KR100518367B1 - Antimicrobial finishing method of fibers using a natural antimicrobial agent extracted from gallnut and newly synthesized multi-functional compound - Google Patents

Abstract

The present invention relates to an antimicrobial processing method of a natural antimicrobial agent for fibers using a multifunctional compound, and more particularly, to a fibrous form of the natural antimicrobial agent by treating a fiber with a multifunctional compound in the process of antimicrobial processing of a natural antimicrobial agent extracted from a gall bladder. It is to be firmly bonded to to enhance the laundry durability and antimicrobial effect of the natural antimicrobial agent on the fiber.

An object of the present invention is to synthesize a novel multifunctional compound having two functional groups, α, β-dibromo acrylamide group and dichlorotriazine group, so that the natural antimicrobial agent extracted from the gall bladder is firmly bound to the fiber and processed it on the fiber. To provide a way to.

In order to realize the above object, the antimicrobial processing method of the natural antimicrobial agent for fibers using the multifunctional compound according to the present invention comprises 0.1-10% owf of a multifunctional compound having an α, β-dibromo acrylamide group and a dichlorotriazine group. Dissolving in water corresponding to the bath ratio 1:20 and adding acetic acid to adjust the pH to an acidic condition of 3 to 4; Adding fibers to the mixture at a temperature of 90 ° C. to 100 ° C. for 1 hour to covalently bond the α, β-dibromo acrylamide group of the multifunctional compound with the amine group of the fiber; Dissolving 0.1-20% owf of galoteannin-type natural antimicrobial agents in water corresponding to a bath ratio of 1:20, and then dissolving the alkaline substance at a concentration of 1-10 g / L to adjust the pH to an alkaline state of 10.5-11.5; A multifunctional compound comprising a step of covalently bonding the dichlorotriazine group of the multifunctional compound and the hydroxyl group of gallotannin, which is a natural antibacterial agent, by treating the fiber in the alkaline solution for 1 hour at a temperature of 30 to 40 ° C. Antimicrobial processing method of natural antibacterial agent for fiber using.

Description

Antimicrobial processing method of natural antimicrobial agent for fiber using multifunctional compound {Antimicrobial finishing method of fibers using a natural antimicrobial agent extracted from gallnut and newly synthesized multi-functional compound}

The present invention relates to an antimicrobial processing method of a natural antimicrobial agent for textiles using a multifunctional compound, and more specifically, to a fiber in the process of antimicrobial processing of a natural antimicrobial agent extracted from a gall bladder (mallow) produced from redwood. By treatment, the natural antimicrobial agent is firmly adsorbed on the fiber to enhance the laundry durability and antimicrobial effect of the natural antimicrobial agent on the fiber.

In general, functional fiber is a fiber that newly gives special functions such as deodorization, antibacterial, antifouling, deodorant, aroma, UV protection, far infrared radiation, etc. to the morphological function of the fiber, and in order to increase the added value of textile products in recent years There is increasing interest in these endowed functional fibers.

An example of this is the antibacterial fiber. As the antimicrobial fiber products become more economically rich and the quality of life is gradually improved, the demand is increasing day by day as consumers' desire for a healthy and pleasant life increases. Recently, antimicrobial processing has become commonplace in almost all products, and is expanding to general textiles as well as bedding, interior products, and medical textile products.

In order to impart antimicrobial function to textile products, antimicrobial materials are mixed with fibers or post-treated in an appropriate manner. These antimicrobial materials, that is, antimicrobial agents, are often divided into inorganic and organic systems.

The inorganic antimicrobial agent is initially used organic mercury, organic tin, organic zinc and the like, but the use of the present invention is rarely used because of problems with human stability. This is very expensive and there is a disadvantage in that the production of silver fibers in the yarn stage is more limited in terms of application than the post-treatment method.

The organic antimicrobial agent is mainly a quaternary ammonium salt-based compound, the cationic group (+) of the quaternary ammonium salt is electrostatically adsorbed to the anionic group (-) of the cell surface of the microorganisms to destroy the cell surface structure By showing the antibacterial effect, it occupies most of the currently used antimicrobial agents.

In addition, the inorganic / organic composite system includes an antimicrobial agent in which a copper compound is bonded to a polyacrylonitrile, which has a disadvantage in that the treatment method is too complicated and the copper ions still have a potential risk of causing problems during prolonged exposure to the human body. .

As such, currently used antimicrobial agents are all artificially synthesized to have antimicrobial properties, and these synthetic antimicrobial agents have various problems while having excellent antimicrobial properties.

For example, the synthetic antimicrobial agents have the function of removing harmful microorganisms in order to benefit the human body, but at the same time, these synthetic antimicrobial agents are irritating compounds, even though they do not have toxicity above the standard, It can be harmful, for example, it is known to cause allergic skin diseases such as atopic dermatitis, and may have a more serious effect on children or the elderly, especially those with weak immunity.

In addition, in the case of the synthetic antimicrobial agent, as in the case of other synthetic compounds, there is a problem that inevitably causes environmental pollution from the manufacturing process to use and disposal process.

In addition, when the antimicrobial agent is washed several times, the antimicrobial agent is not firmly bound on the fiber, but also has a disadvantage that the antimicrobial effect is reduced as the most separated from the fiber.

The present invention was developed to solve the above problems, in order to produce antibacterial fibers harmless to the human body by treating the multi-functional compound to the fiber in the previous step of antimicrobial processing of the natural antimicrobial agent extracted from the gall natural fiber even when washed several times The antimicrobial agent is firmly bonded without falling off the fiber to improve the durability and antibacterial effect of the laundry.

In order to achieve the above object, the antimicrobial processing method of the natural antimicrobial agent for fibers using the multifunctional compound according to the present invention is 0.1-10% of a multifunctional compound having an α, β-dibromo acrylamide group and a dichlorotriazine group. dissolving owf in water corresponding to a bath ratio of 1:20 and then adding acetic acid to adjust the pH to an acidic condition of 3 to 4; Adding fibers to the mixture at a temperature of 90 ° C. to 100 ° C. for 1 hour to covalently bond the α, β-dibromo acrylamide group of the multifunctional compound with the amine group of the fiber; Dissolving 0.1-20% owf of galoteannin-type natural antimicrobial agents in water corresponding to a bath ratio of 1:20, and then dissolving the alkaline substance at a concentration of 1-10 g / L to adjust the pH to an alkaline state of 10.5-11.5; The fiber was added to the alkaline solution and treated at a temperature of 30 to 40 ° C. for 1 hour to covalently bond the dichlorotriazine group of the multifunctional compound and the hydroxyl group of gallotannin, which is a natural antimicrobial agent.

Hereinafter, the antimicrobial processing method of the natural antibacterial agent for fibers using the multifunctional compound according to the present invention will be described in detail.

First, looking at the antimicrobial components extracted from the gall bladder, gallotannin (gallateannin: methyl gallate, methyl-digallic acid) formed by condensation of several of these units including gallic acid as shown in Figure 1 below. (m-digallic acid), methyl-m-digallate, meta-trigallic acid, methyl-m-trigallic acid, penta Galloyl

Glucose (penta galloyl glucose).

The gallotannin, a natural antimicrobial agent, is a polyphenol-based antimicrobial agent, so it is possible to produce a natural antimicrobial fiber product by treating it to a fiber, the antimicrobial properties of the fabric according to the treatment of the antimicrobial component 1 is shown.

In order to improve the laundry durability of the natural antimicrobial agent (gallotannin), a material that firmly binds the fiber and the natural antimicrobial agent is required, which will be described in detail.

[1] methods of synthesizing complex functional compounds

Synthesis method of a complex functional reactive compound for firmly binding the natural antibacterial agent extracted from the gall bladder is proceeded in two steps as follows.

(1) step 1

a) 0.025 to 0.06 mole (2.65 to 6.63 g) of an alkaline substance such as sodium carbonate is dissolved in 20 to 60 ml of distilled water.

b) 0.02 to 0.05 mole (3.76 to 9.91 g) of 2,5-diaminobenzenesulfonic acid (structure 1) is dissolved therein, and the resulting reaction solution is heated to a temperature of 0 to 5 ° C. Keep it.

c) Slowly drop 0.02 to 0.05 mole (5.01 to 12.52 g) of 2,3-dibromopropionyl chloride (structure 2) into the reaction solution. The reaction solution produced therefrom was reacted for 30 to 60 minutes with sodium-2-amino-5- (2,3-dibromopropionylamino) -benzenesulfonate (sodium-2-amino-5- (2,3 -dibromopropionylamino)

benzenesulfonate: Structure 3) is synthesized.

d) The material of Structure 3 thus synthesized was filtered under reduced pressure, washed three times with acetone and dried to obtain a solid material.

(2) step 2

a) Dissolve 0.01 to 0.03 mole (1.84 to 5.53 g) of cyanuric chloride (structure 4) in 10 to 50 ml of acetone.

b) The resulting solution is poured into 20 ml of distilled water containing 10 to 30 g of ice and kept at a temperature of 0 to 5 ° C.

c) pH is adjusted to 1-2 by adding 0.1-0.3 ml of 2N aqueous hydrochloric acid solution.

d) The solution obtained by dissolving 0.01 to 0.03 mole (4.24 to 12.725 g) of the substance of Structure 3 synthesized in step 1 in 30 to 50 ml of distilled water is slowly dropped into the reaction solution.

e) 20% aqueous sodium carbonate solution is added thereto to adjust the pH to 6 and react for 30 to 60 minutes while maintaining the temperature at 0 to 5 ° C.

f) Upon completion of the reaction, sodium-2- (2,3-dibromopropionylamino) -5- (4,6-dichloro- [1,3,5] tri, a multifunctional compound according to the present invention. Azin-2-ylamino) -benzenesulfonate (Sodium-2- (2,3-dibromopropionylamino) -5- (4,6-dichloro-

[1,3,5] triazin-2-ylamino) -benzenesulfonate: Structure 5) is produced and dried in vacuo to give a solid state.

For reference, the synthesis method of the newly synthesized multifunctional compound in the present invention is shown in Figure 2 below.

The multifunctional compound is characterized by having two reactors having different reactivity in one compound, one of which binds to the primary amine group (-NH ₂ ) present in silk, wool, or nylon fibers. Dibromo acrylamide (α, β-dibromoacrylamide) group, and the other is a dichlorotriazine group which binds to the hydroxyl group (-OH) of the natural antimicrobial (gallotannin) extracted from the gall bladder. By using the two reactors, the combined functional compound is bonded to the amine group of the fiber and at the same time as the hydroxyl group of the natural antimicrobial agent, the natural antimicrobial agent is firmly fixed without falling out of the fiber to provide the functions of washing durability and antibacterial effect I say to have.

delete

The reaction conditions of the two reactors are different. First, the α, β-dibromo acrylamide group reacts with an amine group in an acidic condition and a temperature of about 90 to 100 ° C., and the dichlorotriazine group is an alkaline condition and a temperature of 30 to 40 degrees. Since it reacts with a hydroxyl group at about ° C, under the conditions of reacting one reactor, the other reactors remain intact and thus can react the two reactors efficiently.

[2] methods for treating complex functional compounds

When the composite functional compound synthesized as described above is treated to a fiber having a primary amine group (-NH ₂ ) such as nylon, wool, or silk, a covalent bond is formed between the fiber and the composite functional compound, thereby firmly bonding to each other. The processing method is as follows.

0.1-10% owf of the multifunctional compound of the present invention is dissolved in water corresponding to a bath ratio of 1:20, and a small amount of acetic acid is added thereto to adjust the pH to an acidic condition of 3-4. Here, "owf" refers to the weight ratio of the dye or the preparation to the fiber weight, and "bath ratio" refers to the weight ratio of the treatment liquid to the fiber weight, and formic acid, hydrochloric acid, sulfuric acid, nitric acid and the like may be used in addition to the acetic acid.

Wool, silk, and nylon are added here and treated for 1 hour at a temperature of 90 to 100 ° C., and the α, β-dibromoacrylamide group of the multifunctional compound and the amine group of the fiber (-NH ₂ ) Is firmly bonded to each other by covalent bonds. At this time, the treatment temperature of 90 to 100 ° C. does not sufficiently react at a temperature of 90 ° C. or lower. This is because it is meaningless.

Subsequently, the multifunctional compound is washed with the treated fiber. As described above, since the α, β-dibromo acrylamide group of the multifunctional compound is covalently bonded to the amine group of the fiber, it does not fall off even if it is washed with water. On the other hand, another reactor, dichlorotriazine group is the reaction occurs in the alkaline conditions, so that it will remain intact.

[3] treatment methods for natural antibacterial agents

The method of treating the natural antimicrobial agent extracted from the gall of the fiber treated with the multifunctional compound is as follows.

The natural antimicrobial agent 0.1-20% owf is dissolved in water corresponding to the bath ratio 1:20, and an alkaline substance such as sodium carbonate is dissolved at a concentration of 1-10 g / L, and the pH is adjusted to an alkaline state of 10.5-11.5. In the treatment solution thus prepared, the fiber previously treated with the multifunctional compound is added and treated at a temperature of 30 to 40 ° C. for 1 hour.

Here, among the multifunctional compounds bonded on the fiber, the α, β-dibromoacrylamide group is already bonded to the amine group (-NH ₂ ) of the fiber, and dichlorotriazine ( The dichlorotriazine group is in an unreacted state and reacts with the hydroxyl group (-OH) of gallotannin, an antimicrobial component extracted from the gall, under alkaline conditions to form a covalent bond.

For reference, Figure 3 below shows a covalent bond between the multifunctional compound and the natural antimicrobial agent (gallotannin) extracted from the gall and fiber treated with the compound.

Mechanism is shown.

As such, when gallotannin having a hydroxy group (-OH) is treated to a fiber having a primary amine group (-NH ₂ ) such as nylon, silk, or wool, the fiber and the gallotannin are completely covalently bonded. Done.

Next, the antibacterial treated fiber is washed with water and dried. Since the antimicrobial gallotannin, which is treated to the fiber, is firmly bound to the fiber by covalent bonding, the fiber is continuously removed without washing even if washed with water. Since it remains in the can have excellent washing durability.

In addition, sodium hydroxide or sodium bicarbonate may be used as the alkaline substance in addition to the above-mentioned sodium carbonate, but in the case of using strong alkali sodium hydroxide, it is used at a concentration of 0.1 to 1 g / L.

In addition, the treatment temperature of the natural antimicrobial agent is 30 ~ 40 ℃, if the temperature is 30 ℃ or less, the reaction rate is too slow, it takes a lot of time, and if it is 40 ℃ or more dichlorotriazine of the complex functional compound (dichlorotriazine ) Part is hydrolyzed by water, so the amount of binding to gallotannin is significantly reduced.

In addition, Table 2 below shows three fibers obtained when the fiber using the multifunctional compound and the fiber using the multifunctional compound are treated with a natural antimicrobial agent extracted from a gall bladder.

The turbidity is shown.

According to the results of Table 2, it was found that the fiber treated with the natural antimicrobial agent after using the multifunctional compound was adsorbed on the fiber even when washed several times as compared to the fiber treated with the natural antimicrobial agent without using the multifunctional compound. Can be.

As described above, the antimicrobial processing method of the natural antimicrobial agent for fiber using the multifunctional compound according to the present invention synthesizes a multifunctional compound having a plurality of functional groups in the process of treating the natural antimicrobial agent extracted from the gall bladder to fiber By co-bonding the fiber with the natural antimicrobial agent and the multifunctional compound as a treatment to the natural antimicrobial agent is washed out of the fiber when the natural antimicrobial agent is processed to wash the fiber can be improved washing durability and antibacterial effect.

Claims (3)

It is characterized by consisting of two functional groups of α, β-dibromo acrylamide group covalently bonded to the amine group present in silk, wool or nylon fiber, and dichlorotriazine group covalently bonded to the hydroxyl group of gallotannins natural antimicrobial agent. Complex functional compound. Dissolving 0.025 to 0.06 moles of alkaline substance in 20 to 60 ml of distilled water, and then dissolving 0.02 to 0.05 moles of 2,5-diamino benzenesulfonic acid (structure 1); Maintaining the solution at a temperature of 0 to 5 ° C. and slowly dropping 0.02 to 0.05 mole of 2,3-dibro mopropionyl chloride (structure 2) thereto; The reaction solution was reacted for 30 to 60 minutes to synthesize sodium-2-amino-5- (2,3-dibromopropionylamino) -benzenesulfonate (structure 3), which was filtered under reduced pressure and washed with acetone. Drying to obtain a solid substance; Mixing a solution obtained by dissolving 0.01 to 0.03 mol of cyanuryl chloride (structure 4) to 10 to 50 ml of acetone in 20 ml of distilled water containing 10 to 30 g of ice; Maintaining the mixture at a temperature of 0 to 5 ° C. and adjusting the pH to 1 to 2 by adding 0.1 to 0.3 ml of 2N aqueous hydrochloric acid solution; In the alkaline reaction solution, a solution of 0.01 to 0.03 mol of the substance of Structure 3 dissolved in 30 to 50 ml of distilled water was slowly dropped, and 20% aqueous sodium carbonate solution was added thereto to adjust the pH to 6 and maintained at a temperature of 0 to 5 ° C. Synthesis method of a multifunctional compound, characterized in that consisting of a step of reacting for 30 to 60 minutes. Dissolving 0.1-10% owf of the multifunctional compound of claim 1 in water corresponding to a bath ratio of 1:20, and then adjusting the pH to an acidic condition of 3 to 4 by adding acetic acid; Adding fibers to the mixture at a temperature of 90 ° C. to 100 ° C. for 1 hour to covalently bond the α, β-dibromo acrylamide group of the complex functional compound with the amine group of the fiber; Dissolving 0.1-20% owf of galoteannin-type natural antimicrobial agents in water corresponding to a bath ratio of 1:20, and then dissolving the alkaline substance at a concentration of 1-10 g / L to adjust the pH to an alkaline state of 10.5-11.5; Put the fiber in the alkaline solution and treated for 1 hour at a temperature of 30 ~ 40 ℃ a multifunctional compound comprising a step of covalently bonding to the hydroxy group of dichlorotriazine of the multifunctional compound and galoteannin, a natural antimicrobial agent Antimicrobial processing method of the natural antibacterial agent used.