CN110313489B - Anti-corrosion sterilization type wet tissue and preparation method and application thereof - Google Patents

Anti-corrosion sterilization type wet tissue and preparation method and application thereof Download PDF

Info

Publication number
CN110313489B
CN110313489B CN201910544783.2A CN201910544783A CN110313489B CN 110313489 B CN110313489 B CN 110313489B CN 201910544783 A CN201910544783 A CN 201910544783A CN 110313489 B CN110313489 B CN 110313489B
Authority
CN
China
Prior art keywords
lae
ion pair
pair compound
acid
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910544783.2A
Other languages
Chinese (zh)
Other versions
CN110313489A (en
Inventor
易正芳
邵婷
仇文卫
王李婷
刘明耀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
East China Normal University
Original Assignee
East China Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by East China Normal University filed Critical East China Normal University
Priority to CN202110317818.6A priority Critical patent/CN112790196B/en
Publication of CN110313489A publication Critical patent/CN110313489A/en
Application granted granted Critical
Publication of CN110313489B publication Critical patent/CN110313489B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44—Guanidine; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
    • A47K10/00—Body-drying implements; Toilet paper; Holders therefor
    • A47K10/16—Paper towels; Toilet paper; Holders therefor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
    • C07C277/08—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of substituted guanidines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/803—Processes of preparation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention provides an antiseptic or mildew inhibitor for wet tissues, which comprises lauroyl arginine ethyl ester (LAE) and ion pair derivatives thereof. The invention also provides a method for preparing the preservative or mildew preventive for the wet tissue and the preservative or mildew preventive for the wet tissue prepared by the method. The preservative or mildew preventive for the wet tissue has the characteristics of being natural, non-toxic, efficient in bacteriostasis, easy to degrade and environment-friendly.

Description

Anti-corrosion sterilization type wet tissue and preparation method and application thereof
Technical Field
The invention relates to an anticorrosive and bactericidal wet tissue, in particular to an anticorrosive and bactericidal wet tissue containing lauroyl arginine ethyl ester and derivatives (ion pair compounds) thereof, wherein the lauroyl arginine ethyl ester and the ion pair derivatives thereof have an antibacterial effect, and can help the wet tissue to play a moisturizing function and an antibacterial and anticorrosive effect.
Background
With the continuous improvement of living standard of people, the consumption of people to wet tissues is also continuously increased, and the variety of the wet tissues is more and more. The manufacturing scale of wet tissues is also expanded from manual workshops to automatic production lines from wet towels of hotels, wet tissues for car wiping, wet tissues for makeup removal, wet tissues for facial masks, wet tissues for sanitary care of children and the like. Regarding various occasions and functions of the wet tissue, wet tissue manufacturers are not required to strictly disinfect the wet tissue in the wet tissue manufacturing process, and have quite good antiseptic and mildew-proof effects in the storage process.
Although the wet tissue is a disinfection product, the process does not include disinfection, and once the wet tissue is polluted in the processes of production, storage and transportation, a plurality of harmful microorganisms are attached to the wet tissue. After the consumer uses the contaminated wet towel, the contaminated wet towel may cause diarrhea and skin diseases, and other diseases.
As the wet tissue is difficult to prevent corrosion and mildew, a great deal of loss caused by serious standard exceeding of microorganisms of the wet tissue, odor and mildew has occurred in many wet tissue production enterprises in China in the past. In order to prevent the propagation of microorganisms on wet tissues, many enterprises adopt a mode of adding preservatives into a preparation liquid to ensure that the product meets the national sanitary standard within the shelf life.
Chinese patent application 2012104006385, an antiseptic and mildew inhibitor composition for wet tissues and a production method thereof, discloses a wet tissue using 2-Methylisothiazolinone (MIT) and/or 5-chloro-2-methylisothiazolinone (CMIT) and/or bronopol (bronopol) as an antiseptic. The invention scientifically combines the effects of sterilization, antisepsis and mildew resistance through the compatibility, and the wet tissue can be protected from being polluted by microorganisms by singly adding the composition, so that the product has stronger antisepsis and mildew resistance effects, and the optimal composition for resisting the microbial hazard is formed. However, the antiseptic is still aimed at killing microorganisms by using toxic compounds to overcome the problem of drug resistance of the existing wet tissues, and the long-term use of the antiseptic still has influence on human bodies and the environment.
In chinese patent publication No. CN101416843A, a method for manufacturing a wet towel with smoke prevention and dust prevention is disclosed, which comprises the following steps: 1. mixing propylene glycol, diazolidinyl urea, iodopropynyl butyl methylamine ester, polyhexamethylene biguanide, distilled water and peppermint liquid to prepare a solution; 2. sterilizing the selected towel at high temperature; 3. soaking the disinfected towel in a prepared solvent completely, and taking out; 4. and (5) filling the towel taken out into an aluminum-plated film packaging bag for aseptic sealing. According to the method, the diazolidinyl urea is adopted as one of anticorrosion components, formaldehyde can be released, meanwhile, a plurality of preservatives need to be added respectively, the use is very inconvenient, iodopropynyl butyl methylamine ester is difficult to dissolve even in propylene glycol, long stirring and dissolving time is needed, meanwhile, high-temperature disinfection is needed for towel pretreatment, energy consumption is achieved, and the production procedure is increased.
In Chinese patent publication No. CN 102613935A, an aromatic disinfectant wet wipe and a preparation method thereof are disclosed, wherein the preparation method comprises the steps of preparing a disinfectant mixed solution from quantitative 2-bromo-2-nitropropanediol, benzethonium chloride, sodium octaborate tetrahydrate and essence, then dripping the disinfectant mixed solution on a carrier paper towel, wherein the dripping amount is 1.5 ml per gram of paper towel, and wetting the paper towel to obtain the aromatic disinfectant wet wipe; the method uses sodium octaborate tetrahydrate as a preservative component, which is a common wood preservative and belongs to a bactericide which cannot contact human bodies, thereby influencing the application of wet tissue products.
Therefore, the research on the natural and non-toxic preservative or mildew preventive of the wet tissue becomes a hot point of research in wet tissue products.
Lauroyl arginine Ethyl ester (LAE) is an organic matter formed by condensing fatty acid and dibasic amino acid, is a white hygroscopic solid, is chemically stable in a pH range of 3-7, has a melting point of 50-58 ℃, can be dispersed in 1kg of water at the temperature of 247g, and has a distribution coefficient of more than 10 in water and oil, namely is mainly in an aqueous phase. Researches find that the lauroyl arginine ethyl ester LAE has the characteristics of strong antibacterial capability, low biological toxicity, good in vivo metabolism effect and high environmental compatibility. The most representative characteristic is that no residue is left in the metabolism of lauroyl arginine ethyl ester, and related researches show that lauroyl arginine ethyl ester can be rapidly metabolized naturally in human bodies and animal bodies, is firstly hydrolyzed into Lauroyl Arginine (LAS) and ethanol, then LAS is hydrolyzed into naturally existing dietary components, namely lauric acid and arginine, the lauric acid is further metabolized into carbon dioxide and water, and the arginine is metabolized into ornithine, urea and carbon dioxide. All primary metabolites and final metabolites produced during the metabolism of lauroyl arginine ethyl ester are non-toxic and harmless, and are the same as the metabolites of food ingested daily by humans and animals in the body. In 2005, the FDA approved LAE as a GRAS (generally recognized as safe) food additive in the united states, passed the safety food certification of the European Food Safety Administration (EFSA) in 2007, and the international food code committee of 2011 listed LAE as a food additive general code standard, and approved LAE as a preservative for 20 kinds of foods and fresh agricultural products.
Chinese patent application CN201710056593, entitled "fruit and vegetable preservative and preparation method and application thereof" discloses a composition taking lauroyl arginine ethyl ester hydrochloride and sodium methyl paraben as main active ingredients to be used as the fruit and vegetable preservative, and can effectively inhibit the growth of bacteria causing fruit and vegetable rot. However, the single bacteriostatic effect of the high-concentration methyl paraben sodium (2000 mug/ml) in the invention is stronger than that of the low-concentration LAE (1000 mug/ml) because the single-concentration sodium paraben sodium has a phenolic hydroxyl structure and the antibacterial performance is far stronger than that of benzoic acid and sorbic acid, so on the premise of ensuring the preservative performance, the method definitely indicates that the use of the sodium paraben sodium instead of the LAE is helpful for reducing the dosage cost of the preservative.
Chinese patent application CN201510748675, entitled "method for inhibiting alcohol fermentation contaminating microorganisms by using lauroyl arginine ethyl ester" discloses a method for inhibiting alcohol fermentation contaminating microorganisms by using lauroyl arginine ethyl ester, which comprises adding LAE and salt compounds thereof into fermentation liquor of saccharomyces cerevisiae at a concentration of less than 50 μ g/ml, and can effectively inhibit the growth of lactic acid bacteria and control the growth of other contaminating microorganisms. However, this bacteriostatic slightly affects yeast growth to some extent and results in a 0.6% decrease in alcohol production.
Chinese patent application CN201610466729, entitled "a mild infant shampoo and bath bubble" discloses a mild infant shampoo and bath bubble, which is characterized by selecting disodium cocoyl glutamate, cocamidopropyl betaine, sodium hydroxypropyl lauryl glucoside cross-linked polymer sulfonate as a surfactant system, selecting camellia oil, alpha-glucan oligosaccharide/inulin complex as a conditioning component, and flos Chrysanthemi Indici extract and lauroyl arginine ethyl ester HCl as an antiseptic system, wherein the raw materials cooperate with each other, and the bubble has good cleaning effect, is mild and has no irritation.
At present, no report is available on the use of LAE and its derivatives for antiseptic and bactericidal wet wipes.
Disclosure of Invention
The prior inventions do not teach the use of a single LAE component as a mildewcide for antiseptic and bactericidal wet wipes, nor do they disclose the use of LAE in appropriate concentrations as a mildewcide for antiseptic and bactericidal wet wipes. Therefore, on one hand, the LAE is used for the first time in the research of the antiseptic and bactericidal wet tissue by utilizing the bacteriostatic effect of the preservative, and the proper use concentration is determined through experiments, so that the negative effects on the environment are small and the toxic and side effects are low while the effective antibacterial and disease preventing effects are achieved. On the other hand, on the basis of the research, according to the characteristics that the lauroyl arginine ethyl ester LAE has strong antibacterial ability, low biotoxicity, good in vivo metabolism effect, high environmental compatibility and no reaction with other compounds at normal temperature, the LAE is further improved to obtain a novel derivative, namely, the LAE and organic acid salt are subjected to condensation reaction, so that the LAE ion pair compound is obtained. The ion pair compound is used as a preservative component of the preservative sterilization type wet tissue, and has the advantages of better bacteriostatic effect and lower using dosage compared with LAE, thereby being more beneficial to preparing natural, nontoxic and stable preservative sterilization type wet tissue.
The first invention aims at providing the application of lauroyl arginine ethyl ester LAE as an antiseptic or mildew preventive for wet tissues.
In one embodiment, the LAE comprises a lauroyl arginine ethyl ester compound of formula (I) (LAE compound) or a hydrate or pharmaceutically acceptable salt thereof.
Figure BDA0002103635180000041
Wherein,
x is halogen or HSO4(ii) a Preferably, Br, Cl or HSO4；
R1Is a linear saturated fatty acid or oxo acid containing 8 to 14 carbon atoms; preferably, a linear oxyacid having 12 carbon atoms;
R2is a straight or branched chain fatty acid or aromatic group containing 1 to 18 carbon atoms; preferably, it is a linear saturated fatty acid containing 2 carbon atoms;
R3is one of the following structures:
Figure BDA0002103635180000042
n ranges from 0 to 4.
In a preferred embodiment, X is Cl and the compound of formula (I) is lauroyl arginine ethyl ester hydrochloride (LAEHCl) having the formula (II):
Figure BDA0002103635180000043
wherein the mass percentage concentration of the LAE in the matrix solution of the wet tissue preservative or the mildew preventive is 0.001-2%; preferably, from 0.001 to 0.01%, from 0.01 to 0.1%, from 0.05 to 0.1%, from 0.1 to 0.2%, from 0.1 to 1%, from 1 to 2% or from 1.5 to 2%; further preferably, it is 0.01 to 0.1% or 0.05 to 0.1%.
The second invention of the present invention is to provide the use of the LAE ion pair compound for preparing a preservative or a mildewcide for wet wipes, wherein the LAE ion pair compound has the structural formula shown in the following formula (III):
Figure BDA0002103635180000051
wherein, the RCOO-The organic acid or salt is selected from salicylic acid, formic acid, ammonium formate, calcium formate, acetic acid, sodium diacetate, propionic acid, ammonium propionate, sodium propionate, calcium propionate, butyric acid, sodium butyrate, lactic acid, benzoic acid, sodium benzoate, sorbic acid, sodium sorbate, potassium sorbate, fumaric acid, citric acid, potassium citrate, sodium citrate, calcium citrate, tartaric acid, malic acid, phosphoric acid, sodium carbonate, oxalic acid or carbonic acid having antibacterial activity. In a preferred embodiment, the organic acid salt is selected from the group consisting of nicotinic acid, tartaric acid, oxalic acid.
Wherein the mass percentage concentration of the LAE ion pair compound in the substrate solution of the wet tissue preservative or the mildew preventive is 0.001-2%; preferably, from 0.001 to 0.01%, from 0.01 to 0.1%, from 0.05 to 0.1%, from 0.1 to 0.2%, from 0.1 to 1%, from 1 to 2% or from 1.5 to 2%; further preferably, it is 0.01 to 0.1% or 0.05 to 0.1%.
It is a third object of the present invention to provide a method for preparing a preservative or fungicide for wet wipes containing the above LAE ion pair compound, comprising the steps of:
(1) heating and dissolving the compound shown in the formula (II), and then adding an organic acid salt solution;
(2) fully stirring and uniformly mixing, and reacting under the condition of heating to obtain the LAE ion pair compound, wherein the reaction is shown as the following reaction formula:
Figure BDA0002103635180000052
wherein, the RCOO-The organic acid or salt is selected from salicylic acid, formic acid, ammonium formate, calcium formate, acetic acid, sodium diacetate, propionic acid, ammonium propionate, sodium propionate, calcium propionate, butyric acid, sodium butyrate, lactic acid, benzoic acid, sodium benzoate, sorbic acid, sodium sorbate, potassium sorbate, fumaric acid, citric acid, potassium citrate, citric acidSodium, calcium citrate, tartaric acid, malic acid, phosphoric acid, sodium carbonate, oxalic acid or carbonic acid;
(3) after full reaction, cooling to room temperature, purifying and then drying in vacuum to prepare the lauroyl arginine ethyl ester organic acid ion pair compound shown in the formula (III);
(4) and adding the matrix solution into a container at normal temperature and normal pressure, adding the LAE ion pair compound, and circulating and fully stirring by a pump to obtain the preservative or the mildew preventive for the wet tissue.
In the step (1), the heating and dissolving temperature is 50-100 ℃; preferably, it is 90 ℃.
In the step (2), the reaction temperature is 50-100 ℃; preferably, it is 90 ℃.
In the step (2), the reaction time is 50-100 ℃; preferably, it is 90 ℃.
In the step (3), the vacuum drying condition is 50-100 ℃; preferably, it is 60 ℃.
In the step (4), the container is preferably made of stainless steel or inert material.
In one embodiment, wherein said RCOO-The organic acid or salt is selected from salicylic acid, formic acid, ammonium formate, calcium formate, acetic acid, sodium diacetate, propionic acid, ammonium propionate, sodium propionate, calcium propionate, butyric acid, sodium butyrate, lactic acid, benzoic acid, sodium benzoate, sorbic acid, sodium sorbate, potassium sorbate, fumaric acid, citric acid, potassium citrate, sodium citrate, calcium citrate, tartaric acid, malic acid, phosphoric acid, sodium carbonate, oxalic acid or carbonic acid having antibacterial activity. In a preferred embodiment, the organic acid salt is selected from sodium nicotinate, sodium tartrate, sodium oxalate.
In another embodiment, the RCOO-The preparation method of the organic acid salt comprises the following steps: adding the organic acid into methanol solution, adding a proper amount of NaOH, stirring at room temperature until white solid is separated out, carrying out suction filtration, and washing with methanol to obtain the organic acid salt.
The fourth object of the present invention is to provide a preservative or antifungal agent for wet wipes containing the above LAE or its ion-pair compound as a bacteriostatic or antiseptic agent, which comprises 0.001 to 2% by mass of the LAE ion-pair compound; preferably, from 0.001 to 0.01%, from 0.01 to 0.1%, from 0.05 to 0.1%, from 0.1 to 0.2%, from 0.1 to 1%, from 1 to 2% or from 1.5 to 2%; more preferably, 0.01-0.1%, 0.05-0.1% of the LAE ion pair compound.
Terms and definitions:
lauroyl arginine Ethyl ester (LAE) is an organic matter formed by condensing fatty acid and dibasic amino acid, is a white hygroscopic solid, is stable in chemical property within the range of pH 3-7, has a melting point of 50-58 ℃, can be dispersed in 1kg of water at the temperature of 247g, and has a distribution coefficient of more than 10 in water and oil, namely is mainly in a water phase. Researches find that the lauroyl arginine ethyl ester LAE has the characteristics of strong antibacterial capability, low biological toxicity, good in vivo metabolism effect and high environmental compatibility. The most representative characteristic is that no residue is left in the metabolism of lauroyl arginine ethyl ester, and related researches show that the lauroyl arginine ethyl ester can be rapidly and naturally metabolized in human bodies and animal bodies to generate lauric acid and arginine which are further metabolized into ornithine, urea, carbon dioxide and water. All primary metabolites and final metabolites produced during the metabolism of lauroyl arginine ethyl ester are non-toxic and harmless, and are the same as the metabolites of food taken by human and animals in the body.
The invention improves the derivatives of the LAE, breaks through the traditional thought of the development of the derivatives, namely, the traditional thought is not limited to selecting the proper forms of acid, alkali and salt/ester which are traditionally suitable for the LAE, or treating the LEA with acid, alkali, salt or esterification groups, but creatively selects an acid radical group which can enhance the bacteriostatic synergistic effect of the LAE, and combines the acid radical group and the acid radical group into a new derivative, namely an ion pair compound, through strong intermolecular ionic bonds, so that the application of the LAE derivative in the preservative or mildew preventive of wet tissues is remarkably improved.
Technical effects
The mildew-proof adhesive has the advantages that:
the LAE and the ion pair derivatives thereof are creatively used to replace bacteriostatic agents and preservatives in the wet tissue, so that the advantages of low cost, simple manufacturing process and good stability of the traditional wet tissue are maintained, and the novel wet tissue has the advantages of remarkable bacteriostatic effect, single component, simplicity in preparation, no harm to human bodies, easiness in biological catabolism, easiness in long-term storage and the like.
Drawings
FIG. 1: ESI mass spectrum of cation B + molecular ion peak of LAE ion pair compound;
FIG. 2: ESI mass spectrum of anion A-molecular ion peak of LAE nicotinic acid ion pair compound;
FIG. 3: peak shape and chemical shift pattern of 1H-NMR of LAE;
FIG. 4: peak shape and chemical shift pattern by 1H-NMR of nicotinic acid;
FIG. 5: peak shape and chemical shift pattern by 1H-NMR of LAE nicotinic acid ion pair;
FIG. 6: ESI mass spectrum of LAE tartrate ion on the anion A-molecule ion peak of the compound.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and drawings, and the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected. The procedures, conditions, reagents, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
The first embodiment is as follows: preparation method of ion pair compound synthesized from lauroyl arginine ethyl ester hydrochloride and nicotinic acid
Dissolving 2.0g of sodium nicotinate (purchased from Taishiai (Shanghai) chemical industry development Co., Ltd.) in 50mL of water to prepare a sodium nicotinate saline solution (A); dissolving lauroyl arginine ethyl ester hydrochloride 6.8g in 40mL of water, heating to 90 ℃ until the lauroyl arginine ethyl ester hydrochloride is completely dissolved to prepare lauroyl arginine ethyl ester hydrochloride aqueous solution (B); slowly adding the sodium nicotinate aqueous solution (A) into the lauroyl arginine ethyl ester hydrochloride aqueous solution (B) at 90 ℃, continuously stirring, reacting for 2 hours, cooling to room temperature, filtering, fully washing the precipitate with purified water, and drying the precipitate in vacuum at 60 ℃ to obtain 7.6g of the nicotinic acid ion pair compound.
Example analysis of molecular formula and molecular weight of compound by dilauroyl arginine ethyl ester nicotinic acid ion pair
By mass spectrometry,1H-NMR、13The compound obtained by C-NMR spectroscopy has the formula:
1. mass Spectrometry (ESI) analysis
Cation B+The molecular ion peak has m/z 385.3, see fig. 1;
anion A-The molecular ion peak has m/z of 122.1, see fig. 2.
The theoretical calculation of the niacin ion for the cation in the compound was 507.4, and the observed value coincided with the theoretical value.
NMR analysis
Extracting lauroyl arginine ethyl ester hydrochloride (see FIG. 3), nicotinic acid1H-NMR (see FIG. 4) and of LAE Niacin ion-pair Compounds1H-NMR (see FIG. 5). In the salt forming process of the LAE ion pair compound, the peak shape and chemical shift of lauroyl arginine ethyl ester in the ion pair compound are not changed greatly, but all hydrogen on nicotinic acid has shift change, and the spectral characteristics of the acid and base part are closer to the space distance compared with the original inorganic acid salt (namely LAE hydrochloride), so that the influence is generated, and the corresponding change is generated compared with the original LAE and the hydrochloride thereof, the simple superposition of the acid and base parts is not generated, for example, the solubility is changed when purified water is used for washing and precipitating, which shows that strong interaction is generated between all hydrogen nuclei of the lauroyl arginine ethyl ester and the nicotinic acid, and a stable single compound structure is formed through strong ionic bonds.
Example three: preparation method of ion pair compound synthesized by lauroyl arginine ethyl ester hydrochloride and tartaric acid
2.0g of tartaric acid (purchased from Chiese chemical industry Co., Ltd.) was dissolved in 50mL of methanol, and an equivalent of NaOH was added thereto, and the mixture was stirred at room temperature until a white solid was precipitated, and then the solution was filtered under suction and washed with 30mL of methanol three times to obtain a tartaric acid sodium salt. Dissolving sodium tartrate salt in 50mL of water to prepare a sodium tartrate salt aqueous solution (A); dissolving 5.6g of lauroyl arginine ethyl ester hydrochloride in 40mL of water, heating to 90 ℃ until the lauroyl arginine ethyl ester hydrochloride is completely dissolved to prepare lauroyl arginine ethyl ester hydrochloride aqueous solution (B); slowly adding the tartaric acid sodium salt water solution (A) into the lauroyl arginine ethyl ester hydrochloride water solution (B) at 90 ℃, continuously stirring, reacting for 2 hours, cooling to room temperature, filtering, fully washing the precipitate with purified water, and drying the precipitate at 60 ℃ in vacuum to obtain 6.3g of the tartaric acid ion pair compound.
Example analysis of molecular weight of Compounds by Artocylarginine Ethyl ester tartrate ions
Mass Spectrometry (ESI) analysis of cation B+Molecular ion peak m/z 385.3 (see fig. 1)
Anion A-Molecular ion peak m/z 149.0 (see FIG. 6)
The theoretical calculation of the niacin ion for the cation in the compound was 534.3, and the observed value coincided with the theoretical value.
Example five: preparation method for synthesizing ion pair compound by using lauroyl arginine ethyl ester hydrochloride and oxalic acid
Oxalic acid (purchased from research Co., Ltd.) 1.0g was dissolved in 50mL of methanol, an equivalent amount of NaOH was added, and the mixture was stirred at room temperature until a white solid precipitated, filtered under suction and washed with 30mL of methanol three times to obtain an oxalic acid sodium salt. Dissolving sodium oxalate in 50mL of water to prepare sodium oxalate aqueous solution (A); dissolving 4.7g of lauroyl arginine ethyl ester hydrochloride in 40mL of water, heating to 90 ℃ until the lauroyl arginine ethyl ester hydrochloride is completely dissolved to prepare lauroyl arginine ethyl ester hydrochloride aqueous solution (B); slowly adding the sodium oxalate salt aqueous solution (A) into the lauroyl arginine ethyl ester hydrochloride aqueous solution (B) at 90 ℃, continuously stirring, reacting for 2 hours, cooling to room temperature, filtering, fully washing the precipitate with purified water, and drying the precipitate in vacuum at 60 ℃ to obtain 5.0g of the oxalate ion pair compound.
The results of NMR and ESI analyses performed according to the method of example II show that the ion pair compound does not have a simple superposition of two acid and base parts, which are closely spaced and have an influence on the spectral characteristics, and the spectral data of the ion pair compound has a corresponding change compared with the original LAE and the hydrochloride thereof, for example, the solubility has changed when the precipitate is washed with purified water, which indicates that all hydrogen nuclei of lauroyl arginine ethyl ester have strong interactions with oxalic acid and form a stable single compound structure through strong ionic bonds.
Example six: preparation method of ion pair compound synthesized by lauroyl arginine ethyl ester hydrochloride and carbonic acid
1.0g of sodium carbonate (purchased from research Co., Ltd.) was dissolved in 50mL of water to prepare an aqueous sodium carbonate solution (A); dissolving 4.0g of lauroyl arginine ethyl ester hydrochloride in 40mL of water, heating to 90 ℃ until the lauroyl arginine ethyl ester hydrochloride is completely dissolved to prepare lauroyl arginine ethyl ester hydrochloride aqueous solution (B); slowly adding the sodium carbonate aqueous solution (A) into the lauroyl arginine ethyl ester hydrochloride aqueous solution (B) at 90 ℃, continuously stirring, reacting for 2 hours, cooling to room temperature, filtering, fully washing the precipitate with purified water, and drying the precipitate in vacuum at 60 ℃ to obtain 4.0g of the carbonate ion pair compound.
The results of NMR and ESI analyses performed according to the method of example II show that the ion pair compound does not have a simple superposition of two acid and base parts, which are close in spatial distance and have an influence, and the spectral data of the ion pair compound is changed correspondingly compared with the original LAE and hydrochloride thereof, which indicates that all hydrogen nuclei of lauroyl arginine ethyl ester have strong interactions with carbonic acid and form a stable compound structure through strong single ionic bonds.
Example seven: determination of lauroyl arginine ethyl ester ion pair compound Minimum Inhibitory Concentration (MIC) in vitro
The principle and the purpose are as follows: according to the microbubult dilution method specified by CLSI, the minimum drug concentration at which bacterial growth is inhibited after 24h of co-incubation of the drug with bacteria in a 96-well plate is the minimum inhibitory concentration of the drug.
The method comprises the following steps: all-grass of Laurus nobilisAcylarginine ethyl ester hydrochloride (LAE hydrochloride) and the lauroylarginine ethyl ester organic acid ion pair prepared above are respectively diluted to different concentrations by Trypticase Soy Broth (TSB) twice, the drug and the bacteria are mixed and incubated in a 96-well plate, and a blank control culture medium CK1 without bacteria, a culture medium CK2 added with LAE (1000 mu g/ml) and a normal growth control culture medium CK3 without the drug are additionally arranged. The absorbance at 625nm of each well was measured after incubating the 96-well plate in a 37 ℃ incubator for 24 hours. OD with blank control625Wells with consistent values were considered to have no significant growth of bacteria. The lowest concentration of drug at which bacteria do not significantly grow is the minimum Inhibitory concentration mic (minimum inhibition concentration) of LAE to bacteria.
The results of comparing the antibacterial activity of various LAE derivatives (ion pair compounds) prepared with respect to the original LAE compound are shown in table 1 below.
TABLE 1 in vitro antibacterial Effect of LAE and its ion-pair Compounds on two bacteria
Figure BDA0002103635180000101
Wherein the percentage value in the bracket () represents the mass percentage of each additive in the reaction system.
And (4) analyzing results:
(1) most of the ion pair compounds keep the same antibacterial activity to escherichia coli, and especially the antibacterial activity of the oxalic acid ion pair compounds is improved;
(2) most of the ion pair compounds keep the same antibacterial activity to staphylococcus aureus, the antibacterial activity of the carbonate ion pair compounds is reduced, and the antibacterial activity of the nicotinic acid ion pair compounds is obviously improved;
and (4) conclusion: ion pair compounds of LAE derivatives do not inhibit the antibacterial activity of the original LAE in a single ingredient, but rather are beneficial to the antibacterial activity. Wherein, the nicotinic acid ion pair compound has obvious bacteriostatic effect on staphylococcus aureus.
Example eight: standing method for testing bacteriostatic effect of sanitary wet tissue
The formula mixture of the mildew preventive and the bactericide of the sanitary wet tissue shown in the table 2 is prepared by using a conventional method, and H is removed2O2The amounts of the remaining components are expressed in mass percent (%) except in terms of volume. Wherein, the control 1-2 is mildew inhibitor (nipagin ester) and bactericide (Debio)TMS207), the negative control is blank water.
The white towel was cut into pieces of 10X 10cm and immersed in the solutions of formulations 1-4 and controls 1-2 for 20 minutes. And (4) draining to a humidity of about 35%. Then placing into a sterile sanitary bag, sealing, and storing at room temperature for 1 year. In order to accelerate the test, the test specimen can also be stored at the constant temperature of 35-40 ℃ for 60 days.
The wet wipes were then tested for colony count according to the method of the hygienic Standard for Disposable sanitary articles GB 15979-2002.
The results are shown in Table 2.
TABLE 2
Figure BDA0002103635180000111
+++: out of detection range.
And (4) analyzing results:
the result of the bacteriostatic effect test shows that 0.05 percent of LAE acetate ion pairs are close to the antifungal agents of platinum nicotinate and the bactericide of DebioTMThe combined bacteriostasis effect of S207 is superior to the mildew-proof effect of the single use of the platinum nicotinate.
Although the combined bacteriostatic and mildewproof effect of the 0.2 percent dosage group is the highest in the experiments, and the in vitro cell test data of the applicant's patent application filed earlier (the invention name is: ' the use of the lauroyl arginine ethyl ester derivative as an antibacterial agent for animals ', the application number is 201810648982.3), the bacteriostatic effect is already generated at the concentration of 0.0032 percent, and the bacteriostatic and mildewproof effect can be improved by increasing the dosage of the LAE and the derivative within a certain range, but the bacteriostatic effect is not obviously improved relative to the 0.1 percent dosage group, which shows that the dosage range of 0.01 percent to 0.2 percent meets the production requirement
In addition, according to the existing national relevant standard GB15979-2002 for disposable sanitary products, if the total bacterial colony number is less than 20 and no escherichia coli, pathogenic pus bacteria and fungi are detected within the specified action time of the specified use concentration, the sanitary wet tissue is in accordance with the sanitary regulation. Although increasing the addition of LAE and its derivatives will increase the bacteriostatic and mould-proof rate, too high a bacteriostatic rate means more residue and is not good for human health. Therefore, the bacteriostatic agent components of the LAE and the derivatives thereof belong to natural, environment-friendly and nontoxic components, so that the high-dose addition of the LAE and the derivatives thereof still has the advantage of being friendly to human bodies compared with the traditional chemical bacteriostatic agent, and compared with the combined use of the traditional mildew inhibitor and the traditional bactericide, the single LAE and the derivatives thereof used in the invention have the combined effect of mildew prevention and sterilization.
Therefore, in consideration of the production cost and the actual production requirement, the LAE and the ions thereof can effectively prevent and treat the diseases when the mass percentage concentration of the active ingredients of the anti-mildew and sterilization of the sanitary wet tissue is 0.01-1% or 0.1-1% or 1-2% or 1.5-2%, preferably the effective concentration is 0.01-0.1%, and most preferably 0.05%, and meet the production requirement.

Claims (8)

  1. Use of a LAE ion pair compound for the preparation of a preservative or anti-mold agent for wet wipes, wherein the LAE ion pair compound has the formula shown in formula (III):
    Figure FDA0002998880680000011
    wherein, the RCOO-The organic acid salt of (a) is selected from acetate, nicotinate, oxalate having antibacterial activity; and the number of the first and second groups,
    the LAE ion pair compound is prepared by the condensation reaction of:
    (1) heating and dissolving the compound shown in the formula (II), and then adding an organic acid salt solution of RCOO-;
    Figure FDA0002998880680000012
    (2) fully stirring and uniformly mixing, and carrying out condensation reaction under the condition of heating to 90 ℃ to obtain the LAE ion pair compound, wherein the condensation reaction is shown as the following reaction formula:
    Figure FDA0002998880680000013
    (3) after sufficient reaction, the reaction mixture is cooled to room temperature, washed and purified with purified water and then dried in vacuum, thereby preparing a purified LAE ion pair compound.
  2. 2. The use of claim 1, wherein the LAE ion pair compound is present in the wet wipe preservative or anti-mold base solution in an amount of 0.001 to 2% by weight.
  3. 3. Use according to claim 1 or 2, wherein the organic acid salt of RCOO-is selected from nicotinates, oxalates.
  4. 4. The preparation method of the preservative or the mildew preventive for the wet tissue is characterized by comprising the following steps of:
    (1) heating and dissolving the compound shown in the formula (II), and then adding an organic acid salt solution of RCOO-;
    Figure FDA0002998880680000021
    (2) fully stirring and uniformly mixing, and producing an ion pair compound by the following condensation reaction formula under the condition of heating to 90 ℃;
    Figure FDA0002998880680000022
    wherein the organic acid salt of RCOO-is selected from acetate, nicotinate, oxalate with antibacterial activity;
    (3) after full reaction, cooling to room temperature, washing with purified water, purifying, and vacuum drying to prepare a purified LAE ion pair compound;
    (4) and adding the matrix solution into a container at normal temperature and normal pressure, adding the LAE ion pair compound, and circulating and fully stirring by a pump to obtain the preservative or the mildew preventive for the wet tissue.
  5. 5. The method of claim 4, wherein the organic acid salt of RCOO-is prepared by: adding the organic acid into a methanol solution, adding a proper amount of NaOH, stirring at room temperature until a white solid is separated out, carrying out suction filtration, and washing with methanol to obtain the organic acid salt.
  6. 6. Preservative or fungicide for wet wipes containing a LAE ion-pair compound as claimed in any one of the claims 1 to 3 or containing a LAE ion-pair compound according to the method of claims 4 or 5, characterized in that it comprises a LAE ion-pair compound in a concentration of 0.001-2% by mass.
  7. 7. The antiseptic or antifungal agent for wet wipes of claim 6 comprising a LAE ion pair compound at a concentration of 0.001 to 0.01%, 0.01 to 0.1%, 0.05 to 0.1%, 0.1 to 0.2%, 0.1 to 1%, 1 to 2%, or 1.5 to 2% by weight.
  8. 8. The antiseptic or antifungal agent for wet wipes of claim 7 comprising 0.01 to 0.1% and 0.05 to 0.1% by weight of the LAE ion pair compound.
CN201910544783.2A 2018-06-22 2019-06-21 Anti-corrosion sterilization type wet tissue and preparation method and application thereof Active CN110313489B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110317818.6A CN112790196B (en) 2018-06-22 2019-06-21 Anti-corrosion sterilization type wet tissue and preparation method and application thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2018106488835 2018-06-22
CN201810648883 2018-06-22

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN202110317818.6A Division CN112790196B (en) 2018-06-22 2019-06-21 Anti-corrosion sterilization type wet tissue and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110313489A CN110313489A (en) 2019-10-11
CN110313489B true CN110313489B (en) 2021-07-27

Family

ID=68120105

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201910544783.2A Active CN110313489B (en) 2018-06-22 2019-06-21 Anti-corrosion sterilization type wet tissue and preparation method and application thereof
CN202110317818.6A Active CN112790196B (en) 2018-06-22 2019-06-21 Anti-corrosion sterilization type wet tissue and preparation method and application thereof

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN202110317818.6A Active CN112790196B (en) 2018-06-22 2019-06-21 Anti-corrosion sterilization type wet tissue and preparation method and application thereof

Country Status (1)

Country Link
CN (2) CN110313489B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114376933A (en) * 2022-01-24 2022-04-22 抚顺东科新能源科技有限公司 Antimicrobial composition for infant hand and mouth wet tissue and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101227884A (en) * 2005-08-01 2008-07-23 米雷特实验室股份公司 Corrosion protection system including cationic surfactant
CN101500552A (en) * 2006-08-03 2009-08-05 米雷特实验室股份公司 Antiviral use of cationic surfactant
CN106565546A (en) * 2016-10-21 2017-04-19 武汉桀升生物科技有限公司 Lauroyl arginine ethyl ester glycol acid salt and preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090318557A1 (en) * 2003-12-22 2009-12-24 Stockel Richard F Dermatological compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101227884A (en) * 2005-08-01 2008-07-23 米雷特实验室股份公司 Corrosion protection system including cationic surfactant
CN101500552A (en) * 2006-08-03 2009-08-05 米雷特实验室股份公司 Antiviral use of cationic surfactant
CN106565546A (en) * 2016-10-21 2017-04-19 武汉桀升生物科技有限公司 Lauroyl arginine ethyl ester glycol acid salt and preparation method and application thereof

Also Published As

Publication number Publication date
CN112790196A (en) 2021-05-14
CN110313489A (en) 2019-10-11
CN112790196B (en) 2022-05-06

Similar Documents

Publication Publication Date Title
CN105407729B (en) Wrap polyamine-containing composition and method
TW200534875A (en) Personal care compositions and concentrates for making the same
EP1617915B1 (en) Activated citrus peel extract
CN110313489B (en) Anti-corrosion sterilization type wet tissue and preparation method and application thereof
WO2017129339A1 (en) Aqueous compositions of perillic acid compounds
CN110237065A (en) New antimicrobial compositions and its preparation method and application
CN112790195B (en) Mildew-proof adhesive and preparation method and application thereof
CN110313518B (en) Novel fruit and vegetable fresh-keeping agent and preparation method and application thereof
CN114376933A (en) Antimicrobial composition for infant hand and mouth wet tissue and preparation method thereof
CN112790197B (en) Novel leather mildew-proof nursing agent and preparation method and application thereof
CN112899087B (en) Kitchen oil stain cleaning agent
JP2002233471A (en) Wet tissue
CN110352959B (en) Antibacterial preservative film and preparation method and application thereof
CN110235899B (en) Novel food preservative and preparation method and application thereof
CN115089504A (en) Novel cosmetic compositions, process for their preparation and their use
CN114869793A (en) Novel bath product composition, preparation method and application thereof
CN107821398A (en) A kind of water-soluble amino acids Compositional antiseptic agent
CN110292568B (en) Novel pharmaceutical coated articles, method of manufacture and uses thereof
RU2432741C1 (en) Fungicide material for food and agricultural products
KR100532163B1 (en) Formulation for antibacterial and deodorante agent
Schimmel et al. Preservation of cosmetics
CN114983842A (en) Compound anticorrosive composition and preparation method and application thereof
JP2020180102A (en) Anti-norovirus agent, disinfectant and cleaning agent
JPH0441404A (en) Antibiotic-antibacterial agent for gram positive bacterial and method for antibiotic-antibacterial treatment
CN114869792A (en) Novel oral care compositions, methods of making and uses thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant