阅读说明：本技术 一种复合低温消毒剂及其制备方法 (Composite low-temperature disinfectant and preparation method thereof ) 是由 金星 孙文明 张伟 于 2020-12-09 设计创作，主要内容包括：本发明涉及一种复合低温消毒剂及其制备方法。本发明属于消毒材料技术领域,特别涉及一种工艺简单、应用范围广、低温高效、广谱杀菌、持久抑菌的复合低温消毒剂及其制备方法,通过有机低温材料和无机低温材料复合为低温成分、无机和聚合物复合为消毒成分、缓蚀剂和稳定剂的复配的技术方案,配制出可在-20℃显著杀灭细菌的消毒剂,预计可有效解决常温消毒剂无法在冬天低温环境、冷库及冷链各环节使用的难题。(The invention relates to a composite low-temperature disinfectant and a preparation method thereof. The invention belongs to the technical field of disinfection materials, and particularly relates to a composite low-temperature disinfectant with simple process, wide application range, low temperature, high efficiency, broad-spectrum sterilization and lasting bacteriostasis and a preparation method thereof, wherein the disinfectant capable of obviously killing bacteria at the temperature of minus 20 ℃ is prepared by the technical scheme of compounding an organic low-temperature material and an inorganic low-temperature material into a low-temperature component, compounding an inorganic low-temperature material and a polymer into a disinfection component, and compounding a corrosion inhibitor and a stabilizer, and the problem that the normal-temperature disinfectant cannot be used in low-temperature environments in winter, cold storages and cold chains can be effectively solved.)

1. A composite low-temperature disinfectant and a preparation method thereof are characterized by comprising the following steps: dispersing a low-temperature material in a solvent to obtain a solution A; adding the corrosion inhibitor into the solvent, and quickly stirring to obtain a solution B; mixing and stirring the solution A and the solution B to obtain a solution C; mixing the solution C with a proper amount of disinfection components to obtain a solution D; and adding a stabilizer into the solution D to obtain the low-temperature disinfection material with stable performance.

2. The composite low-temperature disinfectant as claimed in claim 1, wherein the solvent is one or more of water, ethanol, ether, acetone, DMF, glacial acetic acid, chloroform, carbon tetrachloride, toluene, ethylene glycol, propylene glycol, and other common experimental solvents.

3. The composite low-temperature disinfectant as claimed in claim 2, wherein the solvent water is one or more of tap water, spring water, well water, drinking purified water and deionized water, and is free from substances preventing success of experiments.

4. The composite low-temperature disinfectant as claimed in claim 1, wherein the low-temperature material is one or more of calcium chloride, sodium nitrite, a mixture of calcium chloride and sodium chloride, a mixture of calcium chloride and sodium nitrite, ethanol, ethylene glycol, isopropanol, glycerol, glycol ether, 1, 2-propylene glycol, 1, 3-propylene glycol and the like.

5. The composite low-temperature disinfectant and the preparation method thereof as claimed in claim 1, wherein the low-temperature material can be prepared and produced by itself or purchased as a finished product.

6. The composite low-temperature disinfectant and the preparation method thereof as claimed in claim 1, wherein the disinfectant material is prepared and produced by itself or purchased as a finished product.

7. The composite low-temperature disinfectant as claimed in claim 1, wherein the solution A is prepared by stirring for 2-5 hours, heating in water bath at 40-70 ℃, stirring, and aging at room temperature for 24-48 hours.

8. The composite low-temperature disinfectant as claimed in claim 1, wherein the solution B is prepared by stirring for 2-5 hours, heating in water bath at 40-70 ℃, stirring, and aging at room temperature for 24-48 hours.

9. The composite low-temperature disinfectant as claimed in claim 1, wherein the corrosion inhibitor used in the preparation of the solution B is one or more of long-chain fatty acid sodium salt, long-chain fatty acid ammonium salt, Cetyl Trimethyl Ammonium Bromide (CTAB), Span-80 (Span-80), Tween-80 (Tween-80), sodium nitrite, sodium polyacrylate, polyacrylic acid, formic acid, petroleum acid, (Z) -9-octadecenoic acid, fatty acid amide, dodecyl-polyoxyethylene ether, nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, benzalkonium chloride, benzalkonium bromide, and polyhexamethylene biguanide.

10. The preparation method is characterized in that the content of the corrosion inhibitor is within the range of 0.01-35%.

11. The composite low-temperature disinfectant as claimed in claim 1, wherein the solution C is prepared by stirring for 24-48 hours, aging at room temperature for 24-48 hours, and maintaining the temperature of water bath or oil bath at 40-70 ℃.

12. The composite low-temperature disinfectant as claimed in claim 1, wherein the disinfectant material used in preparing the solution C is chloroisocyanuric acid such as sodium dichloroisocyanurate, trichloroisocyanuric acid; single chain quaternary ammonium salts such as dodecyldimethylbenzyl ammonium chloride (benzalkonium chloride), dodecyldimethylbenzyloxyethyl ammonium bromide, tetradecyldimethylpyridinium bromide benzalkonium bromide, hexadecyltrimethylammonium chloride; double-chain quaternary ammonium salts such as didecyldimethylammonium chloride, didodecyldimethylammonium bromide, and (didodecyldimethyl) ethylenediammonium bromide; polyquaternium such as one or more of polyquaternium, polyhexamethylene biguanide, and polyhexamethylene monoguanidine.

13. The composite low-temperature disinfectant as claimed in claim 1, wherein the stabilizer used in the preparation of the solution D is one or more selected from the group consisting of long-chain fatty acid sodium salt, long-chain fatty acid ammonium salt, Cetyl Trimethyl Ammonium Bromide (CTAB), borax, triethanolamine, Span-80 (Span-80), Tween-80 (Tween-80), sodium nitrite, sodium polyacrylate, polyacrylic acid, formic acid, petroleum acid, (Z) -9-octadecenoic acid, fatty acid amide, dodecyl-polyoxyethylene ether, nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, and sodium dodecyl benzene sulfonate.

Technical Field

The invention belongs to the field of preparation of disinfection materials, and particularly relates to a composite low-temperature disinfectant and a preparation method thereof.

Background

The food industry is a civil industry which is concerned with the personal demands of the public and is stable in the economic society, and the importance and the urgency of the food safety problem reach unprecedented height under the background of epidemic situation prevention and control normalization.

An important part of the food safety problem is cold chain food safety. Cold chain sterilization is an important guarantee of cold chain food safety. With regard to cold chain sterilization, in addition to sterilization and sealing down to normal temperature or direct incineration, destruction, landfill, it is necessary to sterilize the surface of all cold chain food products at low temperature (even below-40 ℃). Development of a disinfectant capable of efficiently exerting a disinfecting effect in a low-temperature or ultralow-temperature environment has been a new problem to be faced at present.

Proved by verification, for the common normal-temperature disinfectant taking water as a solvent, the sterilizing performance is obviously reduced along with the rapid reduction of the temperature, and particularly, the normal-temperature disinfectant is frozen without exerting the effect below 0 ℃. Even if the ice is not frozen, the disinfection effect is weakened by times, and the actual low-temperature disinfection requirement cannot be met. At present, related low-temperature disinfection materials for low-temperature disinfection are not available in the market. Therefore, the development of a compound disinfectant which still maintains high-efficiency ideal disinfection effect under low temperature, especially under extremely low temperature (below minus 40 ℃), ensures the safety of cold chain and the safety of packaged food is urgently needed.

The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Disclosure of Invention

(1) The invention provides a preparation method of a composite low-temperature disinfectant with simple process and wide application range, which can be widely used for disinfection (such as civil families, collective offices, cold chain links, cold storage, and the like) under normal temperature and low temperature conditions.

(2) The invention uses the compound of organic and inorganic substances as low-temperature material to ensure the low-temperature antifreezing property.

(3) The invention takes the traditional disinfection material and the polymer disinfection material as the disinfection component, thus ensuring the high efficiency of disinfection and sterilization.

(4) The low-temperature disinfectant has the advantages that: the antibacterial agent has the advantages of low temperature, high efficiency, broad-spectrum sterilization, lasting bacteriostasis, no toxicity, no stimulation, no secondary residue, no flammable and explosive hidden danger, simple operation and suitability for household, office and cold chain.

The invention adopts the following technical scheme: a composite low-temperature disinfectant and a preparation method thereof are characterized by comprising the following steps: dispersing a low-temperature material in a solvent to obtain a solution A; adding the corrosion inhibitor into the solvent, and quickly stirring to obtain a solution B; mixing and stirring the solution A and the solution B to obtain a solution C; mixing the solution C with a proper amount of disinfection components to obtain a solution D; and adding a stabilizer into the solution D to obtain the low-temperature disinfection material with stable performance. The invention has the following advantages: the material source is wide, the performance is stable, the broad spectrum sterilization is realized, the bacteriostasis is durable, the process is simple, the cost is low, the application range is wide, and the method is particularly suitable for the sterilization and disinfection of various cold chain links such as a refrigeration house, a cold chain vehicle and the like.

The preparation method is characterized in that the used solvent is one or a mixture of a plurality of common experimental solvents such as water, ethanol, diethyl ether, acetone, DMF, glacial acetic acid, chloroform, carbon tetrachloride, toluene, ethylene glycol, propylene glycol and the like.

The preparation method is characterized in that the used solvent water can be one or a mixed solution of several of tap water, spring water, well water, drinking purified water and deionized water, and the solvent water is ensured not to contain substances which can prevent the success of the experiment.

The preparation method is characterized in that the low-temperature material is one or more of organic substances such as calcium chloride, sodium nitrite, a mixture of calcium chloride and sodium chloride, a mixture of calcium chloride and sodium nitrite, ethanol, ethylene glycol, isopropanol, glycerol, glycol ether, 1,2 propylene glycol, 1,3 propylene glycol and the like.

The preparation method is characterized in that the used low-temperature material can be prepared and produced by self or can be purchased to obtain finished products.

The preparation method is characterized in that the used disinfection material can be prepared and produced by self or purchased to be finished products.

The preparation method is characterized in that when the solution A is prepared, the stirring time is 2-5 hours, the solution is heated in a water bath at the constant temperature of 40-70 ℃, and the solution is aged for 24-48 hours at room temperature after being stirred.

The preparation method is characterized in that when the solution B is prepared, the stirring time is 2-5 hours, the solution is heated in a water bath at the constant temperature of 40-70 ℃, and the solution is aged for 24-48 hours at room temperature after being stirred.

The preparation method is characterized in that the corrosion inhibitor selected for preparing the solution B is one or more of long-chain fatty acid sodium salt, long-chain fatty acid ammonium salt, Cetyl Trimethyl Ammonium Bromide (CTAB), Span-80 (Span-80), Tween-80 (Tween-80), sodium nitrite, sodium polyacrylate, polyacrylic acid, formic acid, petroleum acid, (Z) -9-octadecenoic acid, fatty acid amide, dodecyl-polyoxyethylene ether, nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, benzalkonium chloride, benzalkonium bromide and polyhexamethylene biguanide.

The preparation method is characterized in that the content of the corrosion inhibitor is within the range of 0.01-35%.

The preparation method is characterized in that when the solution C is prepared, the stirring time is within the range of 24-48 hours, the room temperature aging is 24-48 hours, and the temperature of a water bath or an oil bath is maintained within the range of 40-70 ℃.

The preparation method is characterized in that when the solution C is prepared, the used disinfection material can be chloroisocyanuric acid such as sodium dichloroisocyanurate and trichloroisocyanuric acid; single chain quaternary ammonium salts such as dodecyldimethylbenzyl ammonium chloride (benzalkonium chloride), dodecyldimethylbenzyloxyethyl ammonium bromide, tetradecyldimethylpyridinium bromide benzalkonium bromide, hexadecyltrimethylammonium chloride; double-chain quaternary ammonium salts such as didecyldimethylammonium chloride, didodecyldimethylammonium bromide, and (didodecyldimethyl) ethylenediammonium bromide; polyquaternium such as one or more of polyquaternium, polyhexamethylene biguanide, and polyhexamethylene monoguanidine.

The preparation method is characterized in that the stabilizer selected for preparing the solution D is one or more of long-chain fatty acid sodium salt, long-chain fatty acid ammonium salt, Cetyl Trimethyl Ammonium Bromide (CTAB), borax, triethanolamine, Span-80 (Span-80), Tween-80 (Tween-80), sodium nitrite, sodium polyacrylate, polyacrylic acid, formic acid, petroleum acid, (Z) -9-octadecenoic acid, fatty acid amide, dodecyl-polyoxyethylene ether, nonylphenol polyoxyethylene ether, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.

Detailed Description

In order that those skilled in the art can better understand the present invention, the following embodiments are provided to further illustrate the present invention.

Example 1:

the method comprises the following steps: 350g of 1, 2-propanediol and 30g of sodium chloride were dispersed in 500ml of pure water, and stirred rapidly for 2 hours (bath temperature 40 ℃ C.), and aged at room temperature for 24 hours to obtain a solution A.

Step two: 0.25g of sodium nitrite was added to 100ml of pure water and rapidly stirred for 5 hours (bath temperature: 60 ℃ C.), and aged for 24 hours at room temperature to obtain a solution B.

Step three: the solution A and the solution B were mixed and stirred for 24 hours to obtain a solution C.

Step four: the above solution C was mixed with 5g of didodecyldimethylammonium bromide and 5g of sodium dichloroisocyanurate to obtain a solution D.

Step five: and adding 0.1g of polyacrylic acid into the solution D to obtain the composite low-temperature disinfection material.

Example 2:

the method comprises the following steps: 350g of 1, 2-propanediol and 30g of calcium chloride were dispersed in 500ml of pure water, and stirred rapidly for 2 hours (bath temperature 40 ℃ C.), and aged at room temperature for 24 hours to obtain a solution A.

Step two: 0.25g of sodium polyacrylate was added to 100ml of pure water and rapidly stirred for 5 hours (water bath temperature: 60 ℃ C.), and aged for 24 hours at room temperature to obtain a solution B.

Step three: the solution A and the solution B were mixed and stirred for 24 hours to obtain a solution C.

Step four: the above solution C was mixed with 5g of polyhexamethylene biguanide and 5g of sodium dichloroisocyanurate to obtain solution D.

Step five: and adding 0.1g of sodium nitrite into the solution D to obtain the composite low-temperature disinfection material.

Example 3:

the method comprises the following steps: 350g of 1, 2-propanediol, 15g of calcium chloride and 15g of sodium chloride were dispersed in 500ml of pure water, and stirred rapidly for 2 hours (bath temperature 40 ℃ C.), and aged at room temperature for 24 hours to obtain solution A.

Step two: 0.25g of sodium nitrite was added to 100ml of pure water and rapidly stirred for 5 hours (bath temperature: 60 ℃ C.), and aged for 24 hours at room temperature to obtain a solution B.

Step three: the solution A and the solution B were mixed and stirred for 24 hours to obtain a solution C.

Step four: the above solution C was mixed with 5g of didecyldimethylammonium chloride and 5g of sodium dichloroisocyanurate to obtain solution D.

Step five: and adding 0.4g of triethanolamine into the solution D to obtain the composite low-temperature disinfection material.

It should be noted that each component may be selected from a plurality of compounds listed in the summary of the invention or a combination thereof, and as to the use of the collective compounds, the specific content of each compound is selected and adjusted by those skilled in the art according to the use cases and the production environment. Often, one or both are selected for ease of preparation and are combined, and the above examples are merely illustrative of experiments conducted in connection with applicants.

The above-described embodiments should not be construed as limiting the scope of the invention, and all changes or equivalent substitutions that do not depart from the spirit of the invention are intended to be included therein.

The finished low-temperature disinfection material obtained by the invention is detected as follows:

1. suspension method neutralizer identification test

The test was carried out according to the Disinfection Specification, 2002, 2.1.1.5.5, to determine whether the selected neutralizing agent was able to completely neutralize the disinfecting component, and the test groups were as follows:

group 1 disinfectant + bacterial suspension → culture

And observing whether the disinfectant has the capability of killing or inhibiting the test bacteria.

Group 2 (disinfectant + bacterial suspension) + neutralizer → culture

And (5) observing whether the test bacteria can recover the growth after the residual disinfectant is neutralized and subjected to the action of the disinfectant.

Group 3 neutralizing agent + bacterial suspension → culture

And observing whether the neutralizer inhibits bacteria.

Group 4 (disinfectant + neutralizer) + bacterial liquid → culture

It was observed whether the neutralized product, or the residual disinfectant which was not completely neutralized, had an effect on the growth and reproduction of the test bacteria.

Group 5 dilution + bacterial suspension → culture

As a control for the number of bacteria.

Group 6 dilution + neutralizer + Medium → culture

As a negative control.

2. Quantitative sterilization test detection of suspension

According to the technical specification for disinfection, 2002 edition 2.1.1.7.4, the stock solutions of the embodiment 1 and the embodiment 2 are tested, the disinfection action time is 1min, 5min, 10min and 30min respectively, the neutralization action is 10min, the killing logarithm value of staphylococcus aureus is more than or equal to 5.00 in a quantitative killing test of suspension at the temperature of minus 20 ℃, and the expected effect of high-efficiency sterilization can be completely realized at the low temperature.

Results of the study

2.1 neutralizer identification test

The test concentration is the stock solution of example 1 and example 2, the sterilization time is 1min, the neutralization time is 10min, the neutralizing agent is D/E neutralized broth, the test temperature is-18 ℃ to-20 ℃ for refrigerator freezing, when the neutralizing agent is PBS containing 0.5% of sodium thiosulfate, the average growing colony number of the group 2 is 0cfu/ml, the error rate among the groups 3, 4 and 5 is 5.37%, and the group 6 grows aseptically.

D/E neutralizing broth can effectively neutralize residual toxicity of the disinfectant to test bacteria in a neutralizer identification test of a quantitative staphylococcus aureus suspension test in the stock solution of example 1, the neutralizer and a neutralization product have no toxicity to the test bacteria and no adverse effect on a culture medium, and the results of example 1 prove to be shown in Table 1.

TABLE 1 neutralizer identification test results

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Number of growing colonies (cfu/ml) average number of growing colonies per experiment

Assembly-type-device

1 2 3 (cfu/ml)

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1 0 0 0 0

2 0 0 0 0

3 1.14×10⁷ 1.70×10⁷ 1.47×10⁷ 1.44×10⁷

4 1.16×10⁷ 1.74×10⁷ 1.45×10⁷ 1.45×10⁷

5 1.29×10⁷ 1.94×10⁷ 1.62×10⁷ 1.62×10⁷

6 0 0 0 0

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2.2 quantitative Sterilization test by suspension method

The test concentration is that the stock solutions of the example 1 and the example 2 (the detection report is a carrier method), the sterilization test is respectively carried out at the temperature of 20 ℃ and the temperature of 20 ℃, the neutralization time is 10min, and the test result shows that the stock solutions of the example 1 and the example 2 are acted for 1min, and the average killing logarithm value of staphylococcus aureus is more than 5.00. The sterilization test results under the conditions of 20 ℃ and-20 ℃ are not different, and the colony counting results of-1 dilution gradient are all 0, which indicates that the disinfectant in the suspension state has obvious sterilization capability under the low-temperature condition.

TABLE 2 Sterilization test results

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DisinfectantAverage kill log value and range for different time (min)

(stock solution) 151030

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Example 1 stock solution 20 ℃ >5.00 >5.00 >5.00

Example 1 stock solution-20 ℃ 5.00 >5.00 >5.00

Example 2 stock solution 20 ℃ >5.00 >5.00 >5.00

Example 2 stock solution-20 ℃ 5.00 >5.00 >5.00

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Note: the average colony number of the positive control group is 1.76 multiplied by 10⁷cfu/ml。

The negative control group was grown aseptically.