WO2020243915A1 - Formula and method for immediately and quickly generating peracetic acid disinfectant - Google Patents

Abstract

Disclosed are a formula and method for immediately and quickly generating a peracetic acid disinfectant. According to the formula and method, the dissolution rate and temporary solubility of a solid acetyl compound in an aqueous solution is significantly increased without heating up, a high pH and continuous stirring or shaking at an ambient temperature greater than 10°C, resulting in quick generation of peracetic acid. The formula for immediately and quickly generating peracetic acid comprises a peroxygen donor, a solid acetyl compound, a pH adjuster and water, and may also comprise an alcohol, a surfactant and/or a peroxide stabilizer. These components can be divided into two parts for packaging and three parts for packaging, and these parts are mixed together before use. The present invention has the advantages of convenient carrying and use, fast generation of peracetic acid, and low corrosivity and toxicity.

Description

Formula and method for generating peroxyacetic acid disinfectant immediately and quickly Technical field:

The invention relates to an instant and rapid generation of peroxyacetic acid as a high-efficiency disinfectant for use in the fields of public, household, food, health care, medical equipment, wound treatment and the like.

Background technique:

As we all know, peroxyacetic acid (PAA) can be used as a high-level disinfectant, usually it can be produced by two methods: (1) equilibrium method; (2) non-equilibrium method. Most commercial PAA products are produced through the balance method. In this method, hydrogen peroxide (HP) reacts with acetic acid (AA) to form PAA, but it takes hours or even days to reach equilibrium. Obviously, the PAA generated by the balance method cannot be truly instantaneous PAA. Usually these commercial products contain high concentrations of PAA, HP and AA. Solutions containing more than 6% PAA are considered hazardous, and must be transported in the United States with the DOT mark "organic peroxide", hazard levels 5.2 and 8 (oxidizer, corrosive). The non-equilibrium method relies on the reaction of acetyl compounds and peroxygen donors under alkaline conditions to produce PAA. Commonly used peroxygen donors are HP, sodium perborate or sodium percarbonate. Acetyl compounds are also known as bleach activators, or PAA activators. The most commonly used bleach activators are tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulfonate (SNOBS), glycerol triacetate, glycerol diacetate and propylene glycol diacetate. However, SNOBS cannot produce PAA. In the non-equilibrium method, the rate of PAA generation mainly depends on the chemical and physical properties of the acetyl compound and the peroxygen supply, such as solubility, reactivity of the acetyl functional group, the alkalinity of the peroxygen donor and the pH of the solution. Other additives may have a positive or negative impact on PAA production.

Acetyl compounds can be divided into two groups at room temperature: one is liquid and the other is solid. Most acetyl compounds, whether liquid or solid, have low solubility in aqueous solutions at room temperature and a slow dissolution rate due to their hydrophobicity, which greatly limits the rapid generation of PAA.

1. Liquid group:

Glyceryl triacetate: Harvey et al. used it to generate peroxyacetic acid on the fly (Reference 1, Michael S. Harvey and Jonathan N. Howarth, WO2012128734A1). In the present disclosure, glycerol triacetate is used as a bleach activator in an overbased HP solution with an initial pH between 11.2 and 13.37. Its disadvantages are: 1) Under the condition of discontinuous shaking and stirring at 25°C, the solubility of triacetin in aqueous solution is low, which leads to low yield of PAA at pH<9.5; 2) PAA needs to be generated Very high pH (>11), which will lead to a significant decrease in the stability of PAA and PAA disinfection ability (see the influence of PAA solution pH value on disinfection ability below). Therefore, this is not a real instant disinfectant, and more details will be discussed in the detailed description of the present invention, liquid acetyl compounds.

Glyceryl diacetate and propylene glycol diacetate are used as bleach activators in disinfectants and sterilizers (reference 2. Mark D. Tucker, US 7,271,137 B2). The concentration of the bleach activator is 1-10% by weight. Glyceryl diacetate is water-soluble, but propylene glycol diacetate is insoluble in water. This invention describes a two-component system with an initial pH of <8. In these two-component systems, one part is composed of HP and sodium acetate. The latter is used as a pH adjuster, but carbonate cannot be used as a pH adjuster because it will cause the decomposition of HP. In addition, the patent does not show how long it takes after the two parts are mixed together to produce a sufficient concentration of PAA to kill the spores. In addition to the two-part system, other PAA generation systems use carbonate or other inorganic bases as pH regulators, with an initial pH of about 9.5. Based on our test results, glycerol diacetate and propylene glycol diacetate are not good bleach activators at pH ≤ 9.5 and cannot be used to quickly generate PAA. This point will be discussed in the detailed description of the present invention.

Preto, Andrea (Reference 3, EP 2 388 246 A1) discloses a two-liquid component system and a method for obtaining peroxyacetic acid (PAA) using this system. Its advantage is that it mixes bleach activator and pH adjuster (organic amine, such as N,N-diisopropylethylamine, which has weak or no nucleophilic properties), and has a long shelf life. This allows the PAA generation system to consist of two parts, mixed together before use. However, the disadvantages of this system are: (1) Most organic amines are volatile, toxic and flammable liquids, and the mixed solution needs to be stored in a well-sealed container to avoid evaporation; (2) Since the content of organic amines is small, They cannot be mixed well with solid bleach activators, which makes quantitative transfer difficult; (3) amines and acetyl compounds must be water-free to prevent decomposition of acetyl compounds; (4) N-acetyl caprolactam is very expensive and based on weight considerations The yield of PAA is lower than other acetyl compounds, such as sucrose octaacetate (SOA) and glucose pentaacetate (GPA), because it contains only one acetyl group and has a molecular weight of 155, while GPA has 5 acetyl groups. Its molecular weight is 390, that is, an acetyl group is equivalent to a molecular weight of 78; (5) The most important thing is that when N-acetyl caprolactam is poured into an aqueous solution, if it is not shaken vigorously, it will produce oily beads that are not easily soluble Precipitate, which is not very convenient for manually mixing large amounts of solution.

Copenhafer et al. disclosed a dilute and stable peroxyacetic acid production method (reference 4, US 2009/0043123 A1, submission date: August 6, 2008). In the present disclosure, PAA is produced by the reaction between HP and acetic anhydride. Acetic anhydride is easily hydrolyzed and highly reactive, which can cause trouble for storage and transportation. Moreover, its vapor is very toxic. The publication also describes "adjusting the pH of the aqueous solution containing the peroxyacetic acid reaction product to less than 8 as needed to provide a stable dilute peroxyacetic acid product". However, this additional pH adjustment is not very convenient for users.

2. Solid group:

In the solid group, TAED is the most commonly used bleach activator in detergent compositions. In addition to TAED, the composition also includes peroxides such as HP, percarbonate or perborate, pH adjuster and water, and other additives. The disadvantages of these compositions are: 1) the solubility of TEAD in water is very low (about 0.1% in water); 2) an elevated temperature (>40°C) is required to dissolve TEAD to a reasonable concentration; Renato Tabasso et al. A method for immediate production of a peracetic acid disinfectant system (reference 5, US 6,514,509 B2, February 4, 2003; reference 6, US 2003/0211169A1, November 13, 2003). In the present disclosure, tetraacetyl glycol (TAGU) and TAED are used as bleach activators. In order to make TAUG and TAED have sufficient solubility in water, the water temperature is increased to 70-80°C, and after cooling to 20°C, they are mixed with other components. After mixing, stir the solution continuously for about 15 minutes, and wait another 10 minutes before using it. Obviously, this method cannot produce PAA quickly, so it is not a real instant product.

One method shows that TAED becomes very soluble in water after adding a strong base such as sodium hydroxide (peroxide bleaching method. Reference 7, William, US Patent No. 8,858,650, July 2006 14th). However, TAED hydrolyzes quickly under strong alkaline conditions of pH 10, with a half-life of about 18 minutes (Reference 8. Table 4.1.1.5, pp15, TAED's HERA Target Risk Assessment, October 14, 2002). TAED The main hydrolyzate is N'N'-diacetylethylenediamine (DAED), its solubility in water is greater than 1000g/L, on the contrary, the solubility of TAED in water is about 1-2g/L (Table 3.1.2, pp8, HERA target risk assessment TAED, October 14) When TEAD loses one or more acetyl groups, its solubility in water will increase significantly, but the loss of one or more acetyl groups will result in the loss of the ability to generate PAA.

In the United States, laundry bleaching products are usually based on a combination of SNOBS and sodium perborate. The patent of Ronald Hage et al. can be used to bleach a substrate composition and method. (Reference 9, U.S. Patent #6,563,271, November 25, 2003). In the present invention, the shortcomings of TAED and SNOBS are discussed. For example, in countries where consumers have washing habits that require low dosage, short washing time, low temperature, and low detergent volume, the system cannot be bleached very effectively. In addition, SNOBS cannot generate PAA.

Wayne E. et al. disclosed the composition and preparation method of antimicrobial ice (reference 10, US 2009/0175956 A1). In this disclosure, it is mentioned that liquid and solid acetyl compounds are used as bleaching activators, and the pH of the solution is greater than 10. At such a high pH, peracetic acid is extremely unstable at room temperature and loses its disinfection ability. Although these problems can be solved by adding acid to lower the pH, it is very inconvenient for real instant use. In addition, this invention has not yet solved the problem of low solubility and dissolution rate of acetyl compounds in aqueous solutions.

Based on the above publications and invention patents, the PAA forming methods can only be used for washing and large-scale industrial applications, they are not suitable for small volume and real instant use. Generally, for the instant disinfectant, the PAA molecular concentration should be greater than 0.045% within a reaction time of less than 10 minutes and at low temperature to room temperature, and the maximum PAA concentration that can be achieved should not be greater than 0.2% to avoid strong irritation Sexual odor, which requires a very low concentration of acetyl compounds (usually about 2-8 mg/ml). For a 25mL instant disinfectant package, it contains less than 100mg of acetyl compounds (PGA and SOA are used as PAA activators). If a liquid acetyl compound is used, such a small amount can cause manufacturing and application problems. These problems are: 1) For 100mg of liquid acetyl compound, the packaging tolerance is low; 2) Even if the package can be manufactured, it is difficult to ensure that the liquid acetyl compound in the package can be used in a short time without special tools. Quickly and completely transfer from the packaging to the solution. For solid acetyl compounds, whether in powder or granular form, low solubility and low dissolution rate are always insurmountable obstacles to the rapid formation of PAA. Our experimental results show that it takes several hours to completely dissolve 0.12g TAED in a 50mL 3% HP solution with a pH of about 9 without continuously shaking the bottle. Therefore, it is obvious that TAED is not suitable for instant PAA generation without continuous stirring. Other solid acetyl compounds, such as GPA and SOA, have similar dissolution problems.

The present invention overcomes the above-mentioned problems and can quickly and instantly generate PAA as a high-efficiency disinfectant through ready-to-use packaging, which is very convenient for users.

The above-mentioned patents and patent publications do not teach how to improve the solubility and dissolution rate of insoluble acetyl compounds to realize the rapid generation of PAA as a high-efficiency disinfectant, except for the use of high pH, high temperature and continuous stirring and shaking. In other words, it is obvious that these methods cannot be used at ambient temperature, leading to real rapid and instant generation of PAA as a highly effective disinfectant for use in public, household, food, and medical and health fields.

references:

1.Ref 1. HARVEY, Michael, S, WO 2012128734 A1. WO2012128734A1, METHODS AND COMPOSITIONS FOR THE GENERATION OF PERACETIC ACID ON SITE AT THE POINT-OF-USE.

2.Ref2.Mark D.Tucker, US 7,271,137 B2.US7271137.

DECONTAMINATION FORMULATIONS FOR DISINFECTION AND STERILIZATION.

3.Ref.3.Preto, Andrea, EP 2388246A1.Two liquid component system and a process using such system for obtaining aperoxyacid (peracetic acid).

4.Ref.4.William C.Copenhafer,US 2009/0043123 A1,DILUTE STABILIZED PERACETIC ACID PRODUCTION AND TREATMENT PROCESS.

5.Ref5.Renato Tabasso, San Remo, US 6,514,509B2, METHOD FOR PRODUCTION ON THE SPOT OF A DS INFECTANT PERACETIC ACID SYSTEM, Feb. 4, 2003.

6.Ref6.Renato Tabasso, San Remo, US 2003/0211169 A1, DISINFECTANT PERACETIC ACID SYSTEM, Nov. 13, 2003.

7.Ref7. William Scepanski ,US Patent#8,858,650,July 14,2006,Filed:Jul 14,2008.

8.Ref.8.HERA Targeted Risk Assessment of TAED, Human&Environmental Risk Assessment on Ingredients of European household cleaning products.Oct. 14, 2002

9.Ref9. Simon Marinus Veerman, US Patent#6,653,271. Composition and method for bleaching a substrate Patent, Ronald Hage (Vlaardingen), Filed: Apr 1, 2002).

10.Ref 10. Wayne E. Buschmann, et al, US 2009/0175956 A1, METHOD OF PREPARRATION AND COMPOSITION OF ANTIMICROBIAL ICE.

11.Ref 11.Curties Donskey, US20170265463A1.Sopricidal Composition.

12.Ref 12.S.Leapers, Synergistic Killing of Spores of Bacillus Subtilis by Peracetic Acid and Alcohol, International Journal of Food Science&Technology 19(3):355-360June 1984.

Summary of the invention:

The purpose of the present invention is to overcome the shortcomings of the prior art, and provide a formulation and method that uses a non-equilibrium method to significantly improve the dissolution rate and temporary solubility of insoluble solid acetyl compounds in aqueous solutions to quickly generate peroxyacetic acid as a highly efficient Disinfectant. This formula and method can significantly increase the dissolution rate and temporary solubility of solid acetyl compounds in aqueous solutions without heating, high pH and continuous stirring or shaking at ambient temperature> 10°C, leading to rapid generation of peracetic acid . The so-called high-efficiency disinfectant must be able to kill spores, especially Bacillus atrophaeus Nakamura (ACCT9372). The present invention uses two methods to promote the rapid generation of PAA. 1) By increasing the temporary solubility of the insoluble solid acetyl compound in the aqueous solution, the generation rate of PAA can be significantly increased. The present invention first dissolves the solid acetyl compound in a mixed liquid of alcohol and water to form a mother liquid, and then mixes the mother liquid with the aqueous solution to obtain its temporary solubility far greater than its actual solubility; 2) by increasing the insoluble solid acetyl compound The effective surface area to increase its dissolution rate in aqueous solution, resulting in a significant increase in the rate of PAA generation. The present invention is to coat the insoluble solid acetyl compound on the fiber material to increase its effective surface area, thereby increasing its dissolution rate in an aqueous solution.

The key of the present invention is to increase the dissolution rate and temporary solubility of the solid acetyl compound in the aqueous solution without increasing the temperature, without the use of high pH and constant stirring or shaking, and to make the product produced in less than 10 minutes of reaction time. The concentration of PAA molecules is greater than or equal to 0.045%, and the maximum concentration that can be reached is preferably not greater than 0.2% to reduce the strong pungent odor brought by PAA. In the present invention, two methods and formulation types, solid-liquid type and liquid-liquid type, have been developed for different application purposes.

The formula for generating PAA immediately and quickly includes a peroxygen donor, a solid acetyl compound, a pH adjuster, and water, and may also contain additives. The additives are alcohols, surfactants and/or peroxide stabilizers. The components are divided into two-part packaging and three-part packaging. After mixing the parts together, the theoretical initial concentration of each component in the mixed solution is:

Peroxygen donor: 2-6%,

Acetyl ester compound: 0.2-1%,

Alcohol: 0-15%,

Surfactant: 0-0.4%,

Peroxide stabilizer: 0-0.02%,

The amount of pH adjuster is to make the initial pH of the mixed solution 8.2-9.5,

The rest is water.

The significant increase in the dissolution rate is achieved by coating the solid acetyl ester compound on the fibrous material to significantly increase its effective surface area, thereby leading to an increase in the dissolution rate, and as a result, the rapid production of peracetic acid PAA. This formulation component that leads to increased dissolution rate is packaged in two parts, the liquid part (Part A) and the solid part (Part B). Among them, part A mainly contains peroxygen donors and water, and can also contain other additives, such as alcohols and surfactants, and part B mainly contains solid acetyl compounds and pH regulators coated on the fiber material, and can also contain coating Other additives on fiber materials, such as peroxide stabilizers, etc.

To significantly improve the temporary solubility is to first dissolve the solid acetyl compound in an organic solvent or a mixed solution of organic solvent and water to form its mother liquor. When the mother liquor is mixed with the aqueous solution, the temporary solubility of the acetyl compound will be far greater than its actual solubility, and this condition can be maintained for at least 1 hour. This will lead to the rapid formation of peracetic acid (PAA), because as long as the acetyl compound is dissolved, it reacts with peroxy anions to form peroxyacetic acid (PAA) at a very fast rate. The components in this formulation to improve temporary solubility are packaged in three parts, namely part A, part B and part C. Among them, part A contains peroxygen donors and water, and can also contain other additives, such as alcohols and surfactants; part B is the mother liquor of acetyl ester, containing acetyl compounds and organics/water; part C contains pH regulator and water, and also Other additives such as peroxide stabilizers can be included.

The common feature of the above two formulas and methods is that at 25-10°C, after each part is mixed, it only needs to wait 4-10 minutes, and the mixed solution can be used as a high-efficiency disinfectant.

Within 10 minutes after all parts are mixed and when the ambient temperature is >10℃, the concentration of the generated peroxyacetic acid (PAA) molecules must be ≥0.045% and the highest concentration that can be reached is ≤0.4%, preferably ≤0.2 % To reduce the strong pungent odor caused by PAA.

The peroxygen donor is hydrogen peroxide (HP), or other compounds that can generate hydrogen peroxide in an aqueous solution, and its concentration is 2-6%, preferably 3-4%.

The solid acetyl compound is SOA or GPA, or other compounds with similar chemical and physical properties as SOA or GPA, and the initial concentration after all parts are fully mixed together is 0.2-1%; preferably 0.25-0.5%.

The pH adjuster is an inorganic base, such as sodium carbonate, or a mixture of sodium carbonate and sodium hydroxide, preferably a mixture of sodium carbonate and sodium hydroxide, and the amount used is to make the initial pH of the solution 8.2 after all parts are fully mixed -9.5, preferably 9.0-9.1;

The alcohol is ethanol or isopropanol with a concentration of 0-15%; preferably ethanol has a concentration of 5-9.9%.

Said surfactant is CTAC, sodium lauryl sulfonate or sodium lauryl sulfate, with a concentration of 0-0.4%; if used in the food and medical and health fields, 0% is preferred; such as to accelerate the generation of PAA , Preferably 0.05-0.09% CTAC, if cleaning function is required, preferably 0.1-0.2% CTAC, or 0.2-0.4% sodium lauryl sulfate.

The peroxide stabilizer is HEDP with a concentration of 0-0.02%; if it is used in the food and medical and health fields, it is preferably 0%; if it is used in other fields, it is preferably 0.005-0.009%.

The coating of the solid acetyl compound on the fibrous material or the coating of the solid acetyl compound on the fibrous material refers to coating SOA or GPA, or an acetyl compound with similar chemical and physical properties on white log paper, The coating density is 1-4 mg/cm ² , preferably GPA, and the coating density is 1.4-2.5 mg/cm ² .

The solid acetyl compound mother liquor is an SOA mother liquor or other solid acetyl compound mother liquors with similar chemical and physical properties to SOA, and the concentration of SOA in the mother liquor is 4-12%, preferably 6-7%;

The solid acetyl compound is dissolved in an organic solvent or a mixed solution of organic solvent and water to form a solid acetyl compound mother liquor. The solvent is a mixture of alcohol and water, especially a mixed solution of ethanol and water, or a mixed solution of isopropanol and water. Its concentration, ethanol: 70-95% v/v, preferably 90% v/v; isopropanol: 60-90% v/v, preferably 80% v/v.

The pH adjuster or the mixture of the pH adjuster and the peroxide stabilizer is coated on the fiber material, preferably they are coated on the polyester felt.

Compared with the prior art, the present invention has the following advantages:

The present invention provides the immediate and rapid generation of peroxyacetic acid by significantly improving the dissolution rate and temporary solubility of solid acetyl compounds in aqueous solutions when the ambient temperature is greater than 10°C and without the need for heating, high pH and continuous stirring or shaking. Used as a high-efficiency disinfectant formula and method. All the ingredients in the formula are divided into two parts or three parts, or called two-part packaging, or three-part packaging, which is very convenient for users to mix all the parts together before use. At 25-10°C, you only need to wait about 4-10 minutes after the parts are mixed, and the mixed solution can be used as a high-efficiency disinfectant. The disinfectant can be used for disinfection in public, household, food and medical and health fields. Especially two-part packaging, namely solid-liquid packaging, has obvious advantages in transportation, personal carrying, convenient use and safety. This is because it is not flammable and toxic, so there are no special restrictions on transportation and storage. , Besides, the operation during use is very convenient, no tools are needed, no heating and continuous stirring for a long time.

Attached drawings:

Figure 1: The relationship between the concentration of peroxyacetic acid (PAA) molecules and the total concentration of PAA and pH;

Figure 2a: The relationship between the killing effect of Staphylococcus aureus and pH;

Figure 2b: The relationship between the killing efficacy of Staphylococcus aureus and the concentration of peroxyacetic acid (PAA) molecules:

Note: KE=5 means that the killing effect is greater than the 5-log reduction in the number of colonies. The contact time is 2 minutes, and the experimental temperature is 20°C. The bacterial concentration is greater than 1.33×10 ⁷ colonies/mL. A mixture of sodium hydroxide and sodium carbonate was used to adjust the pH of the solution. This mixture contained 0.5 g NaCO 3, 0.5 g NaOH and 10 mL DW. The PAA solution includes 3% HP and is prepared by diluting 15% PAA and 30% HP. T= represents the total PAA concentration, and the molecular concentration is calculated based on the dissociation constant of PAA and pH.

Figure 3: Peroxyacetic acid (PAA) yield of different acetyl compounds:

Note: The test solution includes 3.2% HP and about 36 mM acetyl. The initial pH is about 9.04 and the test temperature is 20°C.

Except for acetyl compounds, all test solutions contain the same number of acetyl groups. This test can be used to compare the reactivity of acetyl groups in different acetyl compounds under the same reaction conditions;

Figure 4: The relationship between the yield of peracetic acid (PAA) and pH of glycerol diacetate:

Note: The solution includes 3.2% HP, 17.9mM glycerol diacetate, and the pH is adjusted by a mixture of sodium carbonate and sodium hydroxide. The reaction time is 6 minutes. 60-600ppm HEDP is used as a PAA stabilizer.

Figure 5: Peroxyacetic acid (PAA) yield diagram of different solid acetyl compounds in different treatment methods:

Note: The acetyl molar concentration of different acetyl compounds is the same, about 36mM; the initial pH is about 9.04, and the reaction temperature is 20℃.

Figure 6a, Figure 6b: The relationship between the yield of peroxyacetic acid (PAA) and reaction time when liquid-liquid packaging is at 25°C:

Note: The initial concentration of the mixed solution includes 3% HP, 4.2 mg/mL SOA, 9.5% ethanol, and the initial pH is about 9.04, which is adjusted by the mixture of NaOH and Na ₂ CO ₃ ;

Note: "No" means that CTAC and HEDP are not added to the above mixed solution; 50ppm and 100ppm represent the HEDP concentration in the above mixed solution; 0.09% means the CTAC concentration in the above mixed solution;

Figure 7: The graph of the influence of SOA concentration on the productivity of peracetic acid (PAA):

Note: The test solution includes 3% HP and different concentrations of SOA. The initial pH is adjusted to about 8.9 by a mixture of NaOH and Na ₂ CO ₃ . The temperature is 25℃;

Figure 8a, Figure 8b: The influence of liquid-liquid packaging temperature on the yield of peroxyacetic acid (PAA):

Note: The initial concentration of the three parts after mixing: 3% HP, 9.8% EOH, 0.42% SOA, and 0.06% CTAC (only for Figure 8b), the initial pH is about 9.03.

Figure 9: Example diagram of solid-liquid packaging;

Figure 10: A graph of the influence of temperature on the production and use period of peracetic acid (PAA):

Note: The composition of the liquid is listed in Table 7. SOA is used as the PAA activator;

Figure 11a, Figure 11b: The effect of CTAC on the production rate and service life of peracetic acid (PAA) at 20°C:

Note: CTAC concentration is 0% or 0.09%; the composition of the liquid is listed in Table 8. GPA is used as PAA activator;

Figure 12: The influence of the concentration of hydrogen peroxide (HP) on the yield of peracetic acid (PAA):

Note: After A&B is mixed, the solution initially contains: 2.2mg/mL SOA (SOA coated on paper), 0.16% CTAC and different concentrations of hydrogen peroxide (HP), adjusted by the mixture of sodium carbonate and sodium hydroxide The initial pH is about 8.6, and the test temperature is between 20-21°C.

Figure 13: When SOA is used as PAA activator, CTAC influences the yield of PAA

Note: The solution includes 3% HP, 2.2mg/mL SOA (coated on paper), and the initial pH is about 9.02 adjusted by a mixture of sodium carbonate and sodium hydroxide, and CTAC of different concentrations. The test temperature is 25°C.

Detailed ways:

In order to deepen the understanding of the present invention, the present invention will be described in further detail below in conjunction with examples. The examples are only used to explain the present invention and do not constitute a limitation on the protection scope of the present invention.

The present invention provides a formula and method for quickly and instantaneously producing PAA through a non-equilibrium method even at low temperatures, which can be used as a high-efficiency disinfectant. High-efficiency disinfectants must be able to kill spores, especially Bacillus atrophaeus Nakamura (ACCT9372). The key to the rapid and immediate generation of PAA is to increase the dissolution rate and temporary solubility of the solid acetyl compound in the aqueous solution without increasing the temperature, without constant stirring or shaking, so that the generated PAA molecules can be generated within a reaction time of less than 10 minutes. Concentration ≥0.045%. In the present invention, two methods and formulation types (liquid-liquid and solid-liquid) have been developed for different application purposes. Liquid-liquid packaging mainly promotes the rapid generation of PAA by increasing the temporary solubility of solid acetyl ester compounds, while solid-liquid packaging mainly increases the dissolution rate of solid acetyl ester compounds by increasing the effective surface area, resulting in rapid PAA generate.

1. Liquid-liquid packaging (suitable for packaging >500mL): In this packaging, the components of the formula are divided into three liquid parts, A, B and C.

Part A: A liquid contains HP and water, if necessary, alcohol and surfactants;

Part B: A liquid contains a solid acetyl compound dissolved in a mixture of ethanol and water, isopropanol and water or other alcohol and water, and the solid acetyl compound is preferably SOA;

Part C: A liquid includes alkali and water. If necessary, it may also include surfactants and peroxide stabilizers.

The present invention mainly aims to solve the problem of low solubility of solid acetyl compounds in aqueous solutions, even if these solutions contain up to 10% ethanol.

The solubility of several solid acetyl compounds was tested, such as glucose pentaacetate (GPA), sucrose octaacetate (SOA) and tetraacetyl ethylene diamine (TAED). TAED has low solubility in aqueous solutions and the most common organic solvents (such as alcohols, ethyl acetate, acetone and acetonitrile). Therefore, TAED cannot be used for rapid PAA generation under discontinuous stirring and heating (>40°C) conditions. GPA shows very low solubility, about 1 mg/mL in water; about 7 mg/mL in absolute ethanol. However, it is very soluble in some organic solvents, such as acetonitrile and ethyl acetate. However, if the GPA/organic solution is mixed with the aqueous solution, GPA will precipitate quickly. Therefore, as a liquid-liquid formulation, GPA is not suitable for rapid generation of PAA.

The solubility of SOA in water is also very low (≤0.7mg/mL at 20℃), it is also very low in 10% ethanol (≤1.5mg/mL at 20℃), and it is not very soluble in absolute ethanol and isopropyl alcohol. Propanol, but its solubility in methanol, ethyl acetate and acetonitrile is very high. However, methanol and acetonitrile are very toxic, and ethyl acetate has a strong odor. If the SOA/ethyl acetate solution is mixed with the aqueous solution, precipitation will occur. Therefore, these solvents are not conducive to public, personal, food and medical and health applications, and will not cause rapid PAA generation.

Surprisingly, our test results show that SOA is very soluble in 90% ethanol/water, or 80% isopropanol/water, most likely in other alcohol/water solutions with special ratios. In 90% ethanol/water, the SOA solubility is ≥12% at 25°C and ≥6% at 10°C.

Very unexpectedly, if SOA is first dissolved in 90% ethanol (SOA mother liquor), and then mixed with water or HP aqueous solution, the temporary solubility of SOA can reach at least 3mg/mL at about 20°C for about one hour Later, SOA precipitation will be observed. At this temperature, the actual solubility of SOA in water is less than 0.7 mg/mL. If the SOA mother liquor containing 6% SOA is mixed with the HP aqueous solution containing about 3% ethanol, the temporary solubility can be greater than 8mg/mL at 20°C, and after about 1 hour, SOA precipitation is observed. If the SOA concentrate is mixed with an HP solution with an initial pH of about 9, the temporary solubility can reach 8 mg/mL. Within 3-10 minutes after all the components (above A, B and C) are mixed, if the SOA concentration range is 3-8mg/mL, the temperature is ≥10℃, and the pH is about 9, it is enough to quickly and instantly generate PAA used as a highly effective disinfectant. As a disinfectant in public, household, food and medical and health fields, the concentration of PAA molecules is between 0.035% and 0.2%. As a high-efficiency disinfectant, the molecular concentration of PAA should be ≥0.045%, and when it reaches the maximum value, the concentration of PAA should be ≤0.2% to reduce the strong irritating odor produced by PAA, which requires the SOA concentration to be about 4mg /mL. When SOA mother liquor (1.0g SOA dissolved in 19mL of 90% ethanol/water) is mixed with HP solution with a pH of about 9%, the initial concentration of SOA is about 4.2mg/mL. Under the condition of 20℃, the concentration of PAA It can reach more than 0.06% in 5 minutes, and its maximum PAA concentration can reach 0.17%. This concentration range is sufficient to kill the spores of Bacillus subtilis (ACCT9372) in less than 10 minutes of contact time, with a killing rate greater than 5 log values.

The advantages of using ethanol/water or isopropanol/water to prepare SOA mother liquor: 1) When SOA mother liquor is mixed with HP solution, its temporary solubility far exceeds its actual solubility without precipitation within one hour, which will cause PAA Generate quickly. Other solvents, such as ethyl acetate, are not suitable because SOA will precipitate quickly. 2) Ethanol and isopropanol can also significantly improve the sporicidal ability (Reference 11, Reference 12). 3) SOA will not hydrolyze in SOA mother liquor, which is very important for long storage period (at least 2 years).

The key of the present invention is to make SOA temporarily soluble, and its concentration is much higher than its actual solubility in aqueous solution, which can significantly accelerate the rapid formation of PAA.

2. Solid-liquid packaging (preferably suitable for 10-500mL): In this packaging, the components of the formula are divided into two parts, A and B.

Part A (liquid): contains HP and water, if necessary, alcohol, and surfactants.

Part B (solid): Contains a solid acetyl compound and a pH adjuster, and can also contain a peroxide stabilizer if necessary. The solid acetyl compound will be applied as a coating on the fibrous material to form a very thin coating, which will significantly increase the effective contact area between the solid acetyl compound and the liquid component, resulting in rapid diffusion of the solid acetyl compound into the liquid phase . As long as the acetyl compound diffuses into the solution, it quickly reacts with the HP anion to form PAA. A small amount of pH adjusters and stabilizers are also coated on the fiber or felt, which will also help the solid pH adjusters and stabilizers to quickly dissolve into the liquid. The solid acetyl compound must be easily soluble in a low boiling point organic solvent, such as methanol, acetonitrile, ethanol or their mixture. This allows the smallest possible amount of acetyl compound solution to be used to wet the fiber and allow it to dry quickly to form a thin acetyl compound coating on the fiber. These acetyl compounds include SOA, GPA, but not TAED, because it is insoluble in these solvents. SOA and GPA are non-toxic, have relatively high solubility in the above-mentioned organic solvents, and are relatively economical to use. SOA has also been approved as a food additive. However, the acetyl functional group of GPA appears to be more reactive than the acetyl functional group of SOA. Since the solid part contains a pH adjuster (alkali), the liquid acetyl compound is not suitable for coating on the fiber or packaged with the pH adjuster, otherwise the liquid acetyl compound may react with the pH adjuster to form acetate, which will reduce Shelf life of acetyl compound and pH adjuster.

The fiber and felt materials should not react significantly with PAA and other components in the disinfectant to ensure that the mixed disinfectant has a relatively long service life.

Two-part packaging has obvious advantages: 1) The operation when the two parts are mixed is very convenient for users, without the use of tools; 2) When GPA is used as a PAA activator, it does not require continuous stirring or shaking and at 20°C. Under the conditions, only about 5-6 minutes after mixing, its PAA concentration (PAA molecular concentration ≥0.045%) can meet the requirements of high-efficiency disinfectant, and its maximum concentration is less than 0.2% to avoid high concentrations of PAA. 3) Because of its low toxicity and low irritation, it is easy to carry and transport, and it is also very suitable for applications in the fields of medical and health and food; 4) The shelf life of each part is more than 2 years; 5) At 20℃ The shelf life can be up to two weeks, and it can be stored for several months at 4°C.

The key of the present invention is to significantly increase the dissolution rate of the solid acetyl compound, which will lead to the rapid generation of PAA.

Experimental results related to the present invention: These experimental results can deepen the understanding of the novelty and unexpectedness of the present invention.

The influence of the pH value of PAA solution on the disinfection ability: First, it is very important to understand the relationship between the disinfection ability of PAA and the pH value. The reasons are: 1) Non-equilibrium method usually produces PAA under alkaline conditions; 2) PAA It is a weak acid with a dissociation constant pKa of 8.2 (see the following reaction formula).

This reaction formula determines that the concentration of PAA molecules decreases with increasing pH. When the pH is greater than 7, the concentration of PAA molecules decreases significantly as the pH increases (Figure 1). Our test results show that as the pH increases, the microbicidal ability decreases (Figure 2a), and the concentration of PAA molecules affects this killing ability (Figure 2b). Even if the total PAA concentration (molecule + ion) is 0.5%, its killing efficiency is significantly reduced when the pH is 9.51, because the PAA molecule concentration is about 0.023% at this pH. The test results clearly show that the concentration of PAA molecules rather than the total PAA concentration dominates the killing efficacy (Figure 2b). According to the test results, at 20°C and a contact time of 2 minutes, a PAA molecular concentration of >0.03% is sufficient to kill Staphylococcus aureus with a killing rate greater than 5-log (Figure 2b).

In addition, preliminary test results show that as the pH value increases, the killing effect of PAA on black var. subtilis (ACCT9372) will decrease. For example, at 20°C and a contact time of less than 10 minutes, a 5-log kill rate to kill the black mutant subtilis spores, the molecular concentration of PAA is required to be greater than >0.045%.

Conclusion: As the pH value increases, the bactericidal ability of PAA decreases, especially when pH>7.2. As a high-efficiency disinfectant, the concentration of PAA molecules should be greater than 0.045%. Therefore, to develop a non-equilibrium method to generate PAA as an effective disinfectant, not only the total concentration of PAA must be considered, but also the pH value of the solution.

Selection of Acetyl Compounds: The main problem of generating PAA quickly and instantaneously by non-equilibrium methods is the low solubility and dissolution rate of acetyl compounds in aqueous solutions and the reactivity of acetyl functional groups under different pH conditions.

1. Liquid acetyl compounds: As mentioned above, liquid acetyl compounds are not a good choice. The main reasons are: 1) the packaging and transfer of a small amount of liquid; 2) the water solubility of triacetin and propylene glycol diacetate problem. When glycerol triacetate or propylene glycol diacetate is mixed with water, oily particles are observed, which will result in a low PAA yield. At the initial pH of about 9 and 20°C, triacetin is used as a PAA activator. At a reaction time of 10 minutes, the PAA concentration is only about 0.031% (Figure 3), which is not high enough to be used as a high Horizontal disinfectant; 3) Even under the condition of complete dissolution of glycerol diacetate, the PAA production at an initial pH of about 9 is low (the concentration at 10 minutes is about 0.022%, Figure 3). In order to increase the production of PAA, the initial pH needs to be increased (Figure 4). If the initial pH is 9.9, when the total PAA concentration is 0.166% after 25 minutes of reaction, the pH drops to 9.13, which results in a PAA molecule concentration of about 0.017% (Table 1). The concentration of this molecule is not sufficient to kill Staphylococcus aureus with a 5-log kill rate in a 2-minute contact time (see Figure 2). This means that a solution with an initial pH of 9.9 cannot be a real high-efficiency disinfectant for immediate use.

Conclusion: Liquid acetyl compounds, such as glycerol diacetate, glycerol triacetate and propylene glycol diacetate, are not suitable for immediate production of high-efficiency disinfectant PAA due to their low solubility or low reactivity leading to low PAA production Activator.

Table 1. When glycerol diacetate is used as a PAA activator, the reaction time and the total concentration of PAA, and the relationship between the concentration of PAA molecules and pH

Note: The solution includes 3.2% HP, 17.9mM glycerol diacetate (about 36mM acetyl), a mixed solution of sodium carbonate and sodium hydroxide for pH adjustment, HEDP (60-600ppm) is used as a PAA stabilizer, and the temperature is 20℃ .

2. Solid acetyl compounds: Most solid acetyl compounds, such as TAED, SNOBS, GPA and SOA, have the problem of low water solubility. When a solid acetyl compound is used as a PAA activator, in order to increase the rate of PAA generation, the present invention is to increase the dissolution rate and temporary solubility of the solid acetyl compound in an aqueous solution instead of increasing the pH and temperature, and use continuous stirring or shaking. . The present invention uses the following two methods to promote the immediate and rapid generation of PAA.

1) Increasing the temporary solubility of solid acetyl compounds: There are two simple methods to increase the solubility, such as using a high concentration of organic solvent and/or increasing the temperature. But these methods are not truly instantaneous generation of disinfectants that can be used in public, household, personal, food and medical and health fields. Our research results show that TEAD is insoluble in most common organic solvents, such as methanol, acetonitrile, ethyl acetate, ethanol, isopropanol, etc. SOA is soluble in methanol, acetonitrile and ethyl acetate, while GPA is soluble in acetonitrile, ethyl acetate, and a mixture of acetonitrile and alcohol, but at room temperature, they are not very soluble in pure ethanol and isopropanol, especially It is almost insoluble in water, HP solution and 10% ethanol aqueous solution.

The solubility test results show that the solubility of SOA in pure ethanol is ≤ 3% (w/v) and ≤ 1% (w/v) at 25 ℃ and 10 ℃, and the solubility at 20 ℃, in water and In 3% HP solution ≤ 0.7mg/mL, in 3% HP solution containing 10% ethanol ≤ 1.5 mg/mL, the dissolution rate of solid SOA powder is very slow, requiring continuous shaking. The low solubility and dissolution rate limit the rapid generation of PAA.

Surprisingly, our test results show that SOA has a high solubility in 90% ethanol or 80% isopropanol. The solubility in 90% ethanol is at least 12% (w/w) at 25°C and at least 6% (w/w) at 10°C. When 1.0 g of SOA was first dissolved in 19 mL of 90% ethanol to form a SOA mother liquor, and then the mother liquor was mixed with an aqueous solution. At about 20°C, the SOA solubility was at least 3 mg/mL, and no precipitation occurred within one hour. One hour later, SOA precipitation appeared. This result indicates that the temporary solubility of SOA can be increased to ≥3mg/mL in water at 20°C, which is far greater than its actual solubility in aqueous solution (≤0.7mg/mL). When SOA mother liquor is mixed with HP solution containing 3% ethanol, the temporary solubility of SOA can reach more than 8mg/mL at 20°C, and no turbidity and precipitation are observed during mixing. However, after about an hour, SOA precipitation appeared. Fortunately, the reaction between dissolved SOA and hydrogen peroxide anion is very fast. Therefore, the temporary high solubility of SOA can be used to promote the rapid generation of PAA. More importantly, the storage period of SOA mother liquor is more than two years. This result indicates that SOA hardly hydrolyzes in an aqueous solution. This is different from most other acetyl compounds, which are relatively easy to hydrolyze in aqueous solutions. As a commercial product, the storage period is a very important consideration.

GPA is not easily soluble in ethanol, isopropanol, ethanol/water and methanol, but it is very soluble in acetonitrile. If the GPA mother liquor (1.0g GPA in 19mL acetonitrile) is mixed with the aqueous solution so that the GPA concentration is >4mg/mL, GPA will precipitate rapidly. Therefore, GPA does not have the solubility characteristics of SOA. In addition, TAED is not easily soluble in the above-mentioned solvents, so the temporary high solubility in aqueous solution cannot be obtained by the above-mentioned method.

Our experimental results show that the acetyl groups in SOA seem to be more reactive than those in triacetin and diacetin (Figure 3). At a reaction time of 6 minutes and at 20°C, the PAA concentrations from SOA, glycerol triacetate and glycerol diacetate were about 0.062%, 0.024% and 0.018%, respectively. SOA and glycerol diacetate are comparable because both are completely dissolved. Glyceryl triacetate has a low PAA concentration, probably due to incomplete dissolution and low reactivity.

2) Increase the dissolution rate of solid acetyl compounds: The dissolution rate of most solid acetyl compounds in aqueous solutions is very slow, because the dissolution rate is controlled by its diffusion rate in the solution. Generally, four methods can be used to increase the dissolution rate of solid acetyl compounds in aqueous solutions: (1) Continuously stirring or shaking the solution; (2) Increase the temperature; (3) Use high-concentration organic solvents; (4) Increase the solid acetyl group The effective surface area of the compound. Methods (1) and (2) are not very convenient for instant PAA generation, while method (3) is not suitable for applications in public, household, food, medical and health fields. Although granular and very fine powders can increase the surface area to increase the dissolution rate, the particles cannot increase their effective surface area too much because the surface in contact with the liquid still has the problem of slow diffusion. Very fine powders tend to aggregate, especially for those acetyl compounds with hygroscopicity, which will reduce their effective surface area. In our invention, acetyl compounds are deposited on the fibers as a coating to increase their effective surface area, which results in a significant increase in the dissolution rate. SOA and GAP are easily soluble in most volatile organic solvents, such as acetonitrile, ethyl acetate and mixtures of alcohol and acetonitrile. When SOA or GAP is dissolved in an organic solvent, and then applied to the fiber and dried, a very thin layer is formed on the fiber, which will significantly increase their dissolution rate and promote the rapid and immediate generation of PAA. Experimental results show that acetyl compounds coated on paper can promote the rapid generation of PAA more than particles and fine powders (Figure 5).

in conclusion:

1. Solid acetyl compounds, such as SOA, can obtain temporarily high solubility, thereby significantly increasing the yield of PAA.

2. Solid acetyl compounds such as SOA and GPA exhibit higher reactivity than liquid acetyl compounds such as glycerol diacetate and glycerol triacetate.

3. The solid acetyl compound coated on the fiber shows a greater dissolution rate than its particles and powders, which leads to the rapid generation of PAA.

example

1. Liquid-liquid formula: This liquid-liquid formula is based on the SOA being very soluble in 90% ethanol/water or 80% isopropanol/water to form SOA mother liquor, and then mixing the mother liquor with the aqueous solution to obtain a temporary high Solubility. When the SOA mother liquor is added to a solution containing about 3.3% HP and 4% ethanol, or a 3.3% HP solution (initial pH is about 9), if there is no shaking, a small amount of SOA precipitation (a bit turbid) may sometimes be observed, which It depends on the concentration and temperature of SOA in its mother liquor. The lower the SOA concentration, the less or no precipitation was observed (Table 2).

Table 2. The influence of SOA concentration in SOA mother liquor on precipitation at 20℃

Note: *Incomplete dissolution (turbid solution), but when alkali is added to make the initial pH value about 9, SOA will be completely dissolved.

The solubility of SOA in 90% ethanol is very sensitive to temperature. Only the mother liquor containing 6% SOA will not produce SOA precipitation at 10°C. Therefore, if used at a temperature of about 10°C, the concentration of SOA in the mother liquor cannot be greater than 6% (w/w).

Only at 10°C, when the 6% SOA mother liquor and the 3.3% HP solution are mixed at about the initial pH 9.04 and the SOA concentration is about 4.2 mg/mL, the solution will become turbid for a while and then become clear. If shaken once, the solution is always clear. This result shows that 4.2mg/mL SOA can be completely dissolved temporarily at 10°C, and its concentration is much greater than its actual solubility at 10°C (estimated to be less than 0.3mg/mL). However, if the temperature is ≥15℃, no turbidity is found regardless of shaking.

At about 18°C, when the 6% SOA mother liquor was mixed with 5 liters of a solution containing 3.3% HP and 4% ethanol with an initial pH of about 9.04, no turbidity or precipitation was observed. At this time, the SOA concentration is about 4.2 mg/mL. The mixed solution at this time contains about 10% ethanol, but the actual solubility of SOA in 10% ethanol is less than 1.5%. In this mixing, there is no need to shake, it is like mixing two miscible solutions. This is one of our inventions.

Examples of general formulations for the liquid-liquid method are listed in Table 3. Based on this general formula, the effects of reaction time, SOA concentration, additives, temperature and pH on PAA production were tested.

Table 3. Example 1: General composition of liquid-liquid packaging.

Note: HP, hydrogen peroxide; CTAC, cetyltrimethylammonium chloride; EOH, ethanol; HEDP, hydroxyethylidene diphosphonate, SOA, sucrose octaacetate; alkali is sodium carbonate and hydroxide A mixture of sodium and deionized water.

(1) The effect of reaction time on PAA production concentration and use period: Figure 6 shows that PAA concentration increases very quickly during the first 6 minutes. When the reaction time is 5 minutes, if there are no additives (CTAC or/and HEDP), the PAA concentration is about 0.068%. If there are additives, the PAA concentration is greater than 0.06% within the 4-minute reaction time. This result means that at 25°C, after all the parts are mixed, the PAA concentration can reach the required concentration of high-efficiency disinfectant in only 4-5 minutes (Figure 6a), and between 1-8 hours after mixing, The maximum PAA concentration of 0.14% and 0.16% can be obtained. CTAC has a negative effect on the use period, but HEDP can increase the use period (>10 days, Figure 6b).

(2) The influence of SOA concentration on PAA production: The following reaction equations 1 and 2 show how to produce PAA through a non-equilibrium method.

Formulas 1 and 2 clearly show that the concentration of acetyl compound and HP as well as pH affect the yield of PAA. Our experimental results confirmed that as the SOA concentration increases, PAA production will increase (Figure 7). If you want to increase the PAA production rate and maximum concentration, one of the methods is to increase the concentration of acetyl compounds. However, if the maximum concentration is too high, it will produce an unacceptable pungent odor, which is not suitable for use in public places, homes, and medical and health occasions.

(3) The effect of additives on PAA: Experimental results show that CTAC increases the rate of PAA production, but it may have a negative impact on the life of PAA due to its reduction characteristics (Figure 6 and Figure 8). The experimental results also show that HEDP can stabilize PAA and slightly increase the rate of PAA generation. If the HEDP concentration is 50-100 ppm, the pot life of the mixed solution is greater than 10 days at 25° C., and the maximum PAA concentration can be about 0.16% (Figure 6b). If there are no additives in the mixed solution, the service life at 25°C is about 8 days (Figure 6b). For applications in the medical and health and food industries, no additives are very important. The molecular concentration of PAA whose lifetime threshold is greater than 0.045%.

(4) The effect of temperature on PAA products: It is well known that temperature not only affects the solubility, but also affects the rate of chemical reactions. Disinfectants may be used at different temperatures, especially at low temperatures. TAED and other solid acetyl compounds cannot be used as acetyl donors to instantly generate PAA and used as daily disinfectants in public, home, and medical care because of their poor solubility and slow dissolution rate at room temperature and low temperature. However, SOA can be used as a PAA activator at relatively low temperatures by significantly increasing its temporarily high solubility. The test results show that the liquid-liquid formula is within the range of 25-10℃, and it only takes about 4-10 minutes to obtain PAA with high-efficiency disinfectant level, and CTAC can shorten the waiting time (Figure 8).

(. 5) Effect of pH: PAA generation reaction based on Formulas 1 and 2 can be expected to increase the pH will increase [HOO ^-] concentration, which leads to increased yield PAA. However, it should be pointed out that although high pH will lead to high PAA production, it may have a negative impact on the bactericidal ability of PAA, because the killing effect is mainly determined by the concentration of PAA molecules rather than the total concentration (Figure 2). Because the molecular concentration is affected by pH (Figure 1), the conclusion is that pH affects the microbicidal ability of PAA. Table 4 shows how the pH changes with the reaction time. After all the parts are mixed together, as the reaction time increases, the pH of the solution will continue to decrease, because the alkali in the solution is gradually being consumed. When all the parts are mixed together, it takes about 4 or 5 minutes at 25°C, and this mixture can be used as a high-efficiency disinfectant (Table 4 and Figure 6a). When HEDP is present, the concentration of PAA molecules is always lower than that when it does not exist. This is because the presence of HEDP makes the pH of its solution higher than that without HEDP. This is probably due to the pH buffering capacity of HEDP. In fact, the total PAA production with HEDP was greater than without HEDP (Table 4 and Figure 6a).

Table 4. The effect of pH on the concentration of PAA molecules

Note: The experimental temperature is 25℃. The test solution contains 3% HP, 0.42% SOA, 6% ethanol, with an initial pH of 9.03, and a mixture of sodium carbonate and sodium hydroxide is used to adjust the pH.

The experimental results in Table 1, Figure 2 and Table 4 indicate that increasing the initial pH to increase PAA production is not a useful method. This factor must be considered when developing instantaneous PAA as a highly effective disinfectant. If PAA is used as a bleaching agent, high pH can increase PAA's oxidizing ability, but if PAA is used as a bactericide, as the pH increases, the bactericidal ability decreases because the two have different mechanisms of action.

2. Solid-liquid formula: The solubility of solid acetyl compounds is poor, and the slow dissolution rate is the main obstacle to the rapid formation of PAA. In order to accelerate the formation of PAA, another method is to increase the dissolution rate of the solid acetyl compound so that it quickly reaches an acceptable concentration. Although the liquid-liquid method can temporarily increase the solubility of SOA, its shortcomings are: 1) It is not very convenient for users to divide into three parts to package; 2) quantitative mixing of a small amount of three parts is not easy to achieve in normal use, especially For small packages, such as 25-mL and 50-mL, because a small amount of SOA precursor is used; 3) The presence of high concentration of alcohol in the SOA mother liquor is flammable; 4) So far, only temporary high solubility of SOA has been found . To overcome these shortcomings, solid-liquid packaging was developed. This method mainly focuses on increasing the dissolution rate of solid acetyl compounds. In order to increase the dissolution rate, there are many methods, such as using organic solvents, increasing the temperature, continuous stirring or shaking, and increasing the surface area of the solid acetyl compound. Using organic solvents, continuous stirring/shaking and heating is not a really good way to instantly generate disinfectants in public, food, home, and healthcare applications. Therefore, the best option is to increase the surface area of the solid acetyl compound. TAED and SNOBS use granular and powder forms in laundry powder formulations, but their limited effective surface area does not significantly increase their dissolution rate.

In the present invention, solid acetyl compounds are coated on fibrous materials to significantly increase their effective surface area, which will lead to a significant increase in their dissolution rate, so that a faster PAA generation rate than granules and powders can be obtained (Figure 5). In order to coat the solid acetyl compound on the fiber material, the acetyl compound must be dissolved in some common volatile organic solvents at a high concentration, such as methanol, acetonitrile or their mixture, or a mixture of ethanol and acetonitrile. Our test results show that TAED is not easily soluble in these solvents, but SOA and GPA are very soluble and can be coated on the fiber in a very thin layer.

The solid-liquid package consists of two parts, one part is the solid part, including solid acetyl compound coated on fibrous materials, such as raw wood paper, and pH buffer (sodium carbonate and sodium hydroxide, if necessary, also contains peroxide stabilizers The mixture) is coated on a fiber material, such as polyester felt, and the other part is a liquid part, including HP and water, and if necessary, it can contain surfactants, alcohol, etc. The solid part is contained in a small plastic bottle, and the liquid part is contained in a relatively large plastic bottle (Figure 9). The shelf life of each component is more than 2 years at 25°C. To use, pour the solid part (in a vial) into the liquid part (HP solution is filled in a relatively large bottle), shake for 1 minute, and then activate for about 4 to 10 minutes, the solution will become highly effective Disinfectant. The waiting time depends on the temperature. The higher the temperature, the shorter the reaction time. Of course, if the concentration of solid acetyl groups is increased, the waiting time can be shortened, but this will increase the maximum concentration of PAA. High PAA concentration (usually >0.2%) will produce unacceptable pungent odor, so it is not suitable for applications in public, household and public health fields. More importantly, this formula and packaging form is very convenient to carry and use.

In addition, the fiber material cannot react with the components in the package and the mixed solution. Pure cotton fiber materials are not suitable because they will react with peracetic acid. Polyester felts are better than pure cotton materials because their reaction rate with PAA is significantly slower than cotton. Our experimental results show that white log paper is the best material because they hardly react with PAA and other compounds in the solution.

The production of the solid part: First, the solid acetyl compound is dissolved in a suitable organic solvent or mixed organic solvent, and then transferred to the raw wood paper. The solution on the paper will spread to a larger area and then dry. The area size is related to the solvent. Generally, acetonitrile>acetonitrile/methanol>acetonitrile/ethanol>methanol. In order to save solvent, the concentration of acetyl compounds should be as high as possible, but the size of the diffusion area must also be considered. For practical applications, the coating density of the acetyl compound is 1-4 mg/cm ² . In addition, the alkali or a mixed solution of alkali and stabilizer is transferred to the felt and then dried. Compress the dried paper and felt together to form the solid part (Figure 9).

Solid-liquid packaging example: (Figure 9) shows the solid part composition of 25mL and 200mL packages and the appearance of solid-liquid products. They can be used for general disinfection of public, food, home and medical care.

Table 5 lists the components of typical solid-liquid packaging. By changing the concentration of various components, it can be used for different purposes.

Table 5. General composition of solid-liquid packaging

Note: *DW: deionized water; **SAC: solid acetyl compound; #WRTW: white log paper.

All solid compounds are coated on paper or felt to form part B (solid part).

(1) Selection of solid acetyl compound: In this selection, SOA, GPA and TAED were tested. Since TAED is not soluble in common organic solvents, it was not selected for coating tests. SOA and GPA exhibit similar coating characteristics, which means that both can be coated on the fiber in a very thin layer. In the PAA generation rate and conversion rate test, GPA has higher reactivity than SOA (Table 6). Based on the test results, GPA is more suitable as a PAA activator in solid-liquid packaging than SOA.

Table 6. The relationship between PAA yield/conversion rate and different acetyl compounds.

Note: Except for different acetyl compounds, other conditions are the same. The temperature is 20℃ and the initial pH is 9.04.

Acetyl group concentration (M) = acetyl compound concentration (M) × number of acetyl groups

*Conversion rate=maximum PAA concentration (M)/initial acetyl group concentration (M)×100.

Actual examples of SOA and GPA as PAA activators in solid-liquid packaging are listed in Table 7 and Table 8, respectively.

Table 7. Example 2. Solid-liquid packaging using SOA as PAA activator.

Table 8. Example 3. Solid-liquid packaging using GPA as PAA activator.

(2) The influence of temperature and reaction time on the PAA product: Similar to the liquid-liquid formula, temperature will affect the rate of PAA formation. When SOA is used as a PAA activator, the effect of temperature on PAA generation speed and lifetime is shown in Figure 10. Usually at 20-30℃, after A and B are mixed, it takes 6-10 minutes to get a high-efficiency disinfectant (Figure 10a), and at 25℃, the service life is at least 8 days, which is also related to additives (Figure 10b). At 20°C, if GPA is used as a PAA activator, it takes 5 minutes to become an efficient disinfectant (Figure 11a), and its pot life is greater than 10 days (Figure 11b), which is also related to additives. Similar to SOA, when GPA is used as PAA activator, its PAA generation speed is still related to temperature, and lower temperature requires longer waiting time.

(3) The influence of HP concentration on PAA: As mentioned above, the PAA produced by the non-equilibrium method depends on the concentration of acetyl compound and HP and pH. Figure 12 shows how the concentration of HP affects the rate of PAA production at 20°C. It can be expected that increasing the HP concentration will increase the PAA production rate. However, as a disinfectant for public, household, skin and wound treatment, the acceptable HP concentration should be less than 6%, the comfort concentration should be less than 4%, and ideally about 3%. If used as a bleaching agent, the HP concentration may be much higher than 6%.

(4) The influence of CTAC and HEDP on the yield and pot life of PAA: Our experimental results show that CTAC can accelerate the formation of PAA, but it will have a negative impact on the pot life (Figures 8, 11 and 13).

The test results also show that, for the impact of PAA generation rate, GPA is less sensitive to CTAC than SOA (compare Figure 11a and Figure 13). The effect of HEDP on the life of PAA is similar to that of liquid-liquid packaging, which can stabilize PAA and slightly accelerate PAA production.

(5) The choice of alkali: If the alkali does not affect the PAA service life, any alkali can be selected to adjust the initial pH. Our test results show that carbonate can stabilize PAA. At the same pH, if no PAA stabilizer is added, sodium carbonate is better than sodium hydroxide for stabilizing PAA. In order to reduce residues, a mixture of sodium carbonate and sodium hydroxide is used to adjust the pH, because sodium hydroxide is more alkaline than sodium carbonate and has a low molecular weight, which determines that sodium hydroxide will produce fewer residues than sodium carbonate.

(6) Sterilization ability and toxicological test results: Tables 9 and 10 list the test results. In these tests, using a solid-liquid formulation, SOA or GPA was used as the PAA activator. The test results show that this rapid and instant PAA can be used as a high-efficiency disinfectant, and its low toxicity can be used for disinfection in food, medical and health fields.

Table 9. Microbicidal efficacy of solid-liquid formulations (Examples 2 and 3).

Note: The test data comes from officially certified laboratories, such as Ningbo Entry-Exit Inspection and Quarantine Bureau Technology Center and Guangzhou Chinese Academy of Sciences Testing Technology Service Co., Ltd. *ACCT9372; **killing effect = the negative log value of the number of colonies found/the number of applied colonies. The disinfectant is used when the mixing time of A and B is 10 minutes. The composition of the disinfection solution is listed in Table 8 or Table 9. The test temperature is 20°C.

Table 10. Toxicological test results of solid-liquid formulations.

Acute oral toxicity test, mice No alcohol LD50>5023.9mg/KG, actual non-toxic grade Acute oral toxicity test, mice Alcohol 10% LD50>5000mg/KG, practically non-toxic Acute inhalation toxicity test, mice No alcohol LD50>11.4mg/L, practically non-toxic Repeated skin irritation test, rabbit No alcohol Light irritation, no other toxicity. Repeated skin irritation test, rabbit Alcohol 10% Light irritation, no other toxicity. Acute eye irritation test, rabbit No alcohol Non-irritating Acute eye irritation test, rabbit Alcohol 10% No irritation. Broken skin, rabbit No alcohol No irritation. Animal micronucleus test (mutagenic), mice No alcohol No chromosomal damage in animals was seen.

Note: The test data comes from an officially certified laboratory, Ningbo Entry-Exit Inspection and Quarantine Bureau Technology Center

1. The formulation and method proposed in this application significantly increase the generation rate of PAA by increasing the temporary solubility of insoluble solid acetyl compounds in aqueous solutions. This method first dissolves the solid acetyl compound in a mixture of alcohol and water, and then mixes it with an aqueous solution to obtain a temporary solubility that is far greater than the actual solubility.

2. This application improves the dissolution rate of insoluble solid acetyl compounds in aqueous solutions

To significantly increase the speed of PAA generation. The method is to coat insoluble solid acetyl compound on the surface of the fiber material to increase its effective surface area, thereby increasing its dissolution rate in aqueous solution.

The applicant further declares that the present invention uses the above embodiments to illustrate the formulation, method and device structure of the present invention, but the present invention is not limited to the above embodiments, which does not mean that the present invention must rely on the above formulation, method and structure Can be implemented. Those skilled in the art should understand that any improvements to the present invention, formulations selected to implement the present invention, equivalent replacement of methods, addition of steps, selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention. Inside.

The present invention is not limited to the above-mentioned embodiments, and all the ways to achieve the objective of the present invention by using a formula similar to the present invention and its method are all within the protection scope of the present invention.

Claims (18)

A formulation and method for generating peracetic acid disinfectant immediately and quickly, which is characterized in that: without heating, without using high pH and continuous stirring or shaking, by improving the dissolution rate and temporary solubility of solid acetyl compounds in aqueous solutions Method to promote the immediate and rapid generation of peroxyacetic acid. The formulation for the immediate and rapid generation of peroxyacetic acid includes a peroxygen donor, a solid acetyl compound, a pH adjuster and water, and may also contain alcohol, surfactant and/or peroxide Oxide stabilizer, etc. The components of this formula are divided into two-part packaging and three-part packaging. Before use, mix the parts in each package together. The theoretical initial concentration of each component in the mixture is: Peroxygen donor: 2-6%, Acetyl compounds: 0.2-1%, Alcohol: 0-9.9%, Surfactant: 0-0.4%, Peroxide stabilizer: 0-0.02%, The amount of pH adjuster is such that the initial pH of the mixture is between 8.2 and 9.5, The rest is water. The formulation and method for generating peroxyacetic acid disinfectant immediately and quickly according to claim 1, wherein the solid acetyl compound is coated on the fibrous material to significantly increase its surface area, thereby causing a significant increase in its dissolution rate to promote The rapid generation of peracetic acid, the instant and rapid generation of peracetic acid formula is divided into two parts packaging, one is the liquid part, namely the A part, and the other is the solid part, namely the B part, the liquid part contains the peroxygen donor And water, and may also contain ethanol and/or surfactant; the solid part includes solid acetyl compound coated on fiber material, and pH adjuster coated on fiber material, or coated on fiber material A mixture of pH adjusters and peroxide stabilizers. The formula and method for generating peracetic acid disinfectant immediately and quickly according to claim 1, characterized in that: the solid acetyl compound is dissolved in a mixed solution of alcohol and water to form its mother liquid, and the mother liquid is mixed with the aqueous solution to significantly improve its Temporary solubility in aqueous solution to promote the rapid generation of peroxyacetic acid, the instant and rapid generation of peracetic acid formula is packaged in three liquid parts, where part A contains peroxygen donor and water, and may also contain alcohol and surfactant; Part B is the mother liquor part of acetyl compound, which contains acetyl compound, alcohol and water; Part C contains pH adjuster and water, and may also contain peroxide stabilizer. The formula and method for generating peroxyacetic acid disinfectant immediately and quickly according to claim 1, characterized in that: within 10 minutes after all parts are mixed and at an ambient temperature of >10°C, the generated peroxy The concentration of acetic acid molecules must be ≥0.045% and the highest concentration it can reach ≤0.4%. The formula and method for generating peroxyacetic acid disinfectant immediately and quickly according to claim 1, characterized in that: within 10 minutes after all parts are mixed and at an ambient temperature of >10°C, the generated peroxy The concentration of acetic acid molecules must be ≥0.045% and the highest concentration it can reach ≤0.2% to reduce the pungent odor produced by PAA. The formula and method for generating peroxyacetic acid disinfectant immediately and quickly according to claim 1, 2, or 3, characterized in that: the peroxygen donor is hydrogen peroxide, or other hydrogen peroxide can be generated in an aqueous solution The initial concentration of the compound when all the parts are mixed together is 2-6%. The formulation and method for generating peracetic acid disinfectant immediately and quickly according to claim 2, wherein the solid acetyl compound coated on the fibrous material increases its effective surface area and thereby increases its dissolution rate. The result is the rapid generation of peroxyacetic acid. The solid acetyl compound is SOA or GPA, or a solid acetyl compound with similar physical and chemical properties to SOA and GPA. The fiber material is preferably white log paper with a coating density of 1-4mg/cm ² . The formula and method for generating peroxyacetic acid disinfectant immediately and quickly according to claim 7, wherein the acetyl compound coated on the white log paper is preferably GPA to increase its effective surface area and thereby increase its dissolution The result is a rapid generation of peroxyacetic acid, with a coating density of 1.4-2.5 mg/cm ² . The formulation and method for generating peracetic acid disinfectant immediately and quickly according to claim 3, characterized in that: the solid acetyl compound mother liquor, the acetyl compound is SOA or an acetyl compound with similar solubility characteristics as SOA, dissolved in alcohol and In the water mixed solution, the SOA concentration is 4-12%. The formula and method for generating peracetic acid disinfectant immediately and quickly according to claim 9, wherein the mixed solution of alcohol and water is a mixed solution of ethanol and water, and the ethanol concentration is 70-95% v/v. The formula and method for generating peracetic acid disinfectant immediately and quickly according to claim 9, characterized in that the mixed solution of alcohol and water is a mixture of isopropanol and water, and the concentration of isopropanol is 60-90%v /v. The formula and method for generating peroxyacetic acid disinfectant immediately and quickly according to claim 1, 2, or 3, characterized in that: the pH adjusting agent is a mixture of sodium carbonate and sodium hydroxide, and its amount must meet the requirements of The initial pH after all parts are well mixed is 8.2-9.5. The formula and method for generating peracetic acid disinfectant immediately and quickly according to claim 1, wherein the alcohol is ethanol or isopropanol, and the initial concentration when all parts are mixed together is 0-15 %. The formula and method for generating peracetic acid disinfectant immediately and quickly according to claim 13, wherein the alcohol is preferably ethanol, and the initial concentration when all parts are mixed together is preferably 5-9.9%. The formulation and method for generating peroxyacetic acid disinfectant immediately and quickly according to claim 1, 2, or 3, characterized in that: the surfactant is CTAC, or sodium lauryl sulfonate, or twelve The initial concentration of sodium alkyl sulfate is 0-0.4% after all parts are mixed. The formulation and method for generating peroxyacetic acid disinfectant immediately and quickly according to claim 15, characterized in that: the surfactant is preferably CTAC, and its initial concentration is 0.05-0.09% after all parts are mixed, which can Help the rapid generation of PAA. The formula and method for generating peroxyacetic acid disinfectant immediately and quickly according to claim 1, 2, or 3, characterized in that: the peroxide stabilizer is HEDP, and after all the parts are mixed, the initial concentration is 0 -0.02%. The formulation and method for generating peroxyacetic acid disinfectant immediately and quickly according to claim 2, characterized in that: the pH adjusting agent coated on the fiber material, or the pH adjusting agent coated on the fiber material And peroxide stabilizer, the pH adjuster is a mixture of sodium carbonate and sodium hydroxide, the pH adjuster and peroxide stabilizer is a mixture of sodium carbonate, sodium hydroxide and HEDP, so The fiber material is preferably polyester felt.

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