Isothiazolinone anti-corrosion decontamination compound and preparation method thereof

Abstract

The invention relates to the technical field of preservatives, in particular to an isothiazolinone antiseptic decontamination compound and a preparation method of the isothiazolinone antiseptic decontamination compound. The invention relates to a corrosion and scale inhibitor, which is prepared from the following raw materials in percentage by weight: 0.1 to 0.4 percent of isothiazolinone preservatives, 0.06 to 0.15 percent of benzene hydroxyl preservatives, 1 to 2 percent of fatty alcohol-polyoxyethylene ether-9, 0.1 to 0.2 percent of dodecyl dimethyl amine oxide, 0.005 to 0.05 percent of chelating agents, 0.3 to 2 percent of solvents and 95.2 to 98.44 percent of EDI pure water. The sum of the weight percentages of the raw materials is 100%. According to the present invention, the benzene hydroxyl preservative is added as the stabilizer and the synergistic agent, such that the problems of easy degradation, obvious yellowing and weak single corrosion resistance of the isothiazolinone preservative at the high temperature are solved, and the decontamination ability of the product is ensured. The isothiazolinone anti-corrosion decontamination compound disclosed by the invention has excellent anti-corrosion performance and high-temperature stability, and is suitable for being used as an anti-corrosion agent in daily chemical products.

Description

Technical Field

[0001] The present invention relates to the technical field of preservatives, and particularly to an isothiazolinone-based anti-corrosion and decontamination complex and a preparation method thereof. Background Art

[0002] Isothiazolinone-based preservatives (such as methylisothiazolinone MIT and benzisothiazolinone BIT) are widely used in the daily chemical field due to their low cost and broad-spectrum antibacterial properties. However, the inherent thiazole ring and active sulfur bond in their molecular structures are prone to multiple degradation reactions: under acid / base catalysis or high-temperature conditions, the thiazole ring is easily hydrolyzed to form inactive amide substances; the active sulfur atom is easily oxidized to destroy the molecular structure; ultraviolet light (UVA / UVB) triggers photolysis reactions, resulting in molecular cleavage. These reactions directly lead to irreversible loss of the anti-corrosion active ingredients, manifested as a significant decrease in content and solution yellowing after storage at high temperature (>40°C).

[0003] The stability of this preservative highly depends on environmental conditions: it is relatively stable within the pH range of 5 - 7, and strong acid (pH < 3) or strong base (pH > 9) environments will accelerate decomposition; it is significantly temperature-sensitive, with more than 50% loss of activity after storage at 60°C for 1 month; the accumulation of photodegradation products under light exposure further weakens its efficacy. Although its antibacterial efficiency is excellent, the stability defect requires the synergistic effect of stabilizers in the formulation, and it is prone to degradation when used alone, unable to meet the long-term anti-corrosion requirements.

[0004] Therefore, how to improve the chemical stability of isothiazolinone-based preservatives in a wide pH range (especially in extreme acid and base environments), high temperature (>40°C), and light conditions, and at the same time overcome the problem of insufficient anti-corrosion efficacy caused by degradation during single application urgently needs to be solved. Summary of the Invention

[0005] The purpose of the present invention is to overcome the deficiencies in the prior art and provide an isothiazolinone-based anti-corrosion and decontamination complex and a preparation method thereof. By using a preservative with a benzene hydroxyl group, the stability and yellowing reaction of methylisothiazolinone / benzisothiazolinone can be significantly improved, and it synergistically enhances the anti-corrosion performance.

[0006] On the one hand, the present invention provides a stable isothiazolinone-based anti-corrosion and decontamination complex. By weight percentage, its raw materials are composed of 0.1 - 0.4 wt% isothiazolinone-based preservative, 0.06 wt% - 0.15 wt% benzene hydroxyl group-based preservative, 1 - 2 wt% fatty alcohol polyoxyethylene ether-9, 0.1 - 0.2 wt% dodecyldimethylamine oxide, 0.005 - 0.05 wt% chelating agent, 0.3 - 2 wt% solvent, and 95.2 - 98.44 wt% EDI pure water; the sum of the weight percentages of the above raw materials is 100%.

[0007] Through the above technical solutions, the phenylhydroxy preservative forms hydrogen bonds through the hydroxyl group (-OH) in its molecule with the nitrogen atom of the thiazole ring of isothiazolinone, and at the same time produces hydrophobic association through the hydrophobic group of the benzene ring and the hydrophobic region (such as methyl / phenyl) of isothiazolinone. This dual interaction anchors methylparaben to the active site of isothiazolinone directionally. The steric hindrance effect can block the attack of water molecules, oxygen free radicals and ultraviolet photons on the active center, reducing the hydrolysis / oxidation / photolysis rate, thus significantly delaying the degradation of the preservative.

[0008] When the addition amount of the phenylhydroxy preservative is controlled within 0.05%-0.15 wt%, it forms nano-scale micelle structures through self-assembly to uniformly coat isothiazolinone molecules. And within this range, methylparaben reduces the electron cloud density of its reactive active center by triggering the conformational rearrangement of isothiazolinone molecules. This structure-activity synergy increases the activation energy of self-degradation of isothiazolinone without adding external stabilizers, forming a "molecular self-locking" effect to achieve long-term stability.

[0009] Isothiazolinones (MIT / BIT) are prone to combine with trace metal ions (such as Fe 2+ , Cu 2+ ) in the formulation, which will cause the oxidative degradation of MIT (the inactivation rate can be increased by 50% by metal ions at 50 °C); BIT forms insoluble precipitates (such as BIT-Fe complexes) with metal ions. The chelating agent accounts for 0.3-2%, which can efficiently capture free metal ions (such as the chelating capacity of disodium EDTA reaches 99.8%); the solvent accounts for 0.005-0.05% (such as propylene glycol): through hydrogen bonding and synergistic action with the chelating agent, the metal ions are "wrapped" and isolated from the active area of the preservative.

[0010] Furthermore, the isothiazolinone preservatives include methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1.

[0011] Through the above technical solutions, methylisothiazolinone (MIT) disrupts the permeability of the bacterial cell membrane (MIC ≤ 15 ppm against Staphylococcus aureus ATCC6538), and benzisothiazolinone (BIT) relies on the inhibition of quinone reductase (MFC ≤ 50 ppm against Candida albicans ATCC10231) to form a broad-spectrum antibacterial coverage. In the compound system (MIT:BIT = 1:1), the polar structure of MIT forms a molecular complex with BIT through π-π stacking, reducing the critical micelle concentration (CMC) of BIT and increasing the solubility of the system, achieving a double enhancement of anti-corrosion efficacy and physical stability.

[0012] Further, the phenylhydroxy preservative is selected from one or more of methylparaben, propylparaben, p-hydroxyacetophenone, and phenoxyethanol.

[0013] Further, the complex further comprises an acid-base regulator; the addition amount of the acid-base regulator is such that the pH value of the complex is 5.0 - 7.0; wherein, the acid-base regulator is selected from citric acid.

[0014] Further, the chelating agent is selected from EDTA-2NA; the solvent is selected from any one or a combination of at least two of 1,2-propanediol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,2-decanediol, or 1,10-decanediol.

[0015] Through the above technical solution, 1,2-pentanediol (C5) matches the hydrophobic region of MIT / BIT through 5 carbon chain lengths, and improves the bactericidal speed by penetrating the cell membrane; it remains liquid at -20°C, avoiding the precipitation of BIT (in contrast, glycerol is prone to crystallization below 0°C); the hydroxyl group of 1,2-pentanediol (C5) and Na of EDTA-2Na + form an ion-dipole interaction, enhancing the effect of metal ion encapsulation (FT-IR confirms a 10 cm shift in the complexation peak -1 ); the hygroscopicity of 1,3-butanediol (C4) (water absorption rate of 35% at RH50%) is positively correlated with the preservative activity retention rate. This 1,3-butanediol (C4) has excellent skin compatibility (PC value = 0.5) and can neutralize the potential irritation of MIT;

[0016] 1,2-Hexanediol (C6) forms a hydrophobic barrier through 6 carbon chains to protect MIT / BIT from oxidation; this 1,2-hexanediol (C6) itself has antibacterial activity (MIC against Propionibacterium acnes = 0.5%), and achieves a "double bactericidal" effect when compounded with MIT / BIT.

[0017] Further, the detergency of the complex on the object surface reaches 98%.

[0018] Further, after 30 days of accelerated stability test at 54 ± 0.5°C and detected by high performance liquid chromatography, the total content retention rate of isothiazolinone substances is ≥ 98.5%, and there is no obvious yellowing.

[0019] Further, when the complex is used as a water-based decontamination system, microbial index requirements are tested according to the GB15979-2024 standard, and it is measured within a 3-day culture period:

[0020] The total number of bacterial colonies < 5 CFU / mL;

[0021] Total number of fungal colonies < 5 CFU / mL;

[0022] According to the European Pharmacopoeia's method for testing antiseptic efficacy, in the emulsion liquid model of the complex, after 28 days of microbial experiments, it was measured that:

[0023] For Escherichia coli ATCC25922, Staphylococcus aureus ATCC6538, Pseudomonas aeruginosa ATCC15442, Streptococcus hemolyticus CICC10373, and Burkholderia cepacia CICC23648, the log 10 reduction value ≥ 5.6; for Aspergillus niger ATCC16404, the log 10 reduction value ≥ 4.4; for Candida albicans ATCC10231, the log 10 reduction value ≥ 4.3;

[0024] And the microbial survival curves at the time points of 7 days, 14 days, 21 days, and 28 days all meet the European Pharmacopoeia Class A antiseptic standard.

[0025] Also provided is a method for preparing the above complex, comprising the following steps:

[0026] 1) Add a chelating agent according to the above raw material ratio, and stir and mix evenly;

[0027] 2) Add an isothiazolinone preservative, a benzohydroxy preservative, fatty alcohol polyoxyethylene ether - 9, dodecyldimethylamine oxide, a solvent, and EDI pure water, and continuously stir until completely dissolved;

[0028] 3) Add an acid - base regulator to adjust the pH value to 5.0 - 7.0, and obtain the finished product after cooling and filtration.

[0029] Beneficial effects

[0030] Effectively inhibit the hydrolysis, oxidation, and photolysis reactions of isothiazolinone through intermolecular hydrogen bonding and hydrophobic association. At the same time, form a nanoscale protective layer covering the active sites through the self - assembly of methylparaben, and synergistically induce the conformational optimization of isothiazolinone molecules to form a long - term stable structure;

[0031] The synergistic compounding of methylisothiazolinone and benzisothiazolinone achieves broad - spectrum antibacterial coverage (targeting bacterial membranes and inhibiting fungal enzyme activity), significantly improves the solubility of benzisothiazolinone and inhibits crystal precipitation;

[0032] Chelating agents and polyols act synergistically to effectively isolate metal ions, regulate the moisture balance of the system and achieve a slow-release function, and maintain the stability of the active conformation of the preservative in combination with pH adjustment; the optimized step-by-step preparation process ensures the uniformity and high purity of the system, and the accelerated stability verification shows excellent active ingredient retention ability and color stability; the high antibacterial performance is verified through microbial challenge tests at low addition levels, and it meets the requirements of international anti-corrosion standards. Description of the Drawings

[0033] Figure 1 It is a broken line graph showing the detergency of the orthogonal experiments of Examples 1-9 of the present invention;

[0034] Figure 2 It is a broken line graph showing the reduction rate of isothiazolinone preservatives in the orthogonal experiments of Examples 1-9 of the present invention;

[0035] Figure 3 It shows the yellowing phenomenon of Examples 10-13 of the present invention and Comparative Examples 1-3.

[0036] Figure 4 It is a front view before wiping when the present invention is applied to shoes;

[0037] Figure 5 It is a rear view after wiping when the present invention is applied to shoes. Detailed Description of the Invention

[0038] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0039] Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention. The experimental methods without specific conditions noted in the following embodiments are usually carried out under conventional conditions or according to the conditions recommended by the manufacturer. Unless otherwise specified, all percentages, ratios, proportions or parts are by weight.

[0040] The reagents and raw materials used in the embodiments and comparative examples of the present invention can be obtained through commercial channels without special instructions.

[0041] Example 1

[0042] An isothiazolinone-based anti-corrosion and decontamination complex. By weight percentage, its raw materials include 0.1 wt% dodecyldimethylamine oxide, 0.1 wt% isothiazolinone-based preservative, 0.01 wt% EDTA-2NA, 0.5 wt% 1,2-propanediol, and 99.29 wt% EDI pure water; among them, the isothiazolinone-based preservative includes methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0043] After testing:

[0044] The decontamination power of this complex on the object surface reaches 40.11%, and the reduction rate of the isothiazolinone-based preservative after high-temperature treatment is 50.68%.

[0045] Example 2

[0046] An isothiazolinone-based anti-corrosion and decontamination complex. By weight percentage, its raw materials include 0.15 wt% dodecyldimethylamine oxide, 0.3 wt% isothiazolinone-based preservative, 0.06 wt% methylparaben, 0.01 wt% EDTA-2NA, 0.5 wt% 1,2-propanediol, and 98.98 wt% EDI pure water; among them, the isothiazolinone-based preservative includes methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0047] After testing:

[0048] The decontamination power of this complex on the object surface reaches 61.5%, and the reduction rate of the isothiazolinone-based preservative after high-temperature treatment is 8.5%.

[0049] Example 3

[0050] An isothiazolinone-based anti-corrosion and decontamination complex. By weight percentage, its raw materials include 0.2 wt% dodecyldimethylamine oxide, 0.4 wt% isothiazolinone-based preservative, 0.15 wt% methylparaben, 0.01 wt% EDTA-2NA, 0.5 wt% 1,2-propanediol, and 98.74 wt% EDI pure water; among them, the isothiazolinone-based preservative includes methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0051] After testing:

[0052] The detergency of this composite on the object surface reaches 70.07%, and the reduction rate of isothiazolinone preservatives after high-temperature treatment is 0.95%.

[0053] Example 4

[0054] An isothiazolinone anti-corrosion and detergency composite, by weight percentage, its raw materials include 1 wt% fatty alcohol polyoxyethylene ether-9, 0.1 wt% dodecyldimethylamine oxide, 0.3 wt% isothiazolinone preservatives, 0.15 wt% methylparaben, 0.01 wt% EDTA-2NA, 0.5 wt% 1,2-propanediol, and 97.94 wt% EDI pure water; among them, the isothiazolinone preservatives include methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0055] After testing:

[0056] The detergency of this composite on the object surface reaches 70.58%, and the reduction rate of isothiazolinone preservatives after high-temperature treatment is 0.92%.

[0057] Example 5

[0058] An isothiazolinone anti-corrosion and detergency composite, by weight percentage, its raw materials include 1 wt% fatty alcohol polyoxyethylene ether-9, 0.15 wt% dodecyldimethylamine oxide, 0.4 wt% isothiazolinone preservatives, 0.01 wt% EDTA-2NA, 0.5 wt% 1,2-propanediol, and 97.94 wt% EDI pure water; among them, the isothiazolinone preservatives include methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0059] After testing:

[0060] The detergency of this composite on the object surface reaches 80.66%, and the reduction rate of isothiazolinone preservatives after high-temperature treatment is 55.6%.

[0061] Example 6

[0062] An isothiazolinone-based anti-corrosion and decontamination complex. By weight percentage, its raw materials include 1 wt% fatty alcohol polyoxyethylene ether-9, 0.2 wt% dodecyldimethylamine oxide, 0.1 wt% isothiazolinone-based preservative, 0.06 wt% methylparaben, 0.01 wt% EDTA-2NA, 0.5 wt% 1,2-propanediol, and 98.13 wt% EDI pure water; among them, the isothiazolinone-based preservative includes methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0063] After testing:

[0064] The decontamination power of this complex on the object surface reaches 90.27%, and the reduction rate of the isothiazolinone-based preservative after high-temperature treatment is 7.54%.

[0065] Example 7

[0066] An isothiazolinone-based anti-corrosion and decontamination complex. By weight percentage, its raw materials include 2 wt% fatty alcohol polyoxyethylene ether-9, 0.1 wt% dodecyldimethylamine oxide, 0.4 wt% isothiazolinone-based preservative, 0.06 wt% methylparaben, 0.01 wt% EDTA-2NA, 0.5 wt% 1,2-propanediol, and 96.93 wt% EDI pure water; among them, the isothiazolinone-based preservative includes methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0067] After testing:

[0068] The decontamination power of this complex on the object surface reaches 90.86%, and the reduction rate of the isothiazolinone-based preservative after high-temperature treatment is 8.7%.

[0069] Example 8

[0070] An isothiazolinone-based anti-corrosion and decontamination complex. By weight percentage, its raw materials include 2 wt% fatty alcohol polyoxyethylene ether-9, 0.15 wt% dodecyldimethylamine oxide, 0.1 wt% isothiazolinone-based preservative, 0.15 wt% methylparaben, 0.01 wt% EDTA-2NA, 0.5 wt% 1,2-propanediol, and 97.09 wt% EDI pure water; among them, the isothiazolinone-based preservative includes methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0071] After testing:

[0072] The detergency of this complex on the surface of the object reaches 95.78%, and the reduction rate of isothiazolinone preservatives after high-temperature treatment is 0.67%.

[0073] Example 9

[0074] An isothiazolinone anti-corrosion and detergency complex, by weight percentage, its raw materials include 2 wt% fatty alcohol polyoxyethylene ether-9, 0.2 wt% dodecyldimethylamine oxide, 0.3 wt% isothiazolinone preservatives, 0.01 wt% EDTA-2NA, 0.5 wt% 1,2-propanediol, and 96.99 wt% EDI pure water; among them, the isothiazolinone preservatives include methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0075] After testing:

[0076] The detergency of this complex on the surface of the object reaches 99.75%, and the reduction rate of isothiazolinone preservatives after high-temperature treatment is 56.6%.

[0077] Effect examples:

[0078] The detergency and the reduction rate of isothiazolinone preservatives of Examples 1 to 9 were tested respectively.

[0079] Detergency: Wipe the clean surface, wipe the surface with kitchen swill and dust, and after air-drying for 24 h, wipe the dirty surface with the anti-corrosion and detergency complexes of Examples 1-9 respectively, compare the cleanliness before and after, and calculate the detergency.

[0080] Reduction rate of isothiazolinone preservatives: According to the detection method in DB34 / T 3109-2018, first detect the isothiazolinone content of Examples 1-9 respectively, then put Examples 1-9 into an oven at 54 °C, take them out after 30 days, and detect the isothiazolinone content again, and calculate the reduction rate of isothiazolinone preservatives before and after.

[0081] Example / Project Detergency (%) Reduction rate of isothiazolinone preservatives (%) Example 1 40.11 50.68 Example 2 61.5 8.5 Example 3 70.07 0.95 Example 4 70.58 0.92 Example 5 80.66 55.6 Example 6 90.27 7.54 Example 7 90.86 8.7 Example 8 95.78 0.67 Example 9 99.75 56.6

[0082] As Figure 1 shown, the influence degree of different factors on the detergency is given. By calculating the range R, the factor with the greatest influence on the detergency is fatty alcohol polyoxyethylene ether-9; as Figure 2 shown, the influence degree of different factors on the reduction rate of isothiazolinone preservatives. By calculating the range R, the factor with the greatest influence on the reduction rate of isothiazolinone preservatives is benzene hydroxyl preservatives.

[0083] Combined withFigure 1 and Figure 2 As shown in Figure 2 , considering the requirement of anti-corrosion performance, and according to the above orthogonal experiment, the factor with the greatest influence on detergency was obtained by calculating the range R as fatty alcohol polyoxyethylene ether - 9, and the factor with the greatest influence on the reduction rate of isothiazolinone preservatives was benzhydroxy preservatives. The optimal combination was obtained as 2 wt% fatty alcohol polyoxyethylene ether - 9, 0.2 wt% dodecyldimethylamine oxide, 0.4 wt% isothiazolinone preservatives, 0.15 wt% benzhydroxy preservatives, 0.01 wt% EDTA - 2NA, 0.5 wt% 1,2 - propanediol, and 96.74 wt% EDI pure water.

[0084] Example 10

[0085] An isothiazolinone anti - corrosion and detergency complex, by weight percentage, its raw materials include 2 wt% fatty alcohol polyoxyethylene ether - 9, 0.2 wt% dodecyldimethylamine oxide, 0.4 wt% isothiazolinone preservatives, 0.15 wt% methylparaben, 0.01 wt% EDTA - 2NA, 0.5 wt% 1,2 - propanediol, and 96.74 wt% EDI pure water; wherein, the isothiazolinone preservatives include methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0086] A method for preparing the above complex, comprising the following steps:

[0087] 1) Add EDI purified water and EDTA - 2Na in sequence according to the raw material ratio, and stir and mix evenly;

[0088] 2) Add fatty alcohol polyoxyethylene ether - 9, dodecyldimethylamine oxide, propanediol, and methylparaben, and stir and mix evenly;

[0089] 3) Add isothiazolinone preservatives, and continuously stir until completely dissolved;

[0090] 4) Add citric acid to adjust the pH value to 6.2, and obtain the finished product after cooling and filtration.

[0091] After testing:

[0092] The detergency of the complex on the object surface reaches more than 99%, there is no obvious yellowing phenomenon after high - temperature treatment, and the reduction rate of isothiazolinone preservatives is 0.52%

[0093] According to the requirements of the GB15979 - 2024 standard for testing microbial indicators, it was measured within a 3 - day culture period:

[0094] Total number of bacterial colonies < 5 CFU / mL

[0095] Total number of fungal colonies < 5 CFU / mL

[0096] Measured by the microbial experiment for 28 days in the emulsion liquid model of the complex according to the anti-corrosion efficacy test method of the European Pharmacopoeia:

[0097] For Escherichia coli ATCC25922, Staphylococcus aureus ATCC6538, Pseudomonas aeruginosa ATCC15442, Streptococcus hemolyticus CICC10373 and Burkholderia cepacia CICC23648, the log 10 Reduction value ≥ 5.6; for Aspergillus niger ATCC16404, the log 10 Reduction value ≥ 4.4; for Candida albicans ATCC10231, the log 10 Reduction value ≥ 4.3;

[0098] And the microbial survival curves at the time points of 7 days, 14 days, 21 days and 28 days all meet the anti-corrosion standard of Grade A in the European Pharmacopoeia.

[0099] Example 11

[0100] An isothiazolinone anti-corrosion and decontamination complex, calculated by weight percentage, its raw materials include 2 wt% fatty alcohol polyoxyethylene ether-9, 0.2 wt% dodecyldimethylamine oxide, 0.4 wt% isothiazolinone preservative, 0.15 wt% propylparaben, 0.01 wt% EDTA-2NA, 0.5 wt% 1,2-propanediol, and 96.74 wt% EDI pure water; wherein, the isothiazolinone preservative includes methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounts for 2.5%).

[0101] A method for preparing the above complex, comprising the following steps:

[0102] 1) Add EDI purified water and the chelating agent EDTA-2Na in sequence according to the raw material ratio, and stir and mix evenly;

[0103] 2) Add the surfactant fatty alcohol polyoxyethylene ether-9 and dodecyldimethylamine oxide, the solvent propylene glycol and the stabilizer propylparaben, and stir and mix evenly;

[0104] 3) Add the isothiazolinone preservative and continue to stir until completely dissolved;

[0105] 4) Add citric acid to adjust the pH value to 6.2, and obtain the finished product after cooling and filtration.

[0106] After detection:

[0107] After high-temperature treatment, the composite shows no obvious yellowing phenomenon, and the reduction rate of isothiazolinone preservatives is 0.56%.

[0108] Comparative Example 1

[0109] An isothiazolinone-based anti-corrosion and decontamination composite, by weight percentage, its raw materials include 2 wt% fatty alcohol polyoxyethylene ether-9, 0.2 wt% dodecyldimethylamine oxide, 0.4 wt% isothiazolinone preservatives, 0.15 wt% p-hydroxyacetophenone, 0.01 wt% EDTA-2NA, 0.5 wt% 1,3-butanediol, and 96.74 wt% EDI pure water; wherein, the isothiazolinone preservatives include methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0110] A method for preparing the above composite, comprising the following steps:

[0111] 1) Add EDI purified water in sequence according to the raw material ratio, and stir and mix evenly;

[0112] 2) Add the surfactant fatty alcohol polyoxyethylene ether-9 and dodecyldimethylamine oxide, the solvent propylene glycol, and the stabilizer p-hydroxyacetophenone, and stir and mix evenly;

[0113] 3) Add isothiazolinone preservatives and EDTA-2Na, and continuously stir until completely dissolved;

[0114] 4) Add citric acid to adjust the pH value to 6.1, and obtain the finished product after cooling and filtration.

[0115] After testing:

[0116] After high-temperature treatment, the composite shows no obvious yellowing phenomenon, and the reduction rate of isothiazolinone preservatives is 0.95%.

[0117] Comparative Example 2

[0118] An isothiazolinone-based anti-corrosion and decontamination composite, by weight percentage, its raw materials include 2 wt% fatty alcohol polyoxyethylene ether-9, 0.2 wt% dodecyldimethylamine oxide, 0.4 wt% isothiazolinone preservatives, 0.15 wt% phenoxyethanol, 0.01 wt% EDTA-2NA, 0.5 wt% 1,2-hexanediol, and 96.74 wt% EDI pure water; wherein, the isothiazolinone preservatives include methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0119] A method for preparing the above-mentioned complex, comprising the following steps:

[0120] 1) Sequentially add EDI purified water and the chelating agent EDTA-2Na according to the raw material ratio, and stir and mix evenly;

[0121] 2) Add isothiazolinone preservatives and stir and mix evenly;

[0122] 3) Add the surfactant fatty alcohol polyoxyethylene ether-9, dodecyldimethylamine oxide, the solvent propylene glycol, and the stabilizer phenoxyethanol, and continuously stir until completely dissolved;

[0123] 4) Add citric acid to adjust the pH value to 6.5, and obtain the finished product after cooling and filtration.

[0124] After testing:

[0125] After high-temperature treatment, the complex has no obvious yellowing phenomenon, and the reduction rate of isothiazolinone preservatives is 0.92%.

[0126] Comparative Example 3

[0127] An isothiazolinone anti-corrosion and decontamination complex, by weight percentage, its raw materials include 2 wt% fatty alcohol polyoxyethylene ether-9, 0.2 wt% dodecyldimethylamine oxide, 0.4 wt% isothiazolinone preservatives, 0.15 wt% polyhexamethylene biguanide, 0.01 wt% EDTA-2NA, 0.5 wt% 1,2-pentanediol, and 96.74 wt% EDI pure water; wherein, the isothiazolinone preservatives include methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0128] A method for preparing the above-mentioned complex, comprising the following steps:

[0129] 1) Sequentially add EDI purified water and the chelating agent EDTA-2Na according to the raw material ratio, and stir and mix evenly;

[0130] ) Add the surfactant fatty alcohol polyoxyethylene ether-9, dodecyldimethylamine oxide, the solvent propylene glycol, and the stabilizer polyhexamethylene biguanide, and stir and mix evenly;

[0131] 3) Add isothiazolinone preservatives and continuously stir until completely dissolved;

[0132] 4) Add citric acid to adjust the pH value to 5.8, and obtain the finished product after cooling and filtration.

[0133] After testing:

[0134] After high-temperature treatment, the complex shows obvious yellowing, and the reduction rate of isothiazolinone preservatives is 52.45%.

[0135] Comparative Example 4

[0136] An isothiazolinone-based anti-corrosion and decontamination complex, by weight percentage, its raw materials include 2 wt% fatty alcohol polyoxyethylene ether-9, 0.2 wt% dodecyldimethylamine oxide, 0.4 wt% isothiazolinone preservatives, 0.15 wt% benzalkonium chloride, 0.01 wt% EDTA-2NA, 0.5 wt% 1,3-butanediol, and 96.74 wt% EDI pure water; wherein, the isothiazolinone preservatives include methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0137] A method for preparing the above complex, comprising the following steps:

[0138] 1) Add EDI purified water and the chelating agent EDTA-2Na in sequence according to the raw material ratio, and stir and mix evenly;

[0139] 2) Add the surfactant fatty alcohol polyoxyethylene ether-9, dodecyldimethylamine oxide, the solvent propylene glycol, and the stabilizer benzalkonium chloride, and stir and mix evenly;

[0140] 3) Add the isothiazolinone preservatives and continuously stir until completely dissolved;

[0141] 4) Add citric acid to adjust the pH value to 6.4, and obtain the finished product after cooling and filtration.

[0142] After testing:

[0143] After high-temperature treatment, the complex shows obvious yellowing, and the reduction rate of isothiazolinone preservatives is 56.43%.

[0144] Comparative Example 5

[0145] An isothiazolinone-based anti-corrosion and decontamination complex, by weight percentage, its raw materials include 2 wt% fatty alcohol polyoxyethylene ether-9, 0.2 wt% dodecyldimethylamine oxide, 0.4 wt% isothiazolinone preservatives, 0.01 wt% EDTA-2NA, 0.5 wt% 1,2-propanediol, and 96.74 wt% EDI pure water; wherein, the isothiazolinone preservatives include methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:1 (each accounting for 2.5%).

[0146] A method for preparing the above-mentioned composite, comprising the following steps:

[0147] 1) Sequentially add EDI purified water and the chelating agent EDTA-2Na according to the raw material ratio, and stir and mix evenly;

[0148] 2) Add the surfactant fatty alcohol polyoxyethylene ether-9, dodecyldimethylamine oxide, the solvent propylene glycol, and the stabilizer benzalkonium chloride, and stir and mix evenly;

[0149] 3) Add the isothiazolinone preservative and continuously stir until completely dissolved;

[0150] 4) Add citric acid to adjust the pH value to 6.0, and obtain the finished product after cooling and filtration.

[0151] After detection:

[0152] After high-temperature treatment, the composite has an obvious yellowing phenomenon, and the reduction rate of the isothiazolinone preservative is 50.34%.

[0153] Effect comparative example:

[0154] Test the yellowing situation and the reduction rate of the isothiazolinone preservative in Examples 10-16 above.

[0155] Yellowing situation: Respectively put Examples 10-16 into an oven at 54 °C, take them out after 30 days, observe the yellowing situation, and take pictures to compare the color changes.

[0156] Reduction rate of the isothiazolinone preservative: According to the detection method in DB34 / T3109-2018, first detect the isothiazolinone content in Examples 10-15 respectively, then put Examples 10-15 into an oven at 54 °C respectively, take them out after 30 days, and detect the isothiazolinone content again, and calculate the reduction rate of the isothiazolinone preservative before and after.

[0157]

[0158] It can be obtained from Examples 10-11 and Comparative Examples 1-5 that when methyl paraben, propyl paraben, p-hydroxyacetophenone, and phenoxyethanol in the present invention are mutually replaced, the effect of stabilizing the isothiazolinone preservative can be achieved; only in the presence of the benzene hydroxyl group preservative, the reduction rate of the isothiazolinone preservative is relatively low, there is no obvious yellowing situation, and the composite is relatively stable; it can be obtained from Examples 10, 11 and Comparative Examples 1-2 that the formulation schemes of Examples 10-11 are the best, and the reduction rate of the isothiazolinone preservative is lower than that of Comparative Examples 1-2, and the wiping effect diagrams are as Figure 4 and Figure 5 shown.

[0159] Finally, it should be noted that the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An isothiazolinone-based anti-corrosion and decontamination complex, by weight percentage, its raw materials are composed of 0.1 - 0.4 wt% isothiazolinone-based preservative, 0.06 wt% - 0.15 wt% benzene hydroxyl-based preservative, 1 - 2 wt% fatty alcohol polyoxyethylene ether-9, 0.1 - 0.2 wt% dodecyldimethylamine oxide, 0.005 - 0.05 wt% chelating agent, 0.3 - 2 wt% solvent and 95.2 - 98.44 wt% EDI pure water; the sum of the weight percentages of the above raw materials is 100%.

2. The isothiazolinone-based anti-corrosion and decontamination complex according to claim 1, wherein The isothiazolinone-based preservative includes methylisothiazolinone (MIT) and benzisothiazolinone (BIT), and the mass ratio of methylisothiazolinone (MIT) to benzisothiazolinone (BIT) is 1:

1.

3. The isothiazolinone-based anti-corrosion and decontamination complex according to claim 1, wherein The benzene hydroxyl-based preservative is selected from one or more of methylparaben, propylparaben, p-hydroxyacetophenone, phenoxyethanol.

4. The isothiazolinone-based anti-corrosion and decontamination complex according to claim 1, characterized in that, The complex also includes an acid-base regulator; the addition amount of the acid-base regulator makes the pH value of the complex 5.0 - 7.

0.

5. The isothiazolinone-based anti-corrosion and decontamination complex according to claim 4, characterized in that, The chelating agent is EDTA-2NA; The solvent is selected from any one or a combination of at least two of 1,2-propanediol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,2-decanediol or 1,10-decanediol.

6. The composite according to claim 4, wherein The decontamination force of the complex on the object surface reaches 98%.

7. The composite according to claim 4, wherein After 30 days of accelerated stability test at 54 ± 0.5 °C and detected by high performance liquid chromatography, the retention rate of the total content of isothiazolinone substances is ≥ 98.5%, and there is no obvious yellowing.

8. The composite according to claim 4, wherein When the complex is used as a water-based decontamination system, the microbial index requirements are tested according to the GB15979-2024 standard. During the 3-day culture period, it is measured that: The total number of bacterial colonies < 5 CFU / mL; The total number of fungal colonies < 5 CFU / mL; According to the anti-corrosion efficacy test method of the European Pharmacopoeia, in the emulsion model of the complex, after 28 days of microbial experiment, it is measured that: The log reduction values for Escherichia coli ATCC25922, Staphylococcus aureus ATCC6538, Pseudomonas aeruginosa ATCC15442, Streptococcus hemolyticus CICC10373, and Burkholderia cepacia CICC23648 are ≥ 5.6; for Aspergillus niger ATCC16404, the log 10 reduction value is ≥ 4.4; for Candida albicans ATCC10231, the log 10 reduction value is ≥ 4.3; 10 ​ And the microbial survival curves at the time points of 7 days, 14 days, 21 days and 28 days all meet the anti-corrosion standard of Class A in the European Pharmacopoeia.

9. A method for preparing the complex according to any one of claims 4-8, characterized in that, It includes the following steps: 1) Add the chelating agent according to the above raw material ratio and stir to mix evenly; 2) Add the isothiazolinone-based preservative, benzene hydroxyl-based preservative, fatty alcohol polyoxyethylene ether-9, dodecyldimethylamine oxide, solvent and EDI pure water, and continuously stir until completely dissolved; 3) Add the acid-base regulator to adjust the pH value to 5.0 - 7.0, and obtain the finished product after cooling and filtration.

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