CN101766188B - Chitosan antimicrobial agent - Google Patents
Chitosan antimicrobial agent Download PDFInfo
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- CN101766188B CN101766188B CN2008101880304A CN200810188030A CN101766188B CN 101766188 B CN101766188 B CN 101766188B CN 2008101880304 A CN2008101880304 A CN 2008101880304A CN 200810188030 A CN200810188030 A CN 200810188030A CN 101766188 B CN101766188 B CN 101766188B
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- shitosan
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- 239000004599 antimicrobial Substances 0.000 title claims abstract description 47
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- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
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Abstract
The present invention discloses a chitosan antimicrobial agent, comprising a chitosan, a combined synergist, a solubilizer and a stabilizer. The chitosan has a weight-average molecular weight between 1500 and 3000 and a deacetylated degree between 90 and 95%. The combined synergist is polyquaternium and chelant, the chelant is EDTA, the solubilizer and the stabilizer are polyol. The common dosage of the chitosan antimicrobial agent is 0.2 wt%. The invention further discloses a preparation method of the chitosan antimicrobial agent.
Description
Technical field
The present invention relates to a kind of chitosan antimicrobial agent, it comprises shitosan, synergy agent, solubilizer and stabilizing agent.The weight average molecular weight of said shitosan is 1500-3000, and deacetylation is 90-95%.Said synergy agent is polyquaternium and chelating agent.Said chelating agent is EDTA.Said solubilizer and stabilizing agent are polyalcohol.The conventional using dosage of said chitosan antimicrobial agent is: 0.2wt%.And the invention also discloses the preparation method of above-mentioned chitosan antimicrobial agent.
This chitosan antimicrobial agent has that antimicrbial power is strong, the characteristics of has a broad antifungal spectrum, safety gentleness, stable performance, with low cost, environmental protection.
Background technology
Along with human living standard's raising, the enhancing of health perception, the parent that antimicrobial product receives people day by day looks at.The bactericide that is fit to the human body use mainly contains three types: inorganic fungicide, organic bactericide, natural bactericidal agent.
Inorganic fungicide mainly is that silver is bactericide, but because of the discoloration problem of silver ion is not effectively controlled all the time, causes the practical application of this series bactericidal agent to receive very big restriction.
Mostly organic bactericide is synthetic, as: hibitane, quaternary ammonium salt, triclosan etc. are to use maximum bactericide at present, and there are defectives such as poor stability, environmental pollution, consumes energy in this series bactericidal agent.
The principal item of natural bactericidal agent has: shitosan, tea oil, sorbic acid, yellow ginger root alcohol, Hinokitiol, the Meng ancestor's bamboo extract, coptis extract etc.; This series bactericidal agent is because of problems such as effective application dose too big (MIC is high), cost costliness, poorly water-soluble, complicated process of preparation, color instabilities; Be difficult to realize the industrial mass application so far, rest on the laboratory research stage mostly, but take from natural because of it; Human use is especially safe; The main trend that meets the mankind's " back to nature " is pretended and is bactericide, is the important class that academia concentrates on studies, seek assiduously all the time.
Shitosan is with a wide range of applications in medicines and health protection, food fresh keeping, agricultural, the medium field of cosmetics owing to having excellent biological compatibility, biological degradability, having no side effect and antibiotic, ntiviral characteristic in recent years.The shitosan chemical name is (1-4)-2-amino-2-dehydrogenation-callose, is through the deacetylation reaction by chitin.Chitin extensively is present in the cell wall of arthropodan shell, fungi and some algae such as shrimp, crab.The synthetic amount of the annual chitin of natural world reaches tens tons, is that output is only second to the second largest natural polymer of cellulosic natural world.Shrimp shell, crab shell etc. are removed inorganic calcareous through pickling, remove deproteinize through soda boiling, just are chitin.Chitin carries out deacetylated reaction and obtains shitosan in concentrated base.So shitosan is a kind of inexhaustible, nexhaustible natural reproducible resource.At present China's chitin and about 2500 tons of shitosan annual production, mainly the place of production is provinces such as coastal Zhejiang, Jiangsu, Fujian, Guangdong, produces the bullion chitin mostly, has only a small amount of enterprise production shitosan.1979, Allan found that first shitosan has extensive antibiotic property.Academia has carried out extensive studies to the antibacterial action of shitosan afterwards.
The article that Wen Yulin etc. deliver " application in pharmaceutical preparation of chitin and derivative thereof " (Chinese marine organisms, 1989; (1): put down in writing shitosan (Chitosan 33); Deacetylated chitin;
FlonacN; Chitosan; Chitosan; Soluble chitin; Chitosan; Chitan; Chitosan; Soluble chitin) and derivative can be used for the purposes of biologic product.
Disclose a kind of thiocarbamide shitosan-Ag+ complex compound among the CN1712417A, wherein made the thiocarbamide shitosan by shitosan and ammonium thiocyanate reaction, again that thiocarbamide shitosan dissolving back and silver nitrate is mixed.This complex compound is used for antibacterial agent and has has a broad antifungal spectrum, antibacterial effect outstanding feature.
The preparation method of a kind of shitosan/metallic copper complex antimicrobials is disclosed among the CN1685831A; Wherein with raw materials of chitosan purification back and transitional metal ion copper coordination; And with acetone ethanol mixed solvent deposition, the dry shitosan/metallic copper complex antimicrobials that obtains of washing.The organic/inorganic complex antimicrobials of this method preparation has good broad spectrum antibacterial, and the bacteriostatic activity of various pathogens all is improved largely.This antibacterial agent can be used for the antibiotic of food, textile industry and commodity.
Up to now, shitosan has at home and abroad obtained widely using as antibacterial agent, but the main application complex antimicrobials that concentrates on biologic product or shitosan and heavy metal are compounded to form at present.But above-mentioned antibacterial agent preparation cost is high, and big for environmental pollution to the mankind's poor stability, its bio-toxicity can not satisfy the requirement of the green non-poisonous antibacterial agent of current development.
Summary of the invention
To the problem that exists in the above-mentioned prior art, the present invention provides a kind of chitosan antimicrobial agent.This chitosan antimicrobial agent comprises shitosan, synergy agent, solubilizer and stabilizing agent.The synergy agent is polyquaternium and chelating agent.Said chelating agent is EDTA.Solubilizer and stabilizing agent are polyalcohol.This chitosan antimicrobial agent makes the fungicidal effectiveness of simple shitosan improve nearly 30 times, and has solved the technological difficulties that shitosan is used as the bactericide industrial mass, has realized the deep processing and utilization to natural marine resource product.This chitosan antimicrobial agent has that antimicrbial power is strong, the characteristics of has a broad antifungal spectrum, safety gentleness, stable performance, with low cost, environmental protection.These article (0.2wt%) reach more than 99% 2 minutes killing rates of staphylococcus aureus, Escherichia coli, Candida albicans.At least can keep 2 years under the bactericidal action room temperature of these article.Under conventional using dosage, these article are non-stimulated to skin, eyes, mucous membrane, can not cause allergic.
The main sterilization mechanism of shitosan is: 1) chitosan molecule gets in the bacterial cell, and destruction DNA transcribes to RNA's, causes bacterial reproduction and stops; 2) positively charged chitosan molecule makes its respiration inhibition and death through the bacteria cell wall of coulomb interaction adsoption band negative electrical charge.The former is main sterilization approach.Experiment shows, has certain relation between the bacteriostasis of shitosan and its molecular weight.The chitosan molecule amount is less than 2500, is easy to relatively get in the cell and is unfavorable for adsorbing bacterium; Molecular weight is greater than 3500, is easy to relatively adsorb bacterium and is unfavorable for getting in the cell.Other, in the chitosan molecule-NH
3 +Be its important sterilization factors, its relative density size is directly related with fungicidal effectiveness, and-NH
3 +The deacetylation of relative density and shitosan proportional, with the weight average molecular weight relation of being inversely proportional to.Through lot of experiments, find that the technical parameter of the shitosan of relatively tool fungicidal effectiveness is: weight average molecular weight 1500-3000, deacetylation 90-95%.
According to the antifungal mechanism of shitosan, the power of shitosan bacteriostatic activity is relevant with the amino on the shitosan, and its electropositive is strong more, and its bacteriostatic activity is strong more.And find through experiment, to shitosan carry out quaternized after, its bacteriostatic activity has tangible enhancing than shitosan.To the weakness (molecular weight bigger, be difficult for get into cell in) of simple shitosan, according to antibiotic synergy principle at antibiosis; Through a large amount of control experiments; Final definite polyquaternium, ethylenediamine tetra-acetic acid (EDTA) of adopting after the agent of shitosan compound synergic, can make comprehensive fungicidal effectiveness improve nearly 30 times.
To the characteristic of shitosan poorly water-soluble, facile hydrolysis,, confirm that finally polyalcohol is solvent and stabilizing agent through a large amount of screening experiments.
On the basis of measuring MGC (minimum inhibitory concentration), MIC (minimum bactericidal concentration),, confirm that finally the conventional using dosage of chitosan antimicrobial agent is: 0.2wt% according to practical application process condition and concerned countries standard-required.
Variable concentrations is to the influence of chitosan antimicrobial agent anti-microbial property
For above-mentioned experiment, the substitution value of shitosan is 1.02; Temperature is 25 degrees centigrade; PH is 6.3.Experiment shows that the chitosan antimicrobial agent of the present invention's preparation has good antibacterial effect to Escherichia coli and staphylococcus when 0.20wt%.
Experiment shows that its fungistatic effect was best when this chitosan antimicrobial agent was 6.5-7.5 at pH value.Wherein pH value is measured according to the 46th page of pH value determination method of second appendix of Pharmacopoeia of the People's Republic of China version in 2000 and is measured.
Wherein the bactericidal effect test is killed method of testing by disinfection technology standard version 2.1.1.5 in 2002 bar neutralizer characterization test method, 2.1.1.7 bar bacteria quantified base 2.1.1.9 bar fungi.
The relative density of this chitosan antimicrobial agent is 1.15-1.20 (bottle method is measured in according to the 40th page of relative density determination method of second appendix of Pharmacopoeia of the People's Republic of China version in 2000) down at 25 degrees centigrade.
The solid contents of this chitosan antimicrobial agent is 48-52wt%.
The assay method of solid contents is:
In the beaker of oven dry constant weight, taking by weighing 2g sample (being accurate to 0.0002g) dried three hours in 105 ± 1 degrees centigrade of constant temperature ovens.Drier is put in taking-up, is cooled to room temperature, claims its quality (being accurate to 0.0002g).
Solids concentration calculates:
Total solid (%)=(m3-m1) * 100/ (m2-m1)
Wherein: m1 is the quality g of empty beaker;
M2 is the quality g of preceding sample of oven dry and beaker;
M3 is the quality g of oven dry back residue and beaker.The result keeps a decimal.
The preparation method of this chitosan antimicrobial agent is:
The primary raw material of preparation shitosan
Annotate: the viscosity when viscosity fingernail element or shitosan are dissolved in 1% acetic acid solution (test of rotation viscosity apparatus, 25 ℃, Hereinafter the same).
The primary raw material of preparation bactericide
Wherein chelating agent is preferably EDTA.For not restriction of polyalcohol.
Description of drawings:
Fig. 1 is process route and flow chart.
1) Preparation of Chitosan
Ingredient inspection → chitin is pulverized (25-30 order)
Add deionized water and NaOH in the agitated reactor; Start and stir, be made into 40-45% alkali lye, constant temperature to 98-102 ℃ → adding chitin; Soak 1-2h → fill nitrogen reaction some time → addings peroxidating agent, react some time → washing → dehydration → 98-102 ℃ of following vacuum drying → check.
2) bactericide preparation
Ingredient inspection → by above-mentioned weight ratio batch weighing
Polyquaternium, polyalcohol add in the liquid agitation pot, start to stir, constant temperature to 48-52 ℃ → add shitosan, chelating agent, stir 20-30 minute → reduce to normal temperature → blowing, packing → product inspection.
Wherein the peroxidating agent is preferably SODIUM PERCARBONATE, but is not limited thereto.In addition, unless otherwise mentioned, otherwise the % of indicated concentration all refers to percentage by weight.
Bactericide compatibility mechanism
The Preparation of Chitosan technical study
1) deacetylation control experiment
Experiment shows: under the relatively-stationary condition of raw material specification and concentration of lye, reaction temperature, react 2-3 hour comparatively reasonable.
2) molecular weight control experiment
Experiment shows: under the relatively-stationary condition of degradation agent consumption and reaction temperature, react 0.7-1.4 hour comparatively reasonable.
Experiment on Microbiology research
Experimental basis: " disinfection technology standard " (Ministry of Public Health's version in 2002), GB15979-2002 " disposable use amenities sanitary standard "
(1) kills/bacteriostatic experiment
A, single raw material sterilization experiment (experimental strain: Escherichia coli 8099)
Experiment shows: 0.5% aqueous solution of 4 kinds of single raw materials does not all have obvious killing action to Escherichia coli.
B, prescription split sterilization experiment (experimental strain: Escherichia coli 8099)
Experiment shows:
1) 4 kinds of raw materials aqueous solution of share (each 0.5wt%) has strong killing action to Escherichia coli.
2) remove shitosan or polyquaternium in the prescription, Escherichia coli are not had obvious killing action.
3) remove chelating agent in the prescription, colibacillary killing effect is had a significant effect.
4) remove polyalcohol in the prescription, colibacillary killing effect is not had obvious influence.
C, MBC (MIC) experiment
A) shitosan specification screening
Experiment shows: the shitosan fungicidal effectiveness of mean molecule quantity 1500-3000, deacetylation 95-100% is the strongest.
B) shitosan bactericide MIC measures
Experiment shows: shitosan is after the compound synergic agent, and its fungicidal effectiveness has improved nearly 30 times; On behalf of the killing effect of bacterial classification, the shitosan bactericide sort to 3: staphylococcus aureus＞Escherichia coli＞Candida albicans.
D, minimal inhibitory concentration (MGC) experiment
Experiment shows: the shitosan bactericide is to 3 same MIC of inhibition effectiveness ranking that represent bacterial classification.
(2) toxicological experiment
A, skin irritatin test
0.2wt% shitosan bactericide is 0 to the skin irritation index of cavy, belongs to nonirritant.
B, skin allergic reaction test
0.2wt% shitosan bactericide is 0 to the sensitization rate of guinea pig skin, belongs to I level sensitization.
C, vaginal mucosa irritant test
0.2wt% shitosan bactericide is 0.2 to the SI of Female rabbits vaginal mucosa, belongs to nonirritant.
D, eye irritant test
0.2wt% shitosan bactericide is 3 to the acute eye irritation score index of rabbit, belongs to nonirritant.
(3) stable experiment
A, sterilization stability experiment (37 ℃ of accelerated tests)
Experiment conclusion: the bactericidal action of product at room temperature can keep 2 years at least.
B, stability of viscidity experiment
Experiment shows: shitosan bactericide normal temperature condition does not have obvious the decomposition down.
Application study
(1) wet sanitary napkins
A, towel material: spun laced fabric (viscose glue/terylene=70/30,50g/m
2).
B, liquid content: 300%.
C, shitosan bactericide consumption: 0.2wt%.
D, sanitary index:
E, experiment conclusion: product reaches the sanitary standard of GB15979 " wet sanitary napkins ".
(2) antibiotic ES fiber
A, fiber dimensious: line density 2.0～2.6dtex, length 51 ± 3mm, 16 ± 5/25mm of crispation number, oil content 0.35～0.65wt%.
B, shitosan bactericide usage, consumption: directly add during the preparation spinning oil.The actual consumption of bactericide 0.15-0.25wt%.
C, fiber bacteriostasis property (leaching)
D, experiment conclusion: with reference to the GB15979 requirement, product has stronger inhibitory action to experimental strain.
(3) antibacterial non-woven
A, cloth specification: hot rolling type, 18-20g/m
2
B, shitosan bactericide usage, consumption: online coating, masking liquid rate 20-30wt%.The actual consumption of bactericide 0.15-0.25wt%.
C, non-weaving cloth bacteriostasis property (leaching)
D, experiment conclusion: with reference to the GB15979 requirement, product has stronger inhibitory action to experimental strain.
This chitosan antimicrobial agent is reflected at index in the experiment at bactericidal effect and aspect the excitant of skin, sensitization: the 0.2wt% aqueous solution is to 2 minutes killing rate＞99% of staphylococcus aureus, Escherichia coli, Candida albicans; The 0.2wt% aqueous solution carries out disposable irritant test to guinea pig skin, and skin irritation index should be 0.0-0.4, belongs to nonirritant; With the 0.2wt% aqueous solution guinea pig skin is carried out the allergy test, the sensitization rate should be 0-8% (I level), and sensitization intensity is extremely light.
Other index of this product: arsenic content≤0.001%; Lead content≤0.004%.
This product mainly can be used for all kinds of non-weaving cloths and wet disposable use amenities, medical supplies such as towel, sanitary napkin, paper diaper, mouth mask.In addition, also can be used for all kinds of household chemicalss.
The characteristics of this chitosan antimicrobial agent are: sterilizing power is strong, is mainly reflected in 2 minutes killing rates that the 0.2wt% using dosage represents bacterial classification to routine all greater than 99%; Fungicidal spectrum is wide, and representative bacterial classifications such as suppuration bacterium, enteric infection bacterium, saccharomycete are all had produce effects.In addition, this project product safety is gentle, and is non-stimulated to skin, eyes, mucous membrane, can not cause allergic reaction; Stable performance, its sterilization and time storage life are more than 2 years.Once more, project low cost product, application cost are merely import with about 70% of series bactericidal agent; Make, technique for applying is easy; With the natural biological raw material is main, environmentally safe.
Though particular content of the present invention has been described,, scope of the present invention is not limited to above-mentioned, but various modification, variation and replacement under not breaking away from spirit of the present invention still fall in protection scope of the present invention.
Claims (12)
1. chitosan antimicrobial agent; It is characterized in that this chitosan antimicrobial agent comprises shitosan, synergy agent, solubilizer and stabilizing agent; Said synergy agent is polyquaternium and chelating agent; Said solubilizer and stabilizing agent are polyalcohol, and wherein by 100wt% weight, this chitosan antimicrobial agent comprises the shitosan of 40wt%-60wt%, the polyquaternium of 10wt%-20wt%, the chelating agent of 10wt%-20wt% and the polyalcohol of 20wt%-30wt%.
2. chitosan antimicrobial agent according to claim 1, the weight average molecular weight that it is characterized in that said shitosan is 1500-3000, deacetylation is 90-95%.
3. chitosan antimicrobial agent according to claim 1 is characterized in that said chelating agent is an ethylenediamine tetra-acetic acid.
4. according to each described chitosan antimicrobial agent of claim 1-3, it is characterized in that the conventional using dosage of said chitosan antimicrobial agent is: 0.2wt%.
5. chitosan antimicrobial agent according to claim 4, the pH value that it is characterized in that said chitosan antimicrobial agent during for 6.5-7.5 its fungistatic effect best.
6. according to each described chitosan antimicrobial agent of claim 1-3, it is characterized in that the relative density of said chitosan antimicrobial agent is 1.15-1.20 down at 25 degrees centigrade.
7. according to each described chitosan antimicrobial agent of claim 1-3, the solid contents that it is characterized in that said chitosan antimicrobial agent is 48wt%-52wt%.
8. chitosan antimicrobial agent according to claim 4 is characterized in that the relative density of said chitosan antimicrobial agent is 1.15-1.20 down at 25 degrees centigrade.
9. chitosan antimicrobial agent according to claim 4, the solid contents that it is characterized in that said chitosan antimicrobial agent is 48wt%-52wt%.
10. like the preparation method of each described chitosan antimicrobial agent of claim 1-9, comprise the steps: successively
1) preparation of shitosan:
By composition weight is 100wt%, is that 14-16Pa.s and deacetylation are that the 1.5wt%-2.5wt% chitin raw material of 45-50% is ground into the 25-30 order with viscosity, adds the NaOH of 40wt%-45wt%; Constant temperature soaks 1-2h to 98-102 ℃, fills nitrogen reaction 2 then to 3h; Soak afterwards, add the peroxidating agent of 0.5wt%-1.5wt%, add balance of deionized water then and make that the weight of composition is 100wt%; Reaction 0.7-1.4h; Carry out deacetylation, then wash, dewater, 98-102 ℃ of following vacuum drying, obtaining weight average molecular weight is that 1500-3000 and deacetylation are the shitosan of 90-95%;
2) preparation of chitosan antimicrobial agent:
Polyquaternium, solubilizer, stabilizing agent are added in the liquid agitation pot, and said solubilizer and stabilizing agent are polyalcohol, start to stir; Constant temperature is to 48-52 ℃; Add above-mentioned shitosan and chelating agent afterwards, stirred 20-30 minute, reduce to normal temperature and obtain chitosan antimicrobial agent; Wherein by 100wt% weight, this chitosan antimicrobial agent comprises the shitosan of 40wt%-60wt%, the polyquaternium of 10wt%-20wt%, the chelating agent of 10wt%-20wt% and the polyalcohol of 20wt%-30wt%.
11. preparation method according to claim 10 is characterized in that said chelating agent is an ethylenediamine tetra-acetic acid.
12., it is characterized in that said peroxidating agent is a SODIUM PERCARBONATE according to claim 10 or 11 described preparation methods.
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| CN102845512A (en) * | 2012-07-28 | 2013-01-02 | 海南大学 | Water-soluble tea tree oil/chitosan antibacterial compound |
| CN104042791B (en) * | 2014-07-07 | 2017-06-27 | 江苏瑞京科技发展有限公司 | A kind of antibacterial modified chitose foaming agent and preparation method thereof |
| CN104474547A (en) * | 2015-01-07 | 2015-04-01 | 蓝佳堂生物医药（福建）有限公司 | Vaginal infection prevention immune globulin compound preservative |
| CN104830012A (en) * | 2015-05-12 | 2015-08-12 | 安徽雄亚塑胶科技有限公司 | High-performance TPE operating tablecloth and preparation method thereof |
| CN106344605A (en) * | 2016-08-04 | 2017-01-25 | 陈广圣 | Novel antibacterial agent |
| CN107184668A (en) * | 2017-06-12 | 2017-09-22 | 安徽肤彩生物科技有限公司 | A kind of preparation method of low cost hemostasis thimerosal |
| CN108812670A (en) * | 2018-07-13 | 2018-11-16 | 安吉汉洲生物科技有限公司 | Floor anti-mould and moth-proof agent composition and preparation method thereof |
| CN109169706A (en) * | 2018-07-19 | 2019-01-11 | 大美泰康（天津）生态科技有限公司 | Complex antimicrobials and antibacterial bacteriostatic type multifunctional inorganic ecologic coating obtained |
| CN113975294B (en) * | 2021-11-04 | 2022-06-28 | 首都医科大学附属北京口腔医院 | Medicine for eliminating toxin in root canal and its preparation method |
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| CN1676043A (en) * | 2004-03-03 | 2005-10-05 | 卡夫食品集团公司 | Antimicrobial effect of chitosan in beverages |
| CN1904159A (en) * | 2006-07-13 | 2007-01-31 | 苏州大学 | Anti bacteria natural silk composite nano-fiber material and its preparation method |
| CN1912231A (en) * | 2006-08-25 | 2007-02-14 | 江苏欣隆羽绒有限公司 | Antibiotic down and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676043A (en) * | 2004-03-03 | 2005-10-05 | 卡夫食品集团公司 | Antimicrobial effect of chitosan in beverages |
| CN1904159A (en) * | 2006-07-13 | 2007-01-31 | 苏州大学 | Anti bacteria natural silk composite nano-fiber material and its preparation method |
| CN1912231A (en) * | 2006-08-25 | 2007-02-14 | 江苏欣隆羽绒有限公司 | Antibiotic down and its preparation method |
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Assignee: Hangzhou Sian antibacterial Technology Research Institute Co.,Ltd. Assignor: Zhang Zijian Contract record no.: 2012330000421 Denomination of invention: Chitosan antimicrobial agent Granted publication date: 20120321 License type: Exclusive License Open date: 20100707 Record date: 20120711 |
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Effective date of registration: 20231206 Address after: Room 101, Building 37, No. 536 Shunfeng Road, Tangqi Town, Linping District, Hangzhou City, Zhejiang Province, 311100 Patentee after: Hangzhou Sian antibacterial Technology Research Institute Co.,Ltd. Address before: Hangzhou City, Zhejiang province 310023 Leisure Town Yuhang District Jingshan temple building 21 unit 2 Patentee before: Zhang Zijian |