WO2014127713A1 - Method for preparing cyanuric chloride-based halogenoamine antibacterial material - Google Patents

Abstract

Disclosed in the invention is a method for preparing a cyanuric chloride-based halogenoamine antibacterial material, with the process steps as follows: completely dissolving cyanuric chloride in an alkali liquor to prepare a finishing liquor, soaking a material to be finished in the finishing liquor until the material is drenched, taking out and drying after the finishing has been completed, and solidifying at 90-120°C for 10-40 min, washing the surface of the material, and finally halogenating, washing, and drying to prepare the antibacterial material. The method of the present invention has simple operation, cheap costs, mild reaction conditions, and little effect on the mechanical properties of the material, and the finished material has excellent antibacterial properties and is safe and nontoxic.

Description

 Preparation method of halogen amine antibacterial material based on cyanuric chloride Technical field

 The invention belongs to the technical field of antibacterial materials, and particularly relates to a preparation method of a halogen amine antibacterial material based on cyanuric chloride.

Background technique

There are a large number of pathogenic and mildew-causing microorganisms in the human living environment. They can spread on the surface of various materials and products such as fibers, plastics, rubber, paper, etc., which threaten human health. The use of long-lasting antimicrobial materials is the simplest, safe and effective way to effectively prevent the growth, reproduction, spread and spread of harmful microorganisms. The traditional antibacterial agents used for antibacterial finishing of materials include heavy metals, quaternary ammonium salts, triclosan, etc., but all have disadvantages such as high price, weak antibacterial ability, low sterilization efficiency, and harmful to human body. The newly developed halogen amine antibacterial agent makes up for the deficiency of the above antibacterial agent, and has the advantages of wide antibacterial spectrum, rapid sterilization, reproducible antibacterial activity, no toxic by-products, harmless to human body and environment, and antibacterial finishing in materials. The field has broad application prospects.

At present, the preparation process of antibacterial materials based on halogen amine antibacterial agents still has the following disadvantages: involving more reactants, expensive raw materials, harsh reaction conditions, complicated process, high production cost, poor water solubility of raw materials, low utilization rate, and need to be added in a large amount of The combustion of organic solvents helps to increase the finishing cost, and there are safety hazards; the finishing process has a great influence on the mechanical properties of the material, and the textile strength loss is serious; the antibacterial property of the prepared antibacterial material needs to be improved.

technical problem

 The applicant is targeting existing halogen amines The above defects in the preparation process of the antibacterial material provide a preparation method of a halogen amine antibacterial material based on cyanuric chloride. The method of the invention has simple process operation, low cost, mild reaction condition, little influence on mechanical properties of the material, excellent antibacterial property of the material after finishing, safety and non-toxicity.

Technical solution

 The object of the invention is achieved by the following technical solution:

A preparation method of a melamine-based halogen amine antibacterial material, the process steps are as follows: completely dissolving cyanuric chloride in an alkali solution to prepare a finishing liquid, and then immersing the material to be finished in the finishing liquid to be wet Permeate the material, finish it, take it out, and Curing at 90~120°C for 10~40min, cleaning the surface of the material, and finally halogenating, washing and drying to obtain antibacterial material.

 Its further technical solution is:

 The lye includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate solution, and the mass percentage thereof is 1 to 30%. , preferably 2 to 5%.

 In the finishing bath, the mass percentage of the cyanuric chloride is 0.5 to 30%, preferably 1 to 5%.

The halogenation is performed by soaking the material with a solution containing an active halogen, and the active halogen-containing solution includes sodium hypochlorite, sodium hypobromite or calcium hypochlorite solution, and the mass percentage thereof is 0.01~5%, preferably 0.01~0.5%, pH value is 4.0~12.0.

The material to be finished includes natural fiber or synthetic fiber textile, plastic, sponge, natural rubber, synthetic rubber, wood, paper, paint, chitosan or chitin.

The curing treatment may be performed by oven baking, high temperature ironing, drum treatment, hot air treatment, etc.; when the material to be finished is a natural fiber or a synthetic fiber textile, the conventional two-dip two-rolling method is adopted after being immersed in the finishing liquid. Processing, rolling rate 100%.

Beneficial effect

 Compared with the existing preparation process of the halogen amine antibacterial material, the invention has the following advantages:

 1 . Directly using cheap and easily available cyanuric chloride as a raw material, dissolving it in an alkali solution to obtain a finishing liquid.

 High material utilization rate, no need to add flammable organic solvent to help dissolve, the operation is very simple and low cost.

 2 . Mild process conditions and low curing temperature 90~120°C), the time is short, and the mechanical properties of the material are little affected. After testing, the strength loss of the antibacterial textile made by the invention is less than 20%, which is obviously superior to the antibacterial textile prepared by the conventional process.

 3 . The antibacterial material prepared by the invention has excellent antibacterial property and high antibacterial efficiency, and the effective chlorine content thereof is 0.1~1.0%. Within the scope, after the inoculation of the prepared antibacterial cotton fabric and the inoculated bacteria, the antibacterial rate against Staphylococcus aureus within 100 min can reach 100%, and E. coli O157 : H7 within 5 min. The antibacterial rate can reach 100%.

4 . The preparation process and the finished product have no formaldehyde release, and are safe and non-toxic.

DRAWINGS

 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the chemical reaction of antibacterial finishing in Example 1 of the present invention.

 Fig. 2 is a schematic view showing the sterilization and bactericidal activity regeneration of the antibacterial material prepared by the invention.

 Figure 3 is an infrared spectrum analysis of cotton fabric, wherein (A) is a blank sample, and (B) is Example 1 The cotton fabric before chlorination, (C) is the cotton fabric after chlorination in Example 1.

Embodiments of the invention

 The invention will be specifically described below by way of examples with reference to the accompanying drawings.

 As shown in Figure 1, the cyanuric chloride is first reacted with sodium hydroxide to form a soluble sodium salt, which is reactive with the fibrous textile under curing conditions ( Cellulose-OH) undergoes a nucleophilic substitution reaction in which a hydroxyl oxygen on the cellulose replaces the chlorine on the triazine ring, thereby attaching the above sodium salt to the surface of the material.

 Figure 2 As shown, the halogen amine antibacterial agent attached to the surface of the material exerts a bactericidal action through its oxidizing chlorine atom, and when the available chlorine is released, the antibacterial property (regeneration) can be recovered by chlorine bleaching.

 Example 1

 Completely dissolve 1g of cyanuric chloride and 2g of sodium hydroxide in 97g Prepared into a finishing liquid in distilled water, and then immersed the natural fiber textile (pure cotton fabric, purchased from Zhejiang Guandong Printing and Dyeing Garments Co., Ltd.) in the finishing liquid for 15 minutes, two dip and two rolling, and the rolling residual rate is 100%. After finishing, it is taken out and placed in a dryer and dried at 80 °C for 5 minutes, then placed in a baking machine at 120 °C for 10 minutes; the fabric is taken out, and the mass concentration is 0.5%. Wash the surface with a standard soap solution and a large amount of deionized water, and dry at room temperature; soak the air-dried fabric in a 0.01% by weight calcium hypochlorite solution (adjust the pH to 7.0 with dilute sulfuric acid). 1h After the fabric was taken out and washed with a large amount of water, it was dried in a dryer at 45 ° C for 2 h to obtain an antibacterial cotton fabric. The effective chlorine content of the antibacterial cotton fabric was measured by iodometric method to be 0.68%.

 Example 2

 Completely dissolve 8g cyanuric chloride and 7g potassium hydroxide in 87g Prepared into a finishing liquid in distilled water, and then immersed the natural fiber textile (pure cotton fabric, purchased from Zhejiang Guandong Printing and Dyeing Garments Co., Ltd.) in the finishing liquid for 15 minutes, two dip and two rolling, and the rolling residual rate is 100%. After finishing, it is taken out and dried in a dryer at 80 °C for 5 minutes, then placed in a baking machine at 90 °C for 40 minutes; the fabric is taken out, and the mass concentration is 0.5%. Wash the surface with a standard soap solution and a large amount of deionized water, and dry at room temperature; soak the air-dried fabric in a 0.5% by weight sodium hypochlorite solution (adjust the pH to 12.0 with dilute sulfuric acid), 1h After the fabric was taken out and washed with a large amount of water, it was dried in a dryer at 45 ° C for 2 h to obtain an antibacterial cotton fabric. The effective chlorine content of the antibacterial cotton fabric was measured by iodometric method to be 0.86%.

 Example 3

 Completely dissolve 5g of cyanuric chloride and 11g of potassium hydroxide at 84g Prepared into a finishing liquid in distilled water, and then immersed the natural fiber textile (pure cotton fabric, purchased from Zhejiang Guandong Printing and Dyeing Garments Co., Ltd.) in the finishing liquid for 15 minutes, two dip and two rolling, and the rolling residual rate is 100%. After finishing, it is taken out and dried in a dryer at 80 °C for 5 minutes, then placed in a baking machine at 100 °C for 20 minutes; the fabric is taken out, and the mass concentration is 0.5%. Wash the surface with a standard soap solution and a large amount of deionized water, and dry at room temperature; soak the air-dried fabric in a 0.1% by weight sodium hypochlorite solution (adjust the pH to 7.0 with dilute sulfuric acid), 1h After the fabric was taken out and washed with a large amount of water, it was dried in a dryer at 45 ° C for 2 h to obtain an antibacterial cotton fabric. The effective chlorine content of the antibacterial cotton fabric was measured by iodometry to be 0.99 %.

 Antibacterial cotton fabric strength test:

 According to the ASTM D5035 method (trimming method), the first embodiment to the third embodiment The antibacterial cotton fabric was tested for strength, and the strength loss was 16%, 10%, and 15%, both of which were less than 20%. Compared with the conventional finishing process, it proves that the finishing method of the invention has little influence on the mechanical properties of the fabric.

 FT-IRATR infrared spectrum analysis of antibacterial cotton fabric:

 Fourier-attenuated total reflection spectroscopy (FT-IRATR) The test method was tested, and the unwoven cotton fabric (ibid.) was used as a blank sample, and the cotton fabric before and after chlorination in Example 1 was subjected to infrared spectrum analysis. The test results are shown in Fig. 3.

3, (B) appears in the curve at 1713cm ^-1 1610 cm ^-1 and new absorption peak, (C) the curve there is a new absorption peak at 1700 cm ^-1 and at 1605 cm ^-1, as The absorption peak of the carbonyl group and the double bond on the triazine ring proves that the triazine ring is attached to the cotton fabric.

 Antibacterial performance test of antibacterial cotton fabric:

 Tested according to the method described in Amendment AATCC 100-1999 Antimicrobial Performance Test Standard, to Example 2 The cotton fabric before chlorination was used as a blank sample, and the antibacterial property of the antibacterial cotton fabric prepared in Example 2 (effective chlorine content 0.86%) was tested, and the inoculating bacteria were Staphylococcus aureus and Escherichia coli O157 : H7 See Table 1 and Table 2 for test results.

 Table 1 Antibacterial properties of antibacterial cotton fabric against Staphylococcus aureus

	When in contact (min)	Percent reduction	Log reduction
Blank sample	10	89.58	0.98
Antibacterial cotton fabric	1	99.999	4.82
5	99.999	5.13
10	100	7.26

Note: The inoculation concentration of Staphylococcus aureus is 1.80 x 10 ⁷ cfu, and the log reduction is 7.26, ie all kills.

 Table 2 Antibacterial properties of antibacterial cotton fabric against Escherichia coli O157 : H7

	Contact time (min)	Percent reduction	Log reduction
Blank sample	10	27.23	0.14
Antibacterial cotton fabric	1	99.999	5.00
5	100	7.43
10	100	7.43

Note: The inoculation concentration of E. coli O157:H7: 2.67 x 10 ⁷ / sample, the log reduction is 7.43 ie all killed.

 Table 1 and Table 2 The test data shows that the cotton fabric finished by the method of the invention has excellent antibacterial property, and the antibacterial rate of the antibacterial cotton fabric against Staphylococcus aureus within 10 minutes after contact with the inoculated bacteria can reach 100%. The antibacterial rate against E. coli O157 : H7 can reach 100% within 5 min.

The above examples and application examples relate to the fact that each of the raw materials and reagents are commercially available products, and the production equipment used is conventional equipment in the art, wherein Staphylococcus aureus and Escherichia coli O157 : H7 Purchased from the American Model Culture Collection (ATCC).

 The above description is for the purpose of explanation only, and the present invention is not limited to the above embodiments. can

It is to be understood that other modifications and changes may be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims (9)

1. The invention discloses a preparation method of a melamine-based halogen amine antibacterial material, which is characterized in that the process steps are as follows: the cyanuric chloride is completely dissolved in an alkali solution to prepare a finishing liquid, and the material to be finished is immersed in the finishing liquid. According to the wet material, finish it, take it out, and Curing at 90~120°C for 10~40min, cleaning the surface of the material, and finally halogenating, washing and drying to obtain antibacterial material.
2. According to claim 1 The method for preparing the halogen amine antibacterial material, characterized in that the alkali liquid comprises sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate solution, and the mass percentage thereof is 1 ~30% .
3. The method for preparing a halogen amine antibacterial material according to claim 1, wherein in the finishing bath, the mass percentage of the cyanuric chloride is 0.5~30%.
4. According to claim 1 The method for preparing the halogen amine antibacterial material is characterized in that the halogenation is performed by soaking the material with a solution containing an active halogen.
5. According to claim 1 The preparation method of the halogen amine antibacterial material is characterized in that the material to be finished comprises natural fiber or synthetic fiber textile, plastic, sponge, natural rubber, synthetic rubber, wood, paper, paint, chitosan or chitin quality.
6. According to claim 1 The method for preparing the halogen amine antibacterial material further comprises the step of performing two dip and two rolling on the natural fiber or the synthetic fiber textile soaked in the finishing liquid.
7. The method for preparing a halogen amine antibacterial material according to claim 2, wherein the alkali liquid has a mass concentration of 2 to 5% .
8. The method for preparing a halogen amine antibacterial material according to claim 3, wherein in the finishing bath, the mass percentage of the cyanuric chloride is 1 to 5% .
9. According to claim 4 The method for preparing the halogen amine antibacterial material is characterized in that the active halogen-containing solution comprises sodium hypochlorite, sodium hypobromite or calcium hypochlorite solution, and the mass percentage thereof is 0.01 to 5%. .

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