CN114145294A - Composite disinfectant containing alpha-alkyl betaine and application thereof - Google Patents

Composite disinfectant containing alpha-alkyl betaine and application thereof Download PDF

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Publication number
CN114145294A
CN114145294A CN202111201151.XA CN202111201151A CN114145294A CN 114145294 A CN114145294 A CN 114145294A CN 202111201151 A CN202111201151 A CN 202111201151A CN 114145294 A CN114145294 A CN 114145294A
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parts
disinfectant
composite
alkyl betaine
alpha
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邹宇
肖富昌
张艺
张豫红
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Chengdu Kehongda Chemical Co ltd
CHENGDU KEHONGDA TECHNOLOGY CO LTD
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Chengdu Kehongda Chemical Co ltd
CHENGDU KEHONGDA TECHNOLOGY CO LTD
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/02Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02Amines; Quaternary ammonium compounds
    • A01N33/12Quaternary ammonium compounds

Abstract

The invention belongs to the technical field of disinfectants, and discloses a composite disinfectant containing alpha-alkyl betaine and application thereof, wherein each 100 parts of the composite disinfectant comprises the following components in parts by mass: 3-8 parts of glutaraldehyde, 3-8 parts of decamethylammonium bromide, 3-10 parts of alpha-alkylbetaine and the balance of water. The composite disinfectant is used for disinfecting livestock and poultry breeding places and livestock and poultry housing appliances, in particular to the surfaces of objects with complicated structures, such as grooves, meshes, fences and the like. The composite disinfectant prepared by the invention is a foam disinfectant, and is sprayed on the surfaces of objects such as walls, appliances and the like when in use, and the foam is adhered on the surfaces of the objects and does not flow down; and the foam is multiply overlapped, so that the contact time of the disinfectant and the surface of the disinfected object is greatly prolonged, the action time with pathogens is prolonged, and particularly, the disinfectant is more rapid and better in disinfection effect compared with a simple disinfectant on the surface of an object with complicated structures such as grooves, meshes, fences and the like.

Description

Composite disinfectant containing alpha-alkyl betaine and application thereof
Technical Field
The invention belongs to the technical field of disinfectants, and relates to a composite disinfectant containing alpha-alkyl betaine and application thereof.
Background
The disinfectant is used for killing pathogenic microorganisms on a transmission medium, so that the requirement of harmlessness is met, the pathogenic microorganisms are eliminated, the transmission path of infectious diseases is cut off, and the purpose of controlling the infectious diseases is achieved. The disinfectant in the market is various, different disinfectants have different disinfection effects, and in order to improve the disinfection effect and meet the requirements of broad spectrum, high efficiency, proper cost and the like of the disinfectant as much as possible, most of the disinfectants in the market are composite products.
Glutaraldehyde is aldehyde disinfectant, and can kill propagules of bacteria, spores, fungi, viruses, etc.; the aldehyde disinfectant has the function of killing microbes mainly by virtue of aldehyde group which acts on the mercapto group, hydroxyl group, carboxyl group and amino group of mycoprotein, so that the mycoprotein can be alkylated to cause protein coagulation to cause bacterial death. The decamethyl ammonium bromide is a double-long-chain cationic surfactant, and quaternary ammonium cations of the decamethyl ammonium bromide can actively attract and enrich on the surfaces of negatively charged bacteria and viruses, so that the metabolism of the bacteria is hindered, and the permeability of a membrane of the decamethyl ammonium bromide is changed. The glutaraldehyde and the ammonium decamethylammonium bromide are compounded for use, so that the glutaraldehyde can easily enter bacteria and viruses, the activity of proteins and enzymes is damaged, and the quick and efficient disinfection effect is achieved.
Chinese patent application CN107568222A discloses a compound glutaraldehyde decamethylammonium bromide long-acting disinfectant, which consists of glutaraldehyde, decamethylammonium bromide, a smell purifying agent, an adhesive and water, and the disinfectant has lower pungent smell and longer effective disinfection time, but does not accord with the national veterinary drug standard, has poor stability, can generate the phenomena of layering, suspended matters and turbidity after long-term storage, and reduces the sterilization and disinfection effect.
The existing glutaraldehyde decamethylammonium bromide compound disinfectant on the market at present has the concentration of 5g of glutaraldehyde and 5g of decamethylammonium bromide in each 100mL of disinfectant, is mainly used for disinfection of farms and public places, needs to be diluted by water according to a certain proportion before use, adopts a splashing mode for disinfection, and can cause uneven diffusion and incomplete disinfection of the disinfectant due to the fact that disinfectant is distributed in a punctiform or patch shape on the disinfection surface.
The foam type cleaning disinfectant is a new type of product, and is formed from disinfectant and foam disinfectant adjuvant, and the liquid cleaning disinfectant can be converted into gas-phase foam form by means of related foaming device, and the foam can be directly contacted with surface to be cleaned and disinfected so as to attain the goal of disinfection. At present, the glutaraldehyde decamethylammonium bromide composite foam disinfectant is relatively few in reports, multiple surfactants are mostly added to achieve the foam stabilizing effect, the cost is increased, and meanwhile, residual substances left after disinfection are not easy to clean and harm the environment and livestock.
Disclosure of Invention
The invention aims to solve the technical problems of poor stability, multiple types of added surfactants, easiness in residue and the like of the existing foam disinfectant, and provides the composite disinfectant containing the alpha-alkyl betaine, which has the advantages of good stability, quickness and high efficiency in disinfection, no need of cleaning after use and natural drying.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the composite disinfectant containing alpha-alkyl betaine comprises the following components in parts by mass per 100 parts: 3-8 parts of glutaraldehyde, 3-8 parts of decamethylammonium bromide, 3-10 parts of alpha-alkylbetaine and the balance of water.
Preferably, the composite disinfectant containing alpha-alkyl betaine comprises the following components in parts by mass per 100 parts: 5 parts of glutaraldehyde, 5 parts of decamethylammonium bromide, 3-10 parts of alpha-alkyl betaine and the balance of water.
Preferably, the composite disinfectant containing alpha-alkyl betaine comprises the following components in parts by mass per 100 parts: 5 parts of glutaraldehyde, 5 parts of decamethylammonium bromide, 8 parts of alpha-alkyl betaine and the balance of water.
Preferably, the number of alkyl carbon atoms of the alpha-alkyl betaine is 8-18.
Preferably, the preparation method of the composite disinfectant of alpha-alkyl betaine comprises the following steps:
(1) taking water and alpha-alkyl betaine with corresponding weight, and uniformly mixing to obtain a mixture A;
(2) adding glutaraldehyde and ammonium decamethyl bromide with corresponding weights into the mixture A obtained in the first step, and uniformly mixing to obtain a mixture B;
(3) adjusting the pH value of the mixture B obtained in the second step to 4.0-5.0, and checking to be qualified to obtain the final product.
The invention also provides the application of the composite disinfectant containing the alpha-alkyl betaine, which is used for disinfecting livestock and poultry breeding places and livestock and poultry house appliances, in particular to the surfaces of objects with complicated structures, such as grooves, meshes, fences and the like.
Preferably, the application method of the composite disinfectant containing alpha-alkyl betaine comprises the following steps:
(1) pouring the sample into a foaming gun medicine pot, and assembling the medicine pot filled with the liquid medicine with a foaming gun according to requirements;
(2) then the use requirement of the foaming gun is connected with a water outlet joint of a high-pressure water pump, and a water suction pipe of the water pump is placed in a clean water body;
(3) switching on a power supply of the high-pressure water pump, turning on a switch of the high-pressure water pump, and adjusting the scales of the foaming gun medicine feeding control valve to the required scales;
(4) carrying out foam spraying sterilization work on a target sterilization area by holding a foaming gun;
(5) after spraying, the foam containing the disinfectant stays in the spraying area for 15-30min, and then the foam in the disinfection area is washed away by clean water (if the foam is put into use as soon as possible), or the disinfection work is finished after the foam naturally dissipates.
Compared with the prior art, the invention has the beneficial effects that:
(1) the composite disinfectant is prepared by compounding alpha-alkyl betaine which does not react with glutaraldehyde serving as a foaming agent with glutaraldehyde and ammonium decamethylammonium bromide, and has good stability, the reduction rate of the content of glutaraldehyde in the prepared disinfectant is not more than 3% at room temperature within one year, and the disinfectant can be stably stored.
(2) The composite disinfectant prepared by the invention is a foam disinfectant, and is sprayed on the surfaces of objects such as walls, appliances and the like when in use, and the foam is adhered on the surfaces of the objects and does not flow down; and the foam is multiple overlapping, the contact time of the disinfectant and the surface of the disinfected object is greatly prolonged (the foam maintaining time of the disinfectant can reach 10-15min), so that the action time with the pathogen is prolonged, and particularly, the disinfectant is more rapid and better in disinfection effect compared with a simple disinfectant on the surface of an object with complicated structures, such as a groove, a mesh, a fence and the like.
(3) The composite disinfectant is a foam disinfectant, has strong visibility, avoids disinfection blind areas, and is more uniform and thorough in disinfection.
(4) The invention reduces the repeated spraying of the disinfectant and the waste of water caused by high-pressure spraying, does not need to be cleaned after use, can be naturally dried, has no residue and greatly reduces the pollution to the environment.
Drawings
FIG. 1 is a diagram showing the foaming effect of the composite disinfectant of comparative example 1 (starting time, 1min, and 3min in sequence from left to right);
FIG. 2 is a graph showing the foaming effect of the composite disinfectant of comparative example 2 (starting time, 1min, and 3min in sequence from left to right);
FIG. 3 is a graph showing the foaming effect of the composite disinfectant of example 1 (beginning, 3min, 7min, and 10min from left to right).
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
A composite disinfectant containing alpha-alkyl betaine is prepared by the following steps:
(1) taking 85g of water and 5g of alpha-alkyl betaine, and uniformly mixing to obtain a mixture A;
(2) adding 5g of glutaraldehyde and 5g of ammonium decamethyl bromide into the mixture A obtained in the first step, and uniformly mixing to obtain a mixture B;
(3) adjusting the pH value of the mixture B obtained in the second step to 4.0-5.0, and checking to be qualified to obtain the final product.
Example 2
A composite disinfectant containing alpha-alkyl betaine is prepared by the following steps:
(1) taking 87g of water and 3g of alpha-alkyl betaine, and uniformly mixing to obtain a mixture A;
(2) adding 5g of glutaraldehyde and 5g of ammonium decamethyl bromide into the mixture A obtained in the first step, and uniformly mixing to obtain a mixture B;
(3) adjusting the pH value of the mixture B obtained in the second step to 4.0-5.0, and checking to be qualified to obtain the final product.
Example 3
A composite disinfectant containing alpha-alkyl betaine is prepared by the following steps:
(1) taking 82g of water and 8g of alpha-alkyl betaine, and uniformly mixing to obtain a mixture A;
(2) adding 5g of glutaraldehyde and 5g of ammonium decamethyl bromide into the mixture A obtained in the first step, and uniformly mixing to obtain a mixture B;
(3) adjusting the pH value of the mixture B obtained in the second step to 4.0-5.0, and checking to be qualified to obtain the final product.
Comparative example 1
A composite disinfectant is prepared by the following steps: and (3) uniformly mixing 90g of water, 5g of glutaraldehyde and 5g of ammonium decamethylammonium bromide, adjusting the pH value of the solution to 4.0-5.0, and checking to be qualified to obtain the aqueous solution.
Comparative example 2
A composite disinfectant is prepared by the following steps:
(1) taking 85g of water and 5g of dodecyl dimethyl betaine, and uniformly mixing to obtain a mixture A;
(2) adding 5g of glutaraldehyde and 5g of ammonium decamethyl bromide into the mixture A obtained in the first step, and uniformly mixing to obtain a mixture B;
(3) adjusting the pH value of the mixture B obtained in the second step to 4.0-5.0, and checking to be qualified to obtain the final product.
Analysis of experiments
1. Stability test
The composite disinfectants of example 1, comparative example 1 and comparative example 2 were placed at 60 + -2 deg.C and relative humidity 20 + -10%, at 40 + -2 deg.C and relative humidity 75 + -10%, and at 25 + -2 deg.C and relative humidity 60 + -10% for 0, 5 and 10 days, and the properties, pH, glutaraldehyde and decamethylammonium bromide content were observed, respectively, and the test results are shown in Table 1.
The test data in the table 1 show that the content of glutaraldehyde and the pH value of the composite disinfectant solution are in a descending trend, the content of decamethyl ammonium bromide is in an ascending trend, and the color of the solution is gradually changed from colorless to light yellow along with the passage of time; analyzing the test data in the table, the comparative example 1 and the comparative example 2 have larger changes of the character and the PH and larger decreases of the effective component glutaraldehyde from 5.14 percent and 5.06 percent to 4.22 percent and 3.97 percent respectively when being placed at 60 ℃ for 10 days. The composite disinfectant of the embodiment 1 is placed at 60 ℃, 40 ℃ and 25 ℃ for 10 days, the character and the pH value of the composite disinfectant are basically kept unchanged, the content of effective components of glutaraldehyde and the content of decamethylammonium bromide are slightly changed, and the embodiment 1 of the invention is better in stability.
TABLE 1 stability testing
Figure RE-GDA0003472896770000041
2. Sterilization test
2.1 test method: the detection of the sterilization effect is carried out by taking escherichia coli ATCC 8099 and staphylococcus aureus ATCC 6538 as representatives of bacteria and candida albicans ATCC 10231 as representatives of fungi according to a test method and a judgment basis of disinfection technical specification (2002 edition), wherein the killing logarithm value KL of the bacteria is more than 5, and the killing logarithm value KL of the fungi is more than 4.
Escherichia coli: when the bacterial suspension is diluted to 10-6, the average colony number is 208; when the bacterial suspension is diluted to 10-7, the average colony number is 16, and the average number, namely the average concentration of the stock solution of the bacterial suspension is 1.84 multiplied by 108 cfu/mL. (the concentration of the bacterial suspension in the bacterial suspension meets the disinfection technical specification is 1 multiplied by 108 cfu/mL-5 multiplied by 108 cfu/mL). From this, the concentration of the bacterial suspension stock solution in the positive control group was 1.84 × 106cfu/mL, that is, 10-2. N0 ═ 6.26 was obtained.
Staphylococcus aureus: when the bacterial suspension is diluted to 10-6, the average colony number is 172; when the bacterial suspension is diluted to 10-7, the average number of colonies is 23, and the average number, namely the average concentration of the stock solution of the bacterial suspension is 2.01 multiplied by 108 cfu/mL. (the concentration of the bacterial suspension in the bacterial suspension meets the disinfection technical specification is 1 multiplied by 108 cfu/mL-5 multiplied by 108 cfu/mL). From this, the concentration of the bacterial suspension stock solution in the positive control group was 2.01 × 106cfu/mL, that is, 10-2. N0 is 6.30.
Candida albicans: when the bacterial suspension is diluted to 10-6, the average colony number is 128; when the bacterial suspension is diluted to 10-7, the average colony number is 22, and the average number, namely the average concentration of the bacterial suspension stock solution is 1.74 x 107 cfu/mL. (the concentration of the bacterial suspension in the bacterial suspension meets the disinfection technical specification is 1 multiplied by 107cfu/mL to 5 multiplied by 107 cfu/mL). From this, the concentration of the bacterial suspension stock solution in the positive control group was 1.74 × 105cfu/mL, that is, 10-2. N0 is 5.24.
2.2 test results: after the composite disinfectant of example 1, comparative example 1 and comparative example 2 was diluted by a certain factor, the bactericidal effect on escherichia coli ATCC 8099, staphylococcus aureus ATCC 6538 and candida albicans ATCC 10231 were respectively tested, and the specific results are shown in tables 2 to 4.
TABLE 2 Sterilization of Escherichia coli by different composite disinfectants
Figure RE-GDA0003472896770000051
Note: indicates too much to count.
As can be seen from Table 2, under 300-fold dilution, the killing log values of the three samples are 4.12 and 4.38 under the action conditions of 3min and 4.5min except for the comparative example 2, and the killing log values of the thalli are all more than 5 under the other conditions; under 600 times dilution, the killing logarithm value of comparative example 1 under the action condition of 4.5min is 4.43, the killing logarithm value of example 1 under the action conditions of 3min and 4.5min is 4.28 and 4.81, and the number of colonies is too large to count under the rest conditions; at 1200-fold dilution, the number of colonies was too large to count, except that the log kill of example 1 at 4.5min was 4.23. In conclusion, the composite disinfectant prepared in example 1 has a good antibacterial effect on escherichia coli.
As can be seen from table 3: under 300 times dilution, the three samples have no obvious difference in sterilization effect under different action time, and the killing log values of the thalli are all more than 5; under 600 times dilution, the killing logarithm value of comparative example 1 under the action conditions of 3min and 4.5min is 4.64 and more than 5, the killing logarithm value of comparative example 2 under the action conditions of 4.5min is 4.73, the killing logarithm value of example 1 under the action conditions of 1.5min, 3min and 4.5min is 4.92, more than 5 and more than 5, and the number of colonies is too large to count under the other conditions; at 1200-fold dilution, comparative example 1 had a log kill of 3.61 at 4.5min, and example 1 had log kill of 3.55 and 4.16 at 3min and 4.5min, all of which showed too many colonies to count. In conclusion, the composite disinfectant prepared in example 1 has a good antibacterial effect on staphylococcus aureus.
TABLE 3 Sterilization of Staphylococcus aureus with different composite disinfectants
Figure RE-GDA0003472896770000061
TABLE 4 Sterilization of Candida albicans by different composite disinfectants
Figure RE-GDA0003472896770000062
As can be seen from table 4: under 300 times dilution, the three samples have no obvious difference in sterilization effect under different action time, and the killing log values of the thalli are all more than 4; under 600 times dilution, the killing logarithm value of comparative example 1 under the action conditions of 3min and 4.5min is 3.11 and more than 4, the killing logarithm value of comparative example 2 under the action conditions of 4.5min is 3.07, the killing logarithm value of example 1 under the action conditions of 1.5min, 3min and 4.5min is 2.60, 3.31 and more than 4, and the number of colonies is too large to count under the other conditions; at 1200-fold dilution, comparative example 1 had a log kill of 2.49 at 4.5min, example 1 had a log kill of 2.80 at 4.5min, and all other conditions showed too many colonies to count. In conclusion, the composite disinfectant prepared in example 1 has a good antibacterial effect on candida albicans.
By combining the above analysis, the composite disinfectant prepared in the embodiment 1 of the invention has better sterilization effect on different bacteria compared with the comparative examples 1 and 2, and the formula of the embodiment of the invention adopts the alpha-alkyl betaine as the foaming agent of the composite disinfectant, so that the stability and foaming performance of the composite disinfectant can be improved, and the sterilization effect of the composite disinfectant of glutaraldehyde and decamethylammonium bromide can be enhanced.
3. Foaming Property
3.1 test method: respectively pouring the composite disinfectants prepared in the example 1, the comparative example 1 and the comparative example 2 into a foaming gun, and connecting the foaming gun with a high-pressure water pump (the pressure of the pump is set to be 6-22 mpa, and the water flow is 14L/min); opening a high-pressure water pump switch, and adjusting the scales of the foaming gun medicine feeding control valve to the required scales (the consumption of the disinfectant is 0.6L/min); respectively sprayed on the glass surfaces with the same size, and the spraying effect, namely the wall hanging time, is observed.
3.2 test results: the concrete results are shown in the attached drawings 1-3, and the specific results of the composite disinfectants of comparative examples 1 and 2 show that the composite disinfectants of example 1 have more foams on the glass surface during initial spraying, but only a small amount of foams exist on the glass surface after 3min, and the composite disinfectants of example 1 still have a large amount of foams on the glass surface even after 10min spraying, which shows that the composite disinfectants of example 1 have longer contact time on the object surface than those of comparative examples 1 and 2, and also prove that the composite disinfectants of the invention have good bactericidal efficacy.
The experiment results show that the alpha-alkyl betaine is used as the foaming agent of the glutaraldehyde and decamethylammonium bromide composite disinfectant, the raw material formula components are simple, the foaming effect of the composite disinfectant is improved, the sterilization effect and the stability of the composite disinfectant can be enhanced, the prepared composite disinfectant is obviously superior to the existing foam disinfectant product, and the composite disinfectant has wide market application prospect.
The foregoing is considered as illustrative of the preferred embodiments of the invention, but is made merely for the purpose of providing an understanding of the principles of the embodiments; meanwhile, for a person skilled in the art, according to the present embodiment, there may be a change in the specific implementation and application scope, and in summary, the present disclosure should not be construed as a limitation to the present invention.

Claims (5)

1. A composite disinfectant containing alpha-alkyl betaine is characterized in that: every 100 parts by mass of the composition comprises the following components in parts by mass: 3-8 parts of glutaraldehyde, 3-8 parts of decamethylammonium bromide, 3-10 parts of alpha-alkylbetaine and the balance of water.
2. The complex disinfectant containing α -alkyl betaine according to claim 1, wherein: every 100 parts by mass of the composition comprises the following components in parts by mass: 5 parts of glutaraldehyde, 5 parts of decamethylammonium bromide, 5 parts of alpha-alkyl betaine and the balance of water.
3. The complex disinfectant containing α -alkyl betaine according to claim 1, wherein: every 100 parts by mass of the composition comprises the following components in parts by mass: 5 parts of glutaraldehyde, 5 parts of decamethylammonium bromide, 8 parts of alpha-alkyl betaine and the balance of water.
4. The complex disinfectant containing α -alkylbetaine according to any one of claims 1 to 3, wherein: the number of alkyl carbon atoms of the alpha-alkyl betaine is 8-18.
5. Use of the complex disinfectant containing α -alkyl betaine according to claim 1, wherein: the compound disinfectant is used for disinfecting livestock and poultry breeding places and livestock and poultry housing appliances, in particular to the surfaces of objects with complicated structures, such as grooves, meshes, fences and the like.
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陈玮 等: "新型季铵盐复合消毒剂的研究", 《中国消毒学杂志》 *

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