CN107496176A - Safe and efficient antibacterial wet tissue and preparation method thereof - Google Patents

Abstract

The invention discloses a safe and efficient antibacterial wet tissue and a preparation method thereof. The antibacterial wet wipes are composed of a sterilized nonwoven fabric and a chitosan derivative-based antibacterial liquid loaded on the sterilized nonwoven fabric, and the load of the antibacterial liquid is 50-500wt%; the antibacterial liquid includes the following Raw materials in parts by weight, based on 100 parts by weight: 0.05-5 parts of chitosan derivatives, 0.5-5 parts of surfactant, and the balance of deionized water. The safe and efficient antibacterial wet wipes of the present invention can be used for hands, medical equipment, household daily necessities, etc. due to the use of chitosan derivatives with good biocompatibility, safety, non-toxicity, non-irritation, and broad-spectrum antibacterial properties as antibacterial agents. The antibacterial disinfection of the surface of the article can effectively kill common pathogenic bacteria, viruses and other harmful microorganisms, and it is green, safe, non-toxic, non-skin irritating, non-corrosive, and easy to carry and use.

Description

A kind of safe and efficient antibacterial wet tissue and preparation method thereof

technical field

The invention relates to the field of daily cleaning products and their preparation. More specifically, it relates to a safe and efficient antibacterial wet wipe and a preparation method thereof.

Background technique

The wet wipes currently on the market can be roughly divided into two categories: one type has been sterilized itself, but has no antibacterial protection effect on other items, and contains skin care ingredients, which can only be used for skin moisturizing and maintenance; the other type is not only for itself Disinfectant wipes that are disinfected and can also disinfect other items can be used for disinfection or sterilization of skin and daily necessities.

The commonly used disinfectants for disinfectant wipes mainly include peracetic acid, ethanol, isopropanol, etc. These disinfectants have their own advantages and disadvantages. Peracetic acid is a strong oxidizing agent with strong oxidizing properties. When it encounters organic matter, it releases new ecological oxygen to oxidize. It is used as a medical or life disinfection drug with sodium hypochlorite (also known as 84 disinfectant) and bleaching powder. It is highly effective and quick-acting. , low toxicity, broad-spectrum fungicide, has killing effect on bacterial propagules, spores, viruses and molds. Therefore, it can be used for sterilization and disinfection. In addition, because peracetic acid has strong volatility in the air, it has a good effect on sterilization and disinfection of the air, and it is cheap. In 2003, the main sterilization and disinfectant used in the prevention of SARS in my country was peracetic acid. However, the peracetic acid solution is unstable, so it should be stored in a ventilated and cool place, and its effective concentration should be measured before use; distilled water, deionized water or purified water is used to prepare the diluent, and the diluent should not be stored at room temperature for more than 48 hours. Peracetic acid is highly corrosive to metals, and will decompose violently when mixed with alkalis or organic substances, or even explode. High-concentration liquid medicine is highly corrosive and irritating, and its smell is unacceptable. The most commonly used alcohol disinfectants are ethanol and isopropanol, which can coagulate proteins and cause the death of microorganisms. They are medium-efficiency disinfectants that can kill bacterial propagules and destroy most lipophilic viruses, such as herpes simplex virus and hepatitis B. viruses, human immunodeficiency virus, etc. However, ethanol sterilization has certain requirements on the concentration, and its effective volume fraction should be 65% to 75%. Water is very necessary for the bactericidal effect of ethanol, so ethanol needs to be diluted when used for disinfection, but when the concentration is lower than 30%, the bactericidal effect is very small, and the bactericidal effect will be reduced if the concentration is too strong or too weak. 75% of the unilateral ethanol disinfection preparation is non-toxic to the human body, but due to the different physiques of people, some people are allergic to ethanol, which can cause rash and erythema after contact. Alcohol disinfection preparations are often used, and the skin will be degreased, dry and rough. The bactericidal effect of isopropanol is stronger than that of ethanol, but it is a mildly toxic substance. When it exceeds a certain concentration, it has a strong stimulating effect on the respiratory mucosa and conjunctiva, and can cause cell tissue necrosis. Isopropanol solution has a strong fat-soluble property, and repeated contact with the skin can dry and degrease the skin.

It can be seen that although the above commonly used disinfectants have good disinfection and antibacterial effects, they all have obvious disadvantages when used in disinfection wet wipes, that is, the smell is strong and irritating, and repeated contact with the skin is easy to cause discomfort or even allergies. Therefore, a safe disinfectant is invented. Efficient antibacterial wet wipes have become a hot spot in the market.

Contents of the invention

An object of the present invention is to provide a safe and efficient antibacterial wet wipe. The wet wipes are prepared with safe and efficient chitosan derivatives as antibacterial agents and sterilized non-woven microcarriers. The wet wipes can comprehensively and effectively kill bacteria on the skin surface, and are non-toxic and non-irritating to the skin. Non-drying, easy to use and easy to carry.

Another object of the present invention is to provide a safe and efficient preparation method of antibacterial wet wipes. The specific manufacturing method of antibacterial wipes is to dissolve chitosan derivatives in corresponding proportions into deionized water to make antibacterial liquid, then immerse the non-woven fabric carrier, absorb enough of the prepared antibacterial liquid, and then seal the package. .

The safe and efficient antibacterial wet wipes of the present invention can be used for hands, medical equipment, household daily necessities, etc. due to the use of chitosan derivatives with good biocompatibility, safety, non-toxicity, non-irritation, and broad-spectrum antibacterial properties as antibacterial agents. The antibacterial disinfection of the surface of the article can effectively kill common pathogenic bacteria, viruses and other harmful microorganisms, and it is green, safe, non-toxic, non-skin irritating, non-corrosive, and easy to carry and use.

To achieve the above object, the present invention adopts the following technical solutions:

A safe and efficient antibacterial wet wipe, the antibacterial wet wipe is composed of a sterilized non-woven fabric and a chitosan derivative-based antibacterial liquid loaded on the sterilized non-woven fabric, and the load of the antibacterial liquid is 50- 500wt%;

Described antibacterial liquid comprises the raw material of following parts by weight, in 100 parts by weight:

Chitosan derivative 0.05-5 parts,

Surfactant 0.5-5 parts,

Deionized water balance.

Further, the chitosan derivative is a substance shown in formula (1) and/or formula (2):

In formula (1), x, y, n are natural numbers, 0<x≦10 ⁷ , 0<y≦10 ⁷ , 10 ² ≦n≦10 ⁷ ;

In formula (2), x, y, and n are natural numbers, 0<x≤5000, 0<y≤5000, 10≤n≤5000.

The substances represented by formula (1) and formula (2) are chitosan derivatives obtained by modifying bifunctional groups on the basis of chitosan or carboxymethyl chitosan. These two substances were synthesized by the applicant for the first time, and they are used as active substances in disinfectants. Compared with existing chitosan disinfectants, they have the advantages of strong antibacterial power and high biological safety. And antibacterial aspect has had considerable improvement and improvement. The applicant found that using these two substances as active substances in antibacterial wet wipes has the characteristics of high safety, no stimulation, and rapid and efficient sterilization.

Preferably, the preparation method of the substance described in formula (1) synthesized by the applicant for the first time is as follows:

1) dissolving chitosan in water or dilute acid solution, heating and stirring in a water bath, fully dissolving water or dilute acid solution to form chitosan;

2) Adjust the pH of the solution to between 5 and 7 with an alkaline solution;

3) Slowly add the guanidinating reagent thiourea trioxide to the water or dilute acid solution of chitosan, and keep stirring at constant temperature for 10 minutes to 60 minutes after the addition is completed;

4) adding the arginine activation solution to the above reaction solution, and reacting at an appropriate temperature for 6 to 48 hours;

5) Adding hydroxylamine hydrochloride equivalent to arginine in the reaction solution to terminate the reaction;

6) The reaction solution is filtered and then dialyzed with deionized water, followed by freeze-drying to obtain the substance described in the product formula (1).

Preferably, the preparation method of the substance described in formula (2) synthesized by the applicant for the first time is as follows:

1) Add carboxymethyl chitosan to deionized water, stir evenly at room temperature to form carboxymethyl chitosan aqueous solution, set aside;

2) Weigh 2,3-epoxypropyltrimethylammonium chloride, dissolve in deionized water and mix for subsequent use;

3) Under heating and stirring conditions, add 2,3-epoxypropyltrimethylammonium chloride solution to carboxymethyl chitosan solution in batches, add within 2 to 8 hours, and then stir at constant temperature for no more than 12 hours;

4) After the reaction is finished, wait for the reaction product to return to room temperature, adjust the pH value of the solution with a buffer solution to 5.0-7.5, and the salt concentration is 0.01-0.5M to obtain a solution S1;

5) Weighing N-hydroxysuccinimide and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and dissolving them in a buffer solution to obtain a solution S2;

6) Weigh arginine or arginine oligomers into solution S2 for activation, and stir at 20-50°C for 1-5 hours to obtain solution S3;

7) adding the S3 solution to the solution S1 in batches, and reacting for 6 to 48 hours under the condition of heating and stirring to obtain the solution S4;

8) After the reaction is over, add hydroxylamine hydrochloride equivalent to the molar equivalent of arginine or arginine oligomers to the solution S4 to terminate the reaction;

9) Filter the reaction product to remove insoluble matter, perform dialysis in deionized water, the molecular weight cut-off of the dialysis bag is <10000Da, and then perform freeze-drying treatment to obtain the solid product described in formula (2).

Further, the chitosan derivative also includes one or more of the following substances:

In formula (3), x, y, n are natural numbers, 0<x≤5000, 0<y≤5000, 1≤n≤30;

In formula (4), X ^- is Cl ^- or HSO ₃ ^- , x and n are natural numbers, 0<x≦10 ⁷ , 10 ² ≦n≦10 ⁷ ;

In formula (5), x and n are natural numbers, 0<x≦10 ⁷ , 10≦n≦10 ⁷ ;

In formula (6), x and n are natural numbers, 0<x≦10 ⁷ , 10 ² ≦n≦10 ⁷ ;

In formula (7), x and n are natural numbers, 0<x≦10 ⁷ , 10 ² ≦n≦10 ⁷ ;

In formula (8), X ^- is F ^- , Cl ^- , Br ^- , HSO ₄ ^- or RCOO ^- , x and n are natural numbers, 0<x≦10 ⁷ , 10 ² ≦n≦10 ⁷ ;

In formula (9), x and n are natural numbers, 0<x≦10 ⁷ , 10 ² ≦n≦10 ⁷ ;

In formula (10), x and n are natural numbers, 0<x≦10 ⁷ , 10 ² ≦n≦10 ⁷ ;

In formula (11), x, y, n are natural numbers, 0<x≦10 ⁷ , 0<y≦10 ⁷ , 10 ² ≦n≦10 ⁷ ;

In formula (12), X ^- is F ^- , Cl ^- , Br ^- , HSO ₄ ^- or RCOO ^- , y and n are natural numbers, 0<y≦10 ⁷ , 10 ² ≦n≦10 ⁷ ;

In formula (13), X ^- is F ^- , Cl ^- , Br ^- , HSO ₄ ^- or RCOO ^- , y and n are natural numbers, 0<y≦10 ⁷ , 10 ² ≦n≦10 ⁷ .

Preferably, the substance described in formula (3) is also synthesized by the applicant for the first time, and the preparation method of the substance is as follows:

1) Weigh carboxymethyl chitosan and add deionized water, stir evenly at room temperature to form carboxymethyl chitosan aqueous solution, set aside;

2) Weighing N-hydroxysuccinimide and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, and dissolving them in a buffer solution to obtain solution S1;

3) Weigh arginine or arginine oligomers and add them to solution S1 for activation, and stir at room temperature for 0.5-4 hours to obtain solution S2;

4) adding solution S2 to carboxymethyl chitosan aqueous solution in batches, reacting under heating and stirring conditions for 6-48 hours to obtain solution S3;

5) After the reaction is over, add hydroxylamine hydrochloride in equimolar equivalents to arginine or arginine oligomers into solution S3 to terminate the reaction;

6) The reaction product is dialyzed in deionized water, the molecular weight cut-off of the dialysis bag is <5000Da, and then freeze-dried to obtain the solid product described in formula (3).

Further, the substance described in formula (11) is also synthesized by the applicant for the first time, and the preparation method of the substance is as follows:

1) carboxymethyl chitosan is dissolved in deionized water, heated and stirred in a water bath, fully dissolved to form an aqueous solution of carboxymethyl chitosan;

2) Slowly add the guanidinating reagent thiourea trioxide to the aqueous solution of carboxymethyl chitosan, and keep stirring at constant temperature for 10 minutes to 60 minutes after the addition is completed;

3) adding the arginine activation solution to the above reaction solution, and reacting at an appropriate temperature for 6 to 48 hours;

4) Adding hydroxylamine hydrochloride equivalent to arginine in the reaction solution to terminate the reaction;

5) The reaction solution is filtered and dialyzed with deionized water, followed by freeze-drying to obtain the substance described in the product formula (11).

Preferably, the surfactant is one or more of Tween series products, triethanolamine, sodium ethoxylated alkyl sulfate, sodium lauryl ether sulfate, stearic acid and its derivatives.

The Tween series products refer to commercially available Tween series products, such as Tween 20, Tween 60, Tween 80 and the like.

The invention also discloses the preparation method of the safe and high-efficiency antibacterial wet wipes as described above: first, 0.05-5 parts by weight of chitosan derivatives and 0.5-5 parts by weight of surfactant are added to the remaining parts by weight of deionized In water, fully stir to dissolve the chitosan derivative completely and turn it into a clear and transparent solution to obtain a chitosan derivative-based antibacterial liquid; then place the sterilized non-woven fabric in the above antibacterial liquid and soak it for 5-10 minutes at room temperature The safe and efficient antibacterial wet wipes can be obtained after taking out and draining the sealed package.

In the prior art, wet wipes are mainly divided into two categories: one type has been sterilized itself, but has no antibacterial protection effect on other items, and contains skin care ingredients, which can only be used for skin moisturizing and maintenance; the other type is not only used by itself Disinfection, and disinfectant wipes that can also disinfect other items can be used to disinfect or sterilize skin and daily necessities, but the antibacterial ingredients contained are mostly peroxides or alcohols, which have a strong odor Strong disadvantages, repeated skin contact can easily cause discomfort or even allergies.

Aiming at the deficiencies in the prior art, the applicant has verified through a large number of experiments that chitosan derivatives are used as antibacterial agents, surfactants are added appropriately, non-woven fabrics are used as carriers, and the load of antibacterial liquid is controlled to be 50-500wt%. A safe and highly effective antibacterial wet wipe was prepared. At the same time, through a large number of experimental verifications, the composition of the antibacterial liquid is limited to 0.05-5 parts of chitosan derivatives in 100 parts by weight, and 0.5-5 parts of surfactants. Get the most out of it.

The wet tissue of the present invention has high-efficiency antibacterial effect, can quickly kill bacteria on the surface of the human body or objects by wiping, is safe, non-toxic, harmless, and non-irritating to the human body, is environmentally friendly, and is easy to carry, and is suitable for hospitals, hotels, and restaurants , families and other occasions, as well as people who go out and accountants.

It should be noted that in the above molecular structural formulas (1)-(13), the arrangement order of each repeating unit is not completely in accordance with the order marked in the structural formula, but is carried out in the polymer chain in an irregular arrangement. arranged in combination.

It should also be noted that if there is no special description, any range described in the present invention includes the end value and any value between the end values and any sub-range formed by the end value or any value between the end values.

The beneficial effects of the present invention are as follows:

The safe and efficient antibacterial wet wipes involved in the present invention are specially designed and developed for the deficiencies of the prior art. The green and environmentally friendly chitosan derivatives, a bionatural polymer modified antibacterial material, are selected as antibacterial agents, which are safe and non-toxic. Toxic, non-irritating, strong antibacterial and long-lasting antibacterial; no need for water, saving water resources.

detailed description

In order to illustrate the present invention more clearly, the present invention will be further described below in conjunction with preferred embodiments. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not limit the protection scope of the present invention.

Example 1

Prepare and synthesize the material described in formula (1) of the present invention:

Take by weighing 0.1 gram of chitosan and join in 100 milliliters of deionized water, mechanically stir at room temperature for half an hour, so that chitosan dissolves completely, thereby obtain the homogeneous solution that mass volume percent concentration is 0.1%; Slowly add thiourea trioxide into the system, the molar ratio of thiourea trioxide and chitosan is 10:1, the feeding time is 30 minutes, and the reaction at room temperature is kept for 60 minutes; A mixed solution of amino acid, N-hydroxysuccinimide (NHS) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl) (solvent: 30mmol/ L of 2-(N-morpholino)ethanesulfonic acid (MES) buffer solution) 20ml was added to the above-mentioned reaction solution, and the stirring reaction was continued at room temperature for 48 hours, wherein chitosan, arginine, NHS, EDC The molar ratio of the solution is 50:1:5:5; then the reaction solution is put into a dialysis bag, the two ends of the dialysis bag are tied tightly and put into deionized water for dialysis treatment, and the water is changed every five hours, and the water is changed eight times. After the dialysate is put into a refrigerator at -86° C. for one hour, put into a lyophilizer until it is lyophilized to obtain a chitosan derivative modified by a bifunctional group of the substance described in formula (1).

To prepare antibacterial wipes:

Weigh 8 grams of the substance described in formula (1) prepared above and 1 gram of Tween 20 surfactant, add it to 100 milliliters of sterilized deionized water, stir fully to make it completely dissolve and become a clear and transparent solution, to obtain Antibacterial liquid a; then soak the sterilized non-woven cloth in the above antibacterial liquid a at room temperature for 5 minutes, take out, drain and seal the package to obtain the safe and efficient antibacterial wet wipe A.

Example 2

Prepare and synthesize the material described in formula (2) of the present invention:

Weigh 0.1g carboxymethyl chitosan (the number average molecular weight is 2×10 ⁵ Da, carboxymethyl substitution degree is 100%, deacetylation degree is 100%), add 100mL deionized water, stir mechanically at room temperature, make carboxymethyl chitosan Base chitosan is completely dissolved, thereby obtaining the solution that the mass volume percent concentration is 0.1%; Weigh 2,3-epoxypropyltrimethylammonium chloride, be dissolved in 50mL deionized water, mechanically stir at room temperature; Under the condition of stirring at 40°C, slowly add the 2,3-epoxypropyltrimethylammonium chloride solution into the carboxymethyl chitosan solution in 3 times, and the feeding time is 4 hours, and then stirred at constant temperature for 4 hours; , when the reaction product returned to room temperature, adjusted with 1M pH 5.0 MES/HCl buffer solution to make the solution pH 5.0, salt concentration 0.01M, to obtain solution S1; weigh NHS and EDC (molar ratio 1:10), dissolve In 30mL 0.01M pH 5.0 MES/HCl buffer solution to obtain solution S2; weigh arginine and add it to solution S2 for activation, stir at room temperature for 1h; pour arginine activation solution into solution S1 in 3 times, React under stirring conditions for 48 hours; after the reaction, add hydroxylamine hydrochloride in an equimolar ratio to arginine to the reaction solution to terminate the reaction; filter the reaction product to remove insoluble matter, and perform dialysis in 2L deionized water, the molecular weight cut-off of the dialysis bag is 1000Da , change the water every 2 hours, after changing the water 10 times, pour the dialysate into a 1L round bottom flask, freeze in liquid nitrogen, and rotate the flask continuously to make the dialysate form a thin layer at the bottom of the bottle, and then freeze-dry. Promptly obtain the material solid double-modified carboxymethyl chitosan derivative described in formula (2). In this reaction, the mass ratio of carboxymethyl chitosan to 2,3-epoxypropyltrimethylammonium chloride is 1:0.1, and the molar ratio of carboxymethyl chitosan, arginine to EDC is 1:1. : 0.5.

To prepare antibacterial wipes:

Take by weighing 10 grams of the substance described in formula (2) prepared above and 5 grams of triethanolamine surfactant, add to 100 milliliters of sterilized deionized water, fully stir to make it dissolve completely and become a clear and transparent solution, to obtain antibacterial Liquid b; then soak the sterilized non-woven cloth in the above antibacterial liquid b at room temperature for 10 minutes, take it out, drain and seal the package to obtain the safe and efficient antibacterial wet wipe B.

Example 3

Prepare and synthesize the material described in formula (3) of the present invention:

Weigh 0.35g of carboxymethyl chitosan (the number average molecular weight is 2×10 ⁵ Da, the degree of carboxymethyl substitution is 100%, the degree of deacetylation is 95%), add 35mL of deionized water, and stir mechanically at room temperature to make the carboxymethyl chitosan The base chitosan was completely dissolved, thereby obtaining a solution with a mass volume percentage concentration of 1%; Weighing NHS and EDC (the molar ratio was 1:1), dissolved in 15mL 0.01M pH5.0MES/HCl buffer solution, to obtain a catalyst solution; Weigh arginine and add it to the catalyst solution for activation, stir at room temperature for 1 hour; pour the arginine activation solution into the carboxymethyl chitosan solution in 3 times, and react for 24 hours under stirring at 45°C; after the reaction , the hydroxylamine hydrochloride with the equimolar ratio of arginine is added to the reaction solution to terminate the reaction; the reaction product is dialyzed in 1L deionized water, the molecular weight cut-off of the dialysis bag is 5000Da, and the water is changed every 2 hours; after changing the water 8 times, the The dialysate is poured into a 250mL round bottom flask, frozen in liquid nitrogen, and the flask is continuously rotated so that the dialysate forms a thin layer on the wall of the bottle, and then freeze-dried to obtain the solid (oligomeric) substance described in formula (3). Arginine modified carboxymethyl chitosan derivatives. In this reaction, the molar ratio of carboxymethyl chitosan, arginine and EDC is 1:0.05:0.25.

To prepare antibacterial wipes:

Take by weighing 5 grams of the substance described in formula (1) prepared above, 1 gram of the substance described in formula (3) and 2 grams of Tween 80 surfactant respectively, join in 100 milliliters of sterilized deionized water, fully stir to make it Completely dissolve into a clear and transparent solution to obtain the antibacterial liquid c; then soak the sterilized non-woven fabric in the above antibacterial liquid c at room temperature for 8 minutes, take it out, drain and seal the package to obtain the safe and efficient antibacterial wet wipe c.

Example 4

To prepare antibacterial wipes:

Take by weighing respectively 2 grams of substances described in formula (1), 3 grams of substances described in formula (10) and 3 grams of surfactant ethoxylated alkylsulfate sodium that are obtained according to the preparation method of Example 1, add to 100 milliliters In sterilized deionized water, stir fully to make it completely dissolve and become a clear and transparent solution to obtain the antibacterial liquid d; then put the sterilized non-woven fabric in the above antibacterial liquid d and soak it for 6 minutes at room temperature, take it out, drain and seal the package. The safe and efficient antibacterial wet wipe D can be obtained.

Example 5

To prepare antibacterial wipes:

Weigh respectively 0.5 g of the substance described in formula (2) obtained according to the preparation method of Example 2, 2 grams of the substance described in formula (4) and 2.5 grams of surfactant sodium lauryl ether sulfate, add to 100 milliliters Bacterial deionized water, fully stirred to make it completely dissolve into a clear and transparent solution, and then the antibacterial liquid e can be obtained; then the sterilized non-woven fabric is soaked in the above antibacterial liquid e for 7 minutes at room temperature, taken out, drained and sealed. Obtain the safe and efficient antibacterial wet tissue E.

Example 6

To prepare antibacterial wipes:

Take by weighing respectively the material described in formula (2) that obtains according to the preparation method of embodiment 2, each 1 gram of material described in formula (7) and surfactant stearic acid 3 grams, join in 100 milliliters of sterilized deionized water, Fully stir to make it completely dissolve into a clear and transparent solution to obtain the antibacterial liquid f; then soak the sterilized non-woven fabric in the above antibacterial liquid f at room temperature for 9 minutes, take it out, drain and seal the package to obtain the safe and efficient The antibacterial wipes F.

Example 7

To prepare antibacterial wipes:

Weigh respectively 2 grams of the substance described in formula (1) obtained according to the preparation method of Example 1 and the substance described in formula (2) prepared in Example 2 and 4 grams of surfactant triethanolamine, add to 100 milliliters Bacterial deionized water, fully stirred to make it completely dissolve into a clear and transparent solution, and then the antibacterial liquid g can be obtained; then sterilized non-woven fabrics are soaked in the above antibacterial liquid g for 5 minutes at room temperature, taken out, drained and sealed. The safe and efficient antibacterial wet wipe G is obtained.

Example 8

To prepare antibacterial wipes:

Weigh 0.5 grams of the substance described in formula (1) obtained according to the preparation method of Example 1, and 2 grams of surfactant triethanolamine are added to 100 milliliters of sterilized deionized water, fully stirred to make it completely dissolve and become a clear and transparent solution , to obtain the antibacterial liquid h; then soak the sterilized non-woven cloth in the above antibacterial liquid h at room temperature for 5 minutes, take out, drain and seal the package to obtain the safe and efficient antibacterial wet wipe H.

Example 9

To prepare antibacterial wipes:

Weigh respectively 0.1 gram of the substance described in the formula (1) obtained according to the preparation method of Example 1, 0.1 gram of the substance described in the formula (2) obtained by the preparation method of Example 2, and 0.1 gram of the substance described in the formula (12) , and 0.1 g of Tween 80 surfactant is added to 100 ml of sterilized deionized water, fully stirred to make it completely dissolve into a clear and transparent solution, and then antibacterial liquid i can be obtained; Soak in liquid i at room temperature for 5 minutes, take out, drain and seal the package to obtain the safe and efficient antibacterial wet wipe I.

Example 10

To prepare antibacterial wipes:

Weigh respectively 0.1 gram of the substance described in formula (2) obtained according to the preparation method of Example 2, 0.1 gram of the substance described in formula (13), and 0.5 g of the substance described in formula (6), and surfactant lauryl alcohol Add 1 g of sodium ether sulfate to 100 ml of sterilized deionized water, stir fully to make it completely dissolve and become a clear and transparent solution, and then get the antibacterial liquid j; then arrange the sterilized nonwoven in the above antibacterial liquid j at room temperature Soak for 5 minutes, take out, drain and seal the package to get the safe and efficient antibacterial wet wipe J.

Comparative example 1

To prepare antibacterial wipes:

Weigh 8 g of commercially available chitosan and 20 1 g of Tween surfactant, add it to 100 ml of sterilized deionized water, add an appropriate amount of acid and fully stir to make it completely dissolve and become a clear and transparent solution to obtain the antibacterial liquid k; then soak the sterilized non-woven cloth in the above antibacterial liquid k at room temperature for 5 minutes, take it out, drain and seal the package to obtain the safe and efficient antibacterial wet wipe K.

Comparative example 2

To prepare antibacterial wipes:

Weigh commercially available carboxymethyl chitosan 8g, and surfactant Tween 20 1g, add to 100 milliliters of sterilized deionized water, fully stir to make it dissolve completely and become a clear and transparent solution to obtain the antibacterial liquid 1; then soak the sterilized non-woven fabric in the above-mentioned antibacterial liquid 1 at room temperature for 5 minutes, take it out, drain and seal the package to obtain the safe and efficient antibacterial wet wipe L.

Comparative example 3

To prepare antibacterial wipes:

Take by weighing 0.01 gram of the substance described in formula (1) obtained according to the preparation method of Example 1, and 20 1 gram of surfactant Tween, join in 100 milliliters of sterilized deionized water, fully stir to make it dissolve completely and become clear transparent solution to obtain the antibacterial liquid m; then soak the sterilized non-woven cloth in the above antibacterial liquid m at room temperature for 5 minutes, take it out, drain and seal the package to obtain the safe and efficient antibacterial wet wipe M.

The antibacterial liquid loads of the antibacterial wet wipes prepared in Examples 1-10 and Comparative Examples 1-3 of the present invention are all between 50-500wt%. Antibacterial wet wipes A-M were tested for microbial bactericidal effect and toxicology test respectively, and the test results are as follows.

The bactericidal effect on microorganisms was observed as follows:

According to the national standard GB15979-2002, the antibacterial wet wipes prepared by the sample of the example and the comparative example were tested for their disinfection effect on the skin disinfection surface. After the antibacterial liquid was placed in a constant temperature oven at 54°C for 15 days, antibacterial wet wipes were prepared to observe the changes in the bactericidal effect.

The bactericidal effect test list of disinfectant A-M is as follows:

Table 1 embodiment and comparative example disinfectant bactericidal effect statistical table

The bactericidal effect test results show that: the antibacterial wet wipe has a good antibacterial effect on common pathogenic bacteria on the skin surface. In Comparative Example K, chitosan dissolved in an acidic solution has certain antibacterial properties, but the antibacterial effect is not good. And in the comparative example L, the carboxymethyl chitosan aqueous solution has no antibacterial performance at all under the same test concentration; In the comparative example M, because the concentration does not reach the concentration range limited by the present invention, the antibacterial performance of the wet tissue is very poor. In addition, after placing the antibacterial liquid in Examples A-J in a constant temperature oven at 54°C for 15 days, the same method was used to prepare the same antibacterial wet wipes, which were resistant to Escherichia coli, Staphylococcus aureus, and Candida albicans. And the antibacterial performance of Pseudomonas aeruginosa was tested in the same way, and it was found that its antibacterial activity had no obvious change, indicating that the antibacterial activity of the antibacterial wet wipe of the present invention was stable and long-lasting.

Toxicological tests are as follows:

Rabbit acute skin irritation test procedure

About 24 hours before the test, the hair on both sides of the back and spine of the experimental animals was cut off without damaging the epidermis. Take about 0.5mL of antibacterial liquid and apply it directly on the skin, then cover it with two layers of gauze (2.5cm×2.5cm) and a layer of cellophane or similar, and then fix it with non-irritating adhesive tape and bandage. The skin on the other side served as a control. The closed test was adopted, and the application time was 4 hours. After the test, remove the residual test substance with warm water or non-irritating solvent.

Observe the skin reaction at the application site 1, 24, 48, 72h and 7 days after the antibacterial liquid is removed, score the skin reaction according to Table 2, and conduct a comprehensive evaluation based on the average value of the points of the tested animals. and the highest integral mean value at each observation point in 7 days, determine the skin irritation intensity according to Table 3.

Table 2 Skin irritation score

Table 3 Grading of skin irritation intensity

integral mean Intensity Grading 0～﹤0.5 non-irritating 0.5～﹤2.0 mild irritant 2.0～﹤6.0 Moderate irritation 6.0～﹤8.0 strong irritant

Rabbit eye irritation test steps:

(1) Fix the rabbit, gently pull the lower eyelid of the rabbit's right eye, give 0.5ml of the test sample to drop (or put) into the conjunctival sac, and passively close the upper and lower eyelids for 30 seconds to prevent the test sample from The product was lost, and the untreated other eye was used as its own control or instilled with vehicle.

(2) Rinse with normal saline after dripping for 30 seconds. Check the eyes at 1h, 24h, 48h, 72h, 4d and 7d after instilling the test sample. If no irritation occurs at 72h, the test can be terminated. If the cornea is found to be involved or there are other eye irritations, and if it does not recover within 7 days, the observation time should be extended to determine the reversibility or irreversibility of the damage, generally not exceeding 21 days.

For the skin sensitization test procedure on guinea pigs, refer to the rabbit acute skin irritation test procedure.

Toxicological test results: The toxicological tests of antibacterial liquids A-J all showed that once the skin of rabbits was exposed to the antibacterial liquid in a skin irritation test, the stimulation integral value was 0, and the skin damage was exposed to the disinfectant. After continuous observation for 7 days, the wound was normal. Healing, no inflammation, no redness and swelling symptoms, it is non-irritating; after an eye irritation test in rabbits, the irritation reaction score of rabbit ocular mucosa (cornea, iris, conjunctiva) is 0, it is non-irritating; 24 hours after guinea pig skin sensitization test , 48h guinea pig skin test area, no obvious erythema and edema occurred, and the sensitization rate of the sample was 0, classified according to the sensitization intensity, and belonged to weak sensitizers (Class I). Therefore, it can be considered that the antibacterial liquid used in the antibacterial wet wipe of the present invention is safe and non-toxic.

The antibacterial liquid K-M is subjected to toxicological tests in the same way. The test results were no skin irritation, no eyelid irritation, and belonged to weak sensitizing chemicals.

This toxicological test result shows: although the antibacterial liquid described in the comparative example also belongs to the disinfectant of safety, non-toxic and non-skin irritation, its antibacterial effect is not good or even does not have antibacterial performance, and chitosan can only be dissolved in weak acid environment, so The practical value is not high.

Apparently, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those of ordinary skill in the art can also make It is impossible to exhaustively list all the implementation modes here, and any obvious changes or changes derived from the technical solutions of the present invention are still within the scope of protection of the present invention.

Claims (9)

1. A kind of 1. safe and efficient antibacterial wet tissue, it is characterised in that：The antibacterial wet tissue is by sterilizing non-woven fabrics and is carried on sterilizing Chitosan derivatives base antibacterial liquid composition on non-woven fabrics, the load capacity of the antibacterial liquid is 50-500wt%；

   The antibacterial liquid includes the raw material of following parts by weight, in terms of 100 parts by weight：

   Chitosan derivatives 0.05-5 parts,

   Surfactant 0.5-5 parts,

   Deionized water surplus.
2. A kind of 2. safe and efficient antibacterial wet tissue according to claim 1, it is characterised in that：The chitosan derivatives are Material shown in formula (1) and/or formula (2)：

   In formula (1), x, y, n are natural number, 0 ＜ x≤10⁷, 0 ＜ y≤10⁷, 10²≦n≦10⁷；

   In formula (2), x, y, n are natural number, 0 ＜ x≤5000,0 ＜ y≤5000,10≤n≤5000.
3. A kind of 3. antibacterial wet tissue of highly effective and safe according to claim 2, it is characterised in that：The system of formula (1) described material Preparation Method is as follows：

   1) chitosan is dissolved into water or dilute acid soln, through heating water bath and stirred, fully dissolving formed chitosan water or Dilute acid soln；

   2) between aqueous slkali regulation solution PH to 5~7；

   3) guanidinated reagent AminoiminomethanesulAcidc Acidc is slowly added into the water or dilute acid soln of chitosan, constant temperature is kept after addition Stirring 10 minutes~60 minutes；

   4) arginine activated solution is added into above-mentioned reaction solution, reacted 6~48 hours at a proper temperature；

   5) the hydroxylamine hydrochloride terminating reaction with arginine equimolar equivalent is added into reaction solution；

   6) dialysed after reacting liquid filtering with deionized water, then carry out freeze-drying process, that is, obtain product type (1) described thing Matter.
4. A kind of 4. antibacterial wet tissue of highly effective and safe according to claim 2, it is characterised in that：The system of formula (2) described material Preparation Method is as follows：

   1) carboxymethyl chitosan is added to deionized water, be stirred at room temperature uniformly, form carboxymethyl chitosan sugar aqueous solution, it is standby；

   2) 2,3- epoxypropyltrimethylchloride chlorides are weighed, be dissolved in deionized water mix it is standby；

   3) under condition of heating and stirring, 2,3- epoxypropyltrimethylchloride chlorides solution by portions is added into carboxymethyl chitosan solution In, added in 2~8 hours, then constant temperature stirring is no more than 12 hours；

   4) after reaction terminates, question response product returns to room temperature, makes solution ph be 5.0~7.5 with cushioning liquid regulation, salt is dense Spend for 0.01~0.5M, obtain solution S 1；

   5) n-hydroxysuccinimide and 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides are weighed, is dissolved in slow Solution is rushed, obtains solution S 2；

   6) weigh arginine or arginine oligomer thing is added to solution S 2 and activated, 20~50 DEG C of 1~5h of stirring, obtain solution S3；

   7) S3 solution by portions is added in solution S 1, is reacted 6~48 hours under condition of heating and stirring, obtain solution S 4；

   8) after reaction terminates, solution S 4 will be added with the hydroxylamine hydrochloride of arginine or arginine oligomer thing equimolar equivalent, with Terminating reaction；

   9) reaction product is filtered to remove insoluble matter, dialysed in deionized water, bag filter molecular cut off<10000Da, Freeze-drying process is then carried out, that is, obtains solid product formula (2) described material.
5. A kind of 5. safe and efficient antibacterial wet tissue according to claim 1, it is characterised in that：The chitosan derivatives are also Including the one or more in material as follows：

   In formula (3), x, y, n are natural number, 0 ＜ x≤5000,0 ＜ y≤5000,1≤n≤30；

   In formula (4), X^-For Cl^-Or HSO₃ ^-, x, n are natural number, 0 ＜ x≤10⁷, 10²≦n≦10⁷；

   In formula (5), x, n are natural number, 0 ＜ x≤10⁷, 10≤n≤10⁷；

   In formula (6), x, n are natural number, 0 ＜ x≤10⁷, 10²≦n≦10⁷；

   In formula (7), x, n are natural number, 0 ＜ x≤10⁷, 10²≦n≦10⁷；

   In formula (8), X^-For F^-、Cl^-、Br^-、HSO₄ ^-Or RCOO^-, x, n are natural number, 0 ＜ x≤10⁷, 10²≦n≦10⁷；

   In formula (9), x, n are natural number, 0 ＜ x≤10⁷, 10²≦n≦10⁷；

   In formula (10), x, n are natural number, 0 ＜ x≤10⁷, 10²≦n≦10⁷；

   In formula (11), x, y, n are natural number, 0 ＜ x≤10⁷, 0 ＜ y≤10⁷, 10²≦n≦10⁷；

   In formula (12), X^-For F^-、Cl^-、Br^-、HSO₄ ^-Or RCOO^-, y, n are natural number, 0 ＜ y≤10⁷, 10²≦n≦10⁷；

   In formula (13), X^-For F^-、Cl^-、Br^-、HSO₄ ^-Or RCOO^-, y, n are natural number, 0 ＜ y≤10⁷, 10²≦n≦10⁷。
6. A kind of 6. antibacterial wet tissue of highly effective and safe according to claim 5, it is characterised in that：The system of formula (3) described material Preparation Method is as follows：

   1) weigh carboxymethyl chitosan and add deionized water, be stirred at room temperature uniformly, form carboxymethyl chitosan sugar aqueous solution, it is standby；

   2) n-hydroxysuccinimide and 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides are weighed, is dissolved in slow Solution is rushed, obtains solution S 1；

   3) weigh arginine or arginine oligomer thing is added to solution S 1 and activated, 0.5~4h is stirred at room temperature, obtains solution S2；

   4) solution S 2 is added portionwise in carboxymethyl chitosan sugar aqueous solution, reacts 6~48 hours, obtain under condition of heating and stirring To solution S 3；

   5) after reaction terminates, solution S 3 will be added with the hydroxylamine hydrochloride of arginine or arginine oligomer thing equimolar equivalent, with end Only react；

   6) reaction product is dialysed in deionized water, bag filter molecular cut off<5000Da, then it is freeze-dried Processing, that is, obtain solid product formula (3) described material.
7. A kind of 7. antibacterial wet tissue of highly effective and safe according to claim 5, it is characterised in that：The system of formula (11) described material Preparation Method is as follows：

   1) carboxymethyl chitosan is dissolved into deionized water, through heating water bath and stirred, fully dissolving forms carboxymethyl chitosan The aqueous solution of sugar；

   2) guanidinated reagent AminoiminomethanesulAcidc Acidc is slowly added into the aqueous solution of carboxymethyl chitosan, constant temperature is kept after addition Stirring 10 minutes~60 minutes；

   3) arginine activated solution is added into above-mentioned reaction solution, reacted 6~48 hours at a proper temperature；

   4) the hydroxylamine hydrochloride terminating reaction with arginine equimolar equivalent is added into reaction solution；

   5) dialysed after reacting liquid filtering with deionized water, then carry out freeze-drying process, that is, obtain product type (11) described thing Matter.
8. A kind of 8. antibacterial wet tissue of highly effective and safe according to claim 1, it is characterised in that：The surfactant is to tell In warm series of products, triethanolamine, ethoxylated alkyl sulfate, laureth sodium sulfovinate, stearic acid and its derivative One or more.
9. 9. the preparation method of the antibacterial wet tissue of the highly effective and safe as described in claim 1-8 is any, it is characterised in that including as follows Preparation process：

   1) according to 100 parts by weight meters, the chitosan derivatives of 0.05-5 parts by weight is weighed and the surface of 0.5-5 parts by weight is lived Property agent, be added in the deionized water of residuals weight number, be sufficiently stirred be completely dissolved chitosan derivatives to become clarification saturating Bright solution, you can obtain chitosan derivatives base antibacterial liquid；

   2) sterilizing nonwoven is arranged in above-mentioned antibacterial liquid and soaks 5-10 minutes at room temperature.