CN115569083B - High-water-content antibacterial wet tissue and preparation method thereof - Google Patents

Abstract

The invention relates to an antibacterial wet tissue with high water content, which comprises the following raw materials: the carrier is a non-woven fabric comprising an upper layer, a middle layer and a lower layer, the fiber raw materials of the upper layer and the lower layer are the same, and the carrier is sodium hyaluronate grafted PET fiber. According to the invention, the antibacterial agent with quick-acting antibacterial property and slow-acting antibacterial property is adopted to be matched as the antibacterial component of the wet tissue liquid, and the wet tissue liquid is immersed or sprayed on a double-layer structure carrier prepared from the sodium hyaluronate grafted PET fiber on the upper layer, so that the prepared wet tissue has good water retention performance. The PET fiber grafted by sodium hyaluronate has the function of improving the antibacterial property and the antibacterial stability of the wet tissue by synergistic colloidal silver, so that the wet tissue can still keep good stability when the total amount of all components except water in the wet tissue liquid is not more than 0.1 weight percent.

Description

High-water-content antibacterial wet tissue and preparation method thereof

Technical Field

The invention belongs to the technical field of wet tissues, and particularly relates to an antibacterial wet tissue with high water content and a preparation method thereof.

Background

The wet tissue is a product which takes non-woven fabric, fabric or dust-free paper as a carrier, takes water, humectant, bactericide, preservative and the like as auxiliary materials and has cleaning and sterilizing effects on the surface of a human body or an object, has high requirements on the antibacterial performance, and as disclosed in patent CN202110387027.0, the wet tissue is mainly prepared from composite non-woven fabric, and the surface of the non-woven fabric is impregnated with disinfectant; the disinfectant comprises the following raw materials in parts by weight: 55-65 parts of purified water, 3-5 parts of ethanol, 4-7 parts of active agent, 3-4 parts of humectant, 2-4 parts of aromatic, 1-3 parts of aloe extract and 0.4-0.6 part of citric acid; the active agent comprises, by weight, 1-2 parts of benzalkonium chloride, 2-3 parts of phosphomolybdic tungsten heteropoly acid and 1-2 parts of polyhexamethylene guanidine; the humectant comprises, by weight, 1-1.5 parts of glycerol and 2-2.5 parts of butanediol; the aromatic comprises, by weight, 1-2 parts of peppermint oil and 1-2 parts of essence. The wet tissue has good sterilization effect by using the wet tissue liquid containing a large amount of antibacterial components, but the quaternary ammonium salt antibacterial agent has high content and high irritation. Patent CN202210353059.3 discloses a biological bactericidal and antiviral composition, sanitary wet towel and application thereof, epsilon-polylysine is 0.01-0.1%, natamycin is 0-0.05%, citrate is required for regulating pH, and the rest is reverse osmosis pure water. The wet tissue liquid adopts epsilon-polylysine and natamycin as antibacterial components, has excellent antibacterial property, is not stimulated to human bodies, is environment-friendly and pollution-free, but has the best antibacterial effect when the molecular weight of epsilon-polylysine is 3600 mu-4300 mu in water, and loses antibacterial activity when the molecular weight is lower than 1300 mu, so that the wet tissue has poor antibacterial stability and cannot be placed for a long time, otherwise, the antibacterial property is attenuated, and the antibacterial effect is reduced.

Therefore, the development of the wet tissue with the antibacterial property has the advantages of small dosage of the antibacterial agent, small irritation to human bodies and great significance for further popularization of the application of the wet tissue in the fields of medical treatment and the like.

Disclosure of Invention

In order to solve the technical problems, the invention provides the high-water-content antibacterial wet tissue and the preparation method thereof, wherein an antibacterial agent with quick-effect antibacterial property and slow-effect antibacterial property is adopted to be matched with an antibacterial component of the wet tissue liquid, and the antibacterial component is sprayed or immersed on a three-layer carrier with upper and lower fiber raw materials of sodium hyaluronate grafted PET fibers, so that the wet tissue with good sterilizing effect and water retention performance is prepared.

In order to achieve the above purpose, the following technical scheme is adopted:

the high-water-content antibacterial wet tissue comprises a carrier and wet tissue liquid, wherein the wet tissue liquid comprises the following raw materials: the carrier is a non-woven fabric comprising an upper layer, a middle layer and a lower layer, the fiber raw materials of the upper layer and the lower layer are the same, and the carrier is sodium hyaluronate grafted PET fiber.

Further, the poorly soluble silver salts such as silver citrate, disodium malate and colloidal silver, preferably colloidal silver, and the wet wipe comprises the following raw materials in parts by weight: 0.01 to 0.08 part of quaternary ammonium salt compound, 0.01 to 0.08 part of colloidal silver and 0.01 to 0.08 part of natamycin clathrate compound, and water is used for supplementing 100 parts, wherein the grafting rate of the sodium hyaluronate grafted PET fiber is 3 to 7.5 weight percent.

Further, the inventors of the present invention have unexpectedly found that a reasonable selection of the combination of antibacterial and bacteriostatic agents can still achieve a sterilization rate of 90% or more with a total amount of antibacterial and bacteriostatic agents of not more than 0.1wt% relative to 100 parts by weight of wet wipe. The wet tissue liquid comprises the following raw materials in parts by weight: 0.03-0.06 part of quaternary ammonium salt compound, 0.01-0.05 part of colloidal silver and 0.01-0.05 part of natamycin clathrate compound, wherein the quaternary ammonium salt compound contains one or more of benzalkonium chloride, cetylpyridinium chloride and dodecylpyridine chloride, more preferably contains benzalkonium chloride, cetylpyridinium chloride and dodecylpyridine chloride; the total weight of the quaternary ammonium salt compound, the colloidal silver and the natamycin inclusion compound is 0.05-0.1 part, and the water is added to 100 parts.

The colloidal silver has very low solubility in water, and the ionization and the decomposition reaction of the visible light into silver are very slow, so that the sterilization effect of the wet tissue is safer, more slowly-released and more durable.

The colloidal silver is a commercially available product.

The weight average molecular weight of the sodium hyaluronate is 10000 or less.

The sodium hyaluronate grafted PET fiber is prepared by a method comprising the following steps:

s1, soaking PET fibers in alkali liquor, heating to a reflux state, stirring at a constant temperature for reaction, adding acid liquor after the reaction is finished for neutralization, filtering, washing and drying for later use;

s2, soaking the fibers obtained in the step S1 in an aqueous solution of a catalyst, filtering and drying; soaking the dried fiber in sodium hyaluronate water solution, filtering and drying; washing and drying to obtain the grafted modified PET fiber.

The titer of the PET fiber in the step S1 is 1-2dtex, and the length is 30-40mm; the alkali liquor is not particularly limited, and is commonly used in the field, including but not limited to sodium hydroxide solution and potassium hydroxide solution, wherein the concentration of the alkali liquor is 10-15wt%, and the reaction time is 0.5-1h; the acid solution is not particularly limited, and is commonly used in the art, and includes, but is not limited to, one or a combination of two or more of hydrochloric acid solution, acetic acid solution and sulfuric acid solution; the washing is to wash with deionized water for 1-5 times;

the catalyst in the step S2 is Lewis acid selected from FeCl ₃ ·6H ₂ O、AlCl ₃ ·6H ₂ O、SnCl ₄ ·5H ₂ O、ZnCl ₂ One or a combination of two or more of the above, wherein the concentration of the catalyst in the aqueous solution of the catalyst is 3-7wt%, the time for soaking the catalyst solution is 5-15min, the drying temperature is 50-80 ℃ and the time is 1-3h; the concentration of the sodium hyaluronate solution is 6-15wt%, the time for soaking in the sodium hyaluronate solution is 10-15min, the drying temperature after soaking is 100-150 ℃ and the time is 20-60min; the washing is to wash and remove the catalyst and unreacted polyhydroxy macromolecule remained on the surface of the fiber by deionized water, the washing times are 1-5 times, and finally the drying temperature is 50-80 ℃ for 6-12 hours.

Step S1 is hydrolysis reaction of PET fiber in alkaline aqueous solution to generate-COOH on the surface of the fiber, and step S2 is esterification reaction of-COOH on the surface of the fiber and-OH on sodium hyaluronate to generate sodium hyaluronate grafted PET fiber.

The inclusion agent adopted by the natamycin inclusion compound is beta-cyclodextrin compound, and is selected from one or a combination of two or more of hydroxypropyl-beta-cyclodextrin, methyl-beta-cyclodextrin and maltosyl-beta-cyclodextrin.

Preferably, the inclusion agent of the natamycin inclusion compound is hydroxypropyl-beta-cyclodextrin.

Natamycin is an antifungal substance of multiolefin macrolides and has a high inhibitory capacity against various fungi and yeasts. The natamycin is difficult to be absorbed by the alimentary canal of human and livestock, has no harmful effects of cancerogenesis, teratogenesis, sensitization and the like on human and livestock, but has low bioavailability because the natamycin has very low water solubility and is unstable, and the cyclodextrin has special cavity inside to clathrate the natamycin, so that the water solubility of the natamycin is obviously improved. The technology of clathrating natamycin with cyclodextrin to achieve the purpose of solubilization is mature, and the preparation method of the natamycin clathrate is not particularly limited, and can be prepared by referring to the preparation method of the natamycin-hydroxypropyl-beta-cyclodextrin clathrate disclosed in patent CN 201210252599.9.

The quaternary ammonium salt compound comprises one or a combination of two or more of dodecyl pyridine chloride, benzalkonium chloride and cetylpyridinium chloride. More preferably, it comprises benzalkonium chloride, cetylpyridinium chloride and dodecylpyridinium chloride.

The fiber raw material of the middle layer is selected from one or a combination of two or more of PET fiber, viscose fiber, PA6 fiber and acrylic fiber.

The square gram weight of the upper layer and the lower layer of the carrier is 10-30, the square gram weight of the middle layer is 15-30, and the square gram weight of the carrier is 40-90.

The invention also provides a preparation method of the high-water-content antibacterial wet tissue, which comprises the following steps:

respectively opening, carding into a net, compounding, prewetting, compacting, water-jet strengthening, drying, curling, sterilizing and cutting the three layers of fiber raw materials to prepare a carrier; and (3) attaching the wet tissue liquid to a carrier through a dipping or spraying process, and packaging to obtain the wet tissue with the water content of more than 99.9% in the solution.

The package is formed by folding and packaging 1-100 wet tissues into a packaging bag or a packaging box.

Compared with the prior art, the invention has the beneficial effects that:

according to the invention, the antibacterial agent with quick-acting antibacterial property and slow-acting antibacterial property is adopted to be matched as the antibacterial component of the wet tissue liquid, and the wet tissue liquid is sprayed or immersed on a three-layer structure carrier prepared by grafting the sodium hyaluronate with PET fibers on the upper layer and the lower layer, so that the prepared wet tissue has good sterilizing effect and water retention property.

The inventor also finds that the PET fiber grafted by the sodium hyaluronate has the function of improving the antibacterial property and the antibacterial stability of the wet tissue by the synergistic colloidal silver, so that the wet tissue can still keep good antibacterial property and antibacterial stability and cannot go moldy and deteriorate when the total amount of antibacterial components in the wet tissue is not more than 0.1wt%, the dosage of the antibacterial components is reduced, the irritation of chemical raw materials to skin is reduced, the cost is also reduced, the safety of the wet tissue is increased, and the pollution to the environment is reduced.

Detailed Description

The invention is further illustrated below in connection with specific examples, but is not limited to the disclosure. Unless otherwise specified, "parts" are parts by weight in the examples of the present invention. All reagents used are those commercially available in the art.

Colloidal silver was purchased from Shanghai dry chemical Co., ltd. And had an average particle size of 50nm.

Sodium hyaluronate was purchased from Shanghai Sanskrit biotechnology Co., ltd. And had a weight average molecular weight of 8000Da.

PET fibers were purchased from Middling petrochemical Co., ltd, with a titre of 1.56dtex and a length of 38mm.

Viscose was purchased from Sanyou group Chengda chemical fiber Co., ltd, with a titre of 1.67dtex and a length of 38mm.

Hydroxypropyl-beta-cyclodextrin was purchased from Shandong Zhi Yuan Biotechnology Co., ltd and had a number average molecular weight of 1548.

Preparation of natamycin clathrate

Preparation example a1

Step one: dissolving 0.1mol of natamycin in 120g of potassium hydroxide solution with the concentration of 0.15 mol/L;

step two: adding 0.55mol of hydroxypropyl-beta-cyclodextrin into the mixed solution obtained in the step one, and carrying out ultrasonic inclusion reaction with natamycin for 40min at 35 ℃ with the ultrasonic frequency of 75KHz and the ultrasonic power of 30W/cm ² ；

Step three: dropwise adding 1mol/L hydrochloric acid solution into the reaction system of the step two to neutralize to neutrality, filtering with a 0.45 mu m micro-membrane, pre-cooling the filtrate in a refrigerator at-20 ℃ for overnight, freeze-drying the filtrate in a freeze dryer at-44 ℃ for 24 hours under the condition of 1.3Pa the next day, taking out to obtain natamycin-hydroxypropyl-beta-cyclodextrin inclusion compound powder, and storing the natamycin-hydroxypropyl-beta-cyclodextrin inclusion compound powder at the condition of shading to-20 ℃.

Preparation of sodium hyaluronate grafted PET fiber

Preparation example b1

S1, soaking PET fibers in 15wt% sodium hydroxide solution, heating to a reflux state, stirring at constant temperature for reaction for 30min, dripping 15wt% dilute hydrochloric acid to neutralize to neutrality after the reaction, filtering, washing with deionized water for 3 times, and drying at 60 ℃ for 6h to constant weight for later use;

s2, soaking the fiber obtained in the step 1) in a catalyst AlCl ₃ ·6H ₂ Filtering in water solution with O concentration of 7wt% for 10min, and oven drying at 60deg.C for 3 hr; soaking the dried fiber in 15wt% sodium hyaluronate solution for 15min, filtering, and oven drying at 150deg.C for 60min; washing with deionized water for 3 times, and drying at 60 ℃ for 12 hours to obtain the sodium hyaluronate grafted PET fiber.

Preparation example b2

The remainder was the same as in preparation example b1 except that the concentration of the sodium hyaluronate aqueous solution at step S2 was 10wt%.

Preparation of high water content antibacterial wet tissue

Example 1

Adding 0.03 part of benzalkonium chloride, 0.01 part of cetylpyridinium chloride, 0.02 part of colloidal silver and 0.04 part of natamycin clathrate prepared in preparation example a1 into 99.9 parts of purified water, adding into water one by one, stirring and dispersing for 30min to obtain wet tissue liquid;

opening the sodium hyaluronate grafted PET fiber prepared in the preparation example b1, and cross-laying to form a carding net, wherein the square gram weight of the fiber net is 15;

opening viscose fibers, and cross-laying to form a carding net, wherein the square gram weight of the fiber net is 20;

compounding a sodium hyaluronate grafted PET fiber web, a viscose fiber web and a sodium hyaluronate grafted PET fiber web from top to bottom, prewetting and compacting the compound web by a prewetting device, reinforcing the compound web by four times of front and back hydroentanglement in a hydroentangling machine, wherein the hydroentangling pressure is 75bar, 110bar and 75bar respectively, so that the upper, middle and lower fiber webs are mutually entangled and compounded into a whole, drying the compound web to constant weight at 120 ℃, naturally cooling the compound web to room temperature, curling, ultraviolet sterilizing and slitting the compound web into 130mm multiplied by 170mm to obtain a hydroentangled non-woven carrier;

spraying wet towel solution into the prepared carrier, folding and sealing 80 pieces of the immersed carrier, and packaging in PE packaging bags.

Example 2

The remainder was the same as in example 1, except that dodecylpyridinium chloride was used instead of cetylpyridinium chloride.

Example 3

The remainder was the same as in example 1, except that the silver malate was silver.

Example 4

The rest was the same as in example 1, except that the fiber raw material of the sodium hyaluronate grafted PET fiber web was prepared in preparation example b 2.

Example 5

The rest is the same as in example 1, except that the colloidal silver in the wet wipe is used in an amount of 0.01 part and purified water is added in an amount of 100 parts.

Example 6

The remainder was the same as in example 1 except that the amount of colloidal silver in the wet wipe was 0.01 part and that cetylpyridinium chloride was 0.02 part.

Example 7

The rest is the same as in example 1, except that in the wet wipe solution, 0.01 part of benzalkonium chloride and 0.03 part of cetylpyridinium chloride are used.

Example 8

The other matters were the same as in example 1 except that the wet wipe was prepared by adding 0.02 part of benzalkonium chloride, 0.02 part of cetylpyridinium chloride, 0.02 part of dodecylpyridinium chloride, 0.02 part of colloidal silver, 0.02 part of the natamycin clathrate prepared in preparation example a1 to 99.9 parts of purified water and stirring and dispersing.

Example 9

The other components were the same as in example 1 except that 0.01 part of natamycin clathrate and 99.93 parts of purified water were contained in the wet wipe.

Comparative example 1

The remainder was the same as in example 1, except that the fibrous raw material of the upper and lower layers of the support was PET.

Comparative example 2

The other matters were the same as in example 1 except that 0.02 part of benzalkonium chloride, 0.03 part of cetylpyridinium chloride, 0.02 part of dodecylpyridinium chloride, 0.03 part of the natamycin clathrate prepared in preparation example a1 was added to 99.9 parts of purified water and mixed by ultrasonic waves.

Comparative example 3

The remainder was the same as in example 1 except that 0.06 parts of colloidal silver, 0 parts of the natamycin clathrate prepared in preparation example a 1.

The sodium hyaluronate grafted PET fiber prepared in preparation examples b1 and b2 was referred to the following formula for calculation of the grafting ratio:

grafting ratio: g= (m ₁ -m ₀ )/m ₀ ×100％

Wherein m is ₁ The mass of the PET fiber grafted by sodium hyaluronate is m ₀ Is the quality of PET fiber.

TABLE 1

Project	Grafting percentage wt%
		Preparation example b1	6.0
Preparation example b2	4.1

The high moisture content antimicrobial towelettes prepared in examples 1-9 and comparative examples 1-3 were subjected to the following performance tests, the results of which are shown in Table 2:

average overflow volume: the multiple wet tissues prepared in examples 1 to 9 or comparative examples 1 to 3 were allowed to stand for one week, then the uppermost 20 and lowermost 20 sheets of the stack were taken out and weighed, the amount of overflow per package of wet tissues was calculated as follows, 3 packages of wet tissues were randomly taken per example or comparative example batch, the average value of the calculated amount of overflow was weighed as the average amount of overflow for the batch,

B _i ＝(W _i -W _i0 )/W _i0 ×100％

wherein B is _i I=1, 2, 3 for the overflow of the i-th wet wipe; wi is the weight of the 20 pieces of wet tissues at the lowest part of the i-th wet tissue, g; w (W) _i0 The weight g of the uppermost 20 wet tissues of the ith wet tissue.

Bactericidal properties: the sterilization performance test of annex C is carried out according to the disposable hygienic product hygienic standard of the standard GB/T15979-2002, the sterilization rate is more than 90% after 20 minutes, and the product has the sterilization effect.

Antibacterial stability: the prepared original packaged wet tissues are placed in a 37 ℃ incubator for 3 months, the relative humidity is kept at 75%, and the C3.2 sterilization performance test is carried out.

TABLE 2

As can be seen from Table 2, the wet tissue prepared by the invention has good disinfection effect and water retention performance, and meanwhile, the inventor also discovers that the PET fiber grafted by the sodium hyaluronate has the effect of improving the antibacterial property and the antibacterial stability of the wet tissue by synergizing the indissoluble silver salt, so that the wet tissue can still keep good antibacterial property when the total amount of antibacterial components in the wet tissue is not more than 0.1wt%, the wet tissue can be normally placed for 2 years without mildew and deterioration, the consumption of the antibacterial components can be reduced, the irritation of chemical raw materials to skin can be reduced, the cost can be reduced, the safety of the wet tissue can be increased, and the pollution to the environment can be reduced.

The foregoing detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but is to be accorded the full scope of all such equivalents and modifications so as not to depart from the scope of the invention.

Claims (10)

1. The high-water-content antibacterial wet tissue comprises a carrier and wet tissue liquid, and is characterized in that the wet tissue liquid comprises the following raw materials in parts by weight: 0.01-0.08 part of quaternary ammonium salt compound, 0.01-0.08 part of colloidal silver serving as insoluble silver salt and 0.01-0.08 part of natamycin clathrate compound, wherein water is supplemented to 100 parts, the carrier is non-woven fabric comprising an upper layer, a middle layer and a lower layer, the fiber raw materials of the upper layer and the lower layer are the same, and sodium hyaluronate grafted PET fiber is adopted; the quaternary ammonium salt compound is one or more of benzalkonium chloride, cetylpyridinium chloride and dodecylpyridine chloride;

the sodium hyaluronate grafted PET fiber is prepared by a method comprising the following steps:

s1, soaking PET fibers in alkali liquor, heating to a reflux state, stirring at a constant temperature for reaction, adding acid liquor after the reaction is finished for neutralization, filtering, washing and drying for later use;

s2, soaking the fibers obtained in the step S1 in an aqueous solution of a catalyst, filtering and drying; soaking the dried fiber in sodium hyaluronate water solution, filtering and drying; washing and drying to obtain the grafted modified PET fiber.

2. The high moisture content antimicrobial wet wipe of claim 1 wherein said sodium hyaluronate grafted PET fiber has a grafting ratio of 3 to 7.5 weight percent.

3. The high water content antimicrobial wet wipe of claim 2 wherein 0.03-0.06 parts quaternary ammonium compound, 0.01-0.05 parts colloidal silver, 0.01-0.05 parts natamycin clathrate; the total weight of the quaternary ammonium salt compound, the colloidal silver and the natamycin inclusion compound is 0.05-0.1 part, and the water is added to 100 parts.

4. The high moisture antimicrobial wipe of claim 1 wherein said colloidal silver has an average particle size of from 15 nm to 150nm.

5. The high moisture content antimicrobial wipe of claim 1 wherein said sodium hyaluronate has a weight average molecular weight of 10000 or less.

6. The high moisture content antimicrobial towelette of claim 1 wherein the PET fiber of step S1 has a denier of 1-2dtex and a length of 30-40mm; the concentration of the alkali liquor is 10-15wt%, and the reaction time is 0.5-1h; the catalyst in the step S2 is Lewis acid selected from FeCl ₃ •6H ₂ O、AlCl ₃ •6H ₂ O、SnCl ₄ •5H ₂ O、ZnCl ₂ One or a combination of two or more of the above, wherein the concentration of the catalyst in the aqueous solution of the catalyst is 3-7wt% and the time for soaking the catalyst solution is 5-15min; the concentration of the sodium hyaluronate solution is 6-15wt%, and the time for soaking in the sodium hyaluronate solution is 10-15min.

7. The high moisture content antimicrobial wet wipe of claim 1 wherein said natamycin clathrate employs a clathrate compound of the beta-cyclodextrin type.

8. The high moisture content antimicrobial towelette of claim 7 wherein the beta-cyclodextrin compound is selected from the group consisting of hydroxypropyl-beta-cyclodextrin, methyl-beta-cyclodextrin, maltosyl-beta-cyclodextrin, and combinations of two or more thereof.

9. The high moisture antimicrobial wipe of claim 8 wherein said beta-cyclodextrin compound is hydroxypropyl-beta-cyclodextrin.

10. A method for preparing the high moisture content antimicrobial wet wipe of any of claims 1-9 comprising the steps of:

respectively opening, carding into a net, compounding, prewetting, compacting, water-jet strengthening, drying, curling, sterilizing and cutting the three layers of fiber raw materials to prepare a carrier; and (3) attaching the wet tissue liquid to a carrier through a dipping or spraying process, and packaging to obtain the wet tissue with the water content of more than 99.9% in the solution.