown in Table 3. __Two processing properties of different low molecular weight chitosan treatments ^ Nature dry anti-wrinkle angle warp strength retention rate Yellowness softness (W -f F) ° (%) Index (cm) 285 52.5 4.8 — 4X~ 285 65.7 4.8 4.9 287 60.6 5.0 5.2 293 56.8 5.2 5.5 297 52.9 5.9 5.8 287 63.9 4.6 4.8 290 59.7 4.8 5.3 297 55.3 5.7 5.4 302 54.1 6.5 5.6 290 63.3 5.0 4.8 297 60.7 5.9 5.0 301 56.4 6.8 5.1 307 53.7 7.2 5.2 U: 10%, MgCl2: 1%, pick-up: 8〇°/Oj drying: LWCS LWCS Concentration (10) Control group 0.5 C5 C10 C15 1.0 2.0 3.0 0.5 1.0 2.0 3.0 0. 5 1.0 2.0 3.0 Control group: Dvmucn, 8 0 °C x 5 5 . , curing: 150〇C x3, as shown in Table 3, I can see the processing of low molecular weight chitosan. Only a few sensitive angles, I, 'Bings 1 t H, and the addition is better, and the dry wrinkle angle increases with the low molecular weight of several * domain molecules, this is the low molecular weight chitosan Although the fiber reacts in addition to Sega and DMdheu in the molecule, it also causes a reticular formation with the fiber bond to form a mesh structure. Secondly, when the molecular weight of the low molecular weight chitosan is reduced, the lower the penetration of the fiber is, the easier it is to penetrate the fiber, so the more resistance to the processing T is, the helper cup. Secondly, due to the permeability of low molecular weight chitosan 200946740

Permeation or coating, so that the strength of the processed cloth is improved, and gradually decreases with the increase of the concentration of low molecular weight chitosan. This may be due to the higher concentration, the more bridges are formed inside the fiber, to the more The size of the kernel knife that is prone to stress concentration does not have much influence on the strength of the processing cloth. As for the effect of yellowing degree and softness, it can be seen from Table 3 that the two properties are affected. In the opposite direction, the degree of yellowing deteriorates as the molecular weight of the low molecular weight chitosan decreases. This is because the lower molecular weight low molecular weight chitosan is more concentrated in the production of hydrogen peroxide. Chitosan is oxidized more intensely; but the softness is better with the decrease of the molecular weight of low molecular weight chitosan. This is because the low molecular weight chitin polymerase with low molecular weight is easy to infiltrate the human fiber (4), which is not easy to cause. The effect of processing temperature on the physical properties of the processed fabric will be discussed below. The physical properties of the processed fabric treated with ci5 low molecular weight chitosan at different heat treatment temperatures are shown in Table 4. Table 4 Properties of processed fabrics heat treated at different temperatures 200946740 Ο 角 f Wrinkle Eliw Desert} S % WCM L Thermodynamics C 钌 Heat

I 40 50 5·ο··0·°·50005000 °·12·3·0·12·3°·12·3 5707147390717 8788988999900 2222222222233 'Μ The strong retaining order 52.5 73.2 70.3 65.5 63.3 68.1 66.2 62.5 57.8 63.3 60.7 57.4 53.7 Degrees 匕曰德 m) J— c 柔{·δ8··°-28· 82510982 445554·5·5·6·5·5·6·7· ·8·8·°·2·3 ····························· : 80°C x5\ curing: 150°C x3! As can be seen from Table 4, the dry wrinkle resistance of the processed fabric increases with the increase of the heat temperature and the LWCS concentration. However, the strength and the degree of yellowing are opposite. This is because the high temperature is more likely to cause the fibers to be oxidized, which leads to a decrease in strength. However, the effect on the fabric feel is not much different from the results in Table 4, but overall, the processing of the low molecular weight chitosan treated fabric is slightly worse than that of the untreated low molecular weight chitosan. . The above results show that the treatment of cotton fabric with low molecular weight chitosan can improve the wrinkle resistance of cotton fabric, and the low molecular weight chitosan is degraded by natural polymer, so the antibacterial anti-wrinkle of the present invention is utilized. The agent can use the more natural ingredients to increase the wrinkle resistance of the cotton fabric, in line with the modern health concept. In addition, since the low molecular weight chitosan itself has antibacterial properties, the cotton fabric can be treated with the low molecular weight chitosan, and the antibacterial property of the cotton fabric can be treated by the antibacterial anti-wrinkle agent of the present invention. Cotton fabrics have a wider range of operability. BRIEF DESCRIPTION OF THE DRAWINGS The first figure is a g-energy analysis map of a low molecular weight chitosan used in the preferred embodiment of the present invention.

The second figure is an H-NMR analysis map of a preferred solid of the present invention. The third panel is an X-Ray analysis map of a preferred solid of the present invention. Low molecular weight used in several examples of low molecular weight used in the example

D [Main component symbol description] None

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Claims (1)

200946740 X. Patent application scope: 1 d, which contains a low molecular weight of 1 cotton fabric antibacterial anti-wrinkle agent / chitosan, the low molecular weight chitosan has a tiller system between 3,000 and 80,000. The cotton fabric antibacterial anti-wrinkle agent according to the invention of claim </RTI> further comprising dimethyl dihydroxyi ethylene urea (DMDHEU). The cotton fabric antibacterial anti-crease agent according to claim 1 or 2, further comprising a softening agent. 4. The cotton fabric anti-g bacteria anti-allergic agent according to claim 3, wherein the softening agent is a fourth-order ammonium salt interface active agent. j: The cotton fabric antibacterial anti-wrinkle agent according to Item 1 or 2, which further contains magnesium gasification. ©11, schema: as the next page