CN105594737A

CN105594737A - Sterilization disinfectant liquid

Info

Publication number: CN105594737A
Application number: CN201510946327.2A
Authority: CN
Inventors: 王芳; 郝香敏
Original assignee: Individual
Current assignee: Individual
Priority date: 2015-12-09
Filing date: 2015-12-09
Publication date: 2016-05-25

Abstract

A sterilization disinfectant liquid comprises antibacterial metal ions and L-cysteine and L-ascorbic acid as main components, the main components comprise surfactants excluding nonionic surfactants, and the sterilization disinfectant liquid comprises a sulfo-group-introduced amorphous carbon powder material. The sulfo-group-introduced amorphous carbon can be a carbon-based solid acid A, a carbon-based solid acid B and a carbon-based solid acid C. Beneficial effects are as follows: the sterilization disinfectant liquid is almost non-toxic and harmless to humans and animals, shows high sterilizing power for pathogenic microorganisms in a wide range, and is excellent in bactericidal sustainability.

Description

Disinfection solution

Technical field

Invention relates to a kind of new disinfection solution not having in concept in the past, and this disinfection solution is to meet life and lifeAmino acid, vitamin and the mineral matter of the base substance of life activity are main component, safe, and have the anti-of broad rangeBacterium spectrum can be used in many objects, multipurpose.

Background technology

For a long time, it has been recognized that the necessity of object surface being carried out to sterilization for healthy and health. PeopleNeed effective method for disinfection for various objects, comprise aseptic packaging, Medical Devices sterilization, biocidal carrier is with protectionEnvironment, fumigation, container sterilization, food preparation etc.

For example, as method for disinfection infectious, pathogenic microbes, conventionally encourage pasteurization method, but becauseIn the situation that being difficult to heat treated or due to hot, produce the reasons such as quality reduction, therefore heating-up temperature is restricted conventionally,Bactericidal effect is also restricted naturally. Replace pasteurization or merge and use compound to arise at the historic moment with pasteurization.The compound sterilizing that prior art is used is generally peracetic acid. In general, peracetic acid is used to aqueous based systems, for example, comprisedThe equilibrium mixture of acetic acid, acetic acid and hydrogen peroxide. Although verified this system is effectively, applies in the applicationTime it is generally acknowledged that solid acid does not have the such bactericidal effect of liquid acid, the inventor studies discovery: contain and imported sulfo groupThe material of amorphous carbon shows that strong bactericidal effect is completely unforeseeable to those skilled in the art.

In addition, as conventional example, in patent documentation 2, disclose in the method for disinfection of microorganism (Escherichia coli), withUnder the existence of allyl isothiocyanate, heating-up temperature is the formation that the mode below 60 DEG C is processed. Public in patent documentation 3In the method for disinfection of the microorganism having opened at water conservancy facility, make silver ion and copper ion, silver ion and residual chlorine, copper ion andThe formation that residual chlorine or silver ion and copper ion and residual chlorine coexist. Killing of a kind of gas or liquid disclosed in patent documentation 4Bacterium method, the material that makes to contain the amorphous carbon that has imported sulfo group contacts with the microorganism in gas or in liquid.

As existing general disinfection sanitizer, have alcohols, phenols, halide, quaternary ammonium salt, biguanides medicament, secondAldehydes etc., recently, in the sterilization of fresh food material, also start to utilize strong oxidized water and Ozone Water etc., as these sterilizationsThe desired condition that should have of disinfectant, is listed below: the scope of antimicrobial spectrum is wide; Just can carry out sterilization with short-time contact(quick-acting); Stability is high, and bactericidal action continues; Even under organic existence, effect declines also few; Few to body harm(hypotoxicity); Easily molten in water, using method is easy; Permeability is strong; There is no unhappy smell; Cheap; Keeping quality is good; Easily uselessAbandon; Do not damage use object; Do not form drug resistance bacterium.

Regrettably the disinfection sanitizer that, meets above-mentioned full terms does not exist. Therefore be, according to application target at presentIn these conditions, determine which condition is the most important existing disinfectant of selecting.

Bacterium as can be seen and the example of antibiotic relation, bacterium to the medicament (compound) of attacking self sooner or laterAlso by acquired resistance. This is the unavoidable fact, has reported multiple alcohol and quaternary ammonium salt or the invalid bacterium of biguanides medicamentAt the example of inside-hospital infection.

Follow the modern medicine dawn from starting in the middle of the 19th century, people are in being subject to grace, also in a lot of poisoningWith shut my eyes in toxicity, on popular sacrifice, obtain medical development and be undisputable fact to the pursuit of truth.

Since entering 21 century, various circles of society and the sight line from the common people, develop " relieved and safely " and be counted asBeyond all else is important and be placed in the prepreerence epoch.

Based on above-mentioned present situation, someone has developed the bactericidal liquid that roughly has both above-mentioned necessary condition, " contains conduct in 1998The bactericidal liquid of iron ion " file an application and obtain patent (patent documentation 5), even if this bactericidal liquid is by also obtaining as food additivesForm to the several compounds that uses accreditation, although be hypotoxicity, in the putting out of tulase and helicobacter pylori, with alsoWith the appearance of the same principle compacting resistant bacterium of various medicaments. In addition, have antimicrobial spectrum extensively, also effective etc. excellent special to brood cellProperty. But the present inventor has carried out distinguishing after further research to the above-mentioned bactericidal liquid that contains iron ion, is subject to mainComposition Fe³⁺The impact of ion, is still used all painted (when placement) and bactericidal liquid gradually of tester in bactericidal liquid itselfFoul smell aspect, in addition in the time interspersing among on crop for sterilisation purpose to its growth generating portion infringement etc., for user andSpeech is not 100% satisfied bactericidal liquid. In addition, although the sterilizing power of the above-mentioned bactericidal liquid that contains iron ion to various pathogensExcellence, but also dissatisfied to viral lethality.

Patent documentation 1:CN201080006823.5

Patent documentation 2: Japanese kokai publication hei 11-322521 communique

Patent documentation 3: TOHKEMY 2007-268402 communique

Patent documentation 4:CN201080036149.5

Patent documentation 5: No. 3853985 communique of Japanese patent gazette

Summary of the invention

For above-mentioned problems of the prior art, the present invention aims to provide a kind of to the almost non-toxic nothing of humans and animalsEvil, and the pathogenic microorganism of wide scope is shown to very high sterilizing power, and also the sterilization of the continuation excellence of bactericidal action disappearsVenom.

To achieve these goals, the present invention takes following technical scheme:

The present invention relates to a kind of disinfection solution that material is carried out to sterilization, this disinfection solution is to have antibacterial actionMetal ion and Cys and L-AA are main component, contain except living on nonionic surface in this main componentProperty surfactant beyond agent, it is characterized in that: the powder that contains the amorphous carbon that has imported sulfo group in this disinfection solutionMaterial.

Preferably, it is that solid acid A, carbon are that solid acid B and carbon are solid that the amorphous carbon that has imported sulfo group can use carbonAcid C, carbon is that solid acid A is by by by organic compound and the sulfur trioxide of not exclusively carbonization or the sulphur that contains sulfur trioxideThereby agent is carried out heat treated and is carried out the solid acid that condensation and sulfonation obtain; Carbon is that solid acid B is by selecting freely 2～7At least a kind in the Ppolynuclear aromatic hydrocarbon that aromatic rings condensation forms is carried out heat treated and carrys out condensation in the concentrated sulfuric acid or oleumThereby the solid acid with sulfonation acquisition; Carbon is that solid acid C is by organic compound is carried out in the concentrated sulfuric acid or oleumHeat treated import sulfo group and solid acid.

Preferably, the metal ion that has an antibacterial action is the iron ion (Fe of trivalent³⁺), the iron ion (Fe of divalence²⁺)、Zinc ion (Zn²⁺), copper ion (Cu²⁺), cobalt ions (Co²⁺), nickel ion (Ni²⁺) or silver ion (Ag⁺)。

Preferably, the concentration that has a metal ion of antibacterial action is 50 in the case of the iron ion of trivalent～200ppm, in the case of the iron ion of divalence, be 110～400ppm, the in the situation that of zinc ion, be 7.5～125ppm, at copperIn the situation of ion, be 15～60ppm, the in the situation that of cobalt ions, be 180～300ppm, the in the situation that of nickel ion, be 85～175ppm, the in the situation that of silver ion, be 1～3ppm.

Preferably, the concentration of Cys is 100～1000ppm, and the concentration of L-AA is 100～500ppm.

Preferably, the surfactant except nonionic surface active agent is to be selected from alkylbenzenesulfonate, straight chain alkaneBase benzene sulfonate, polyoxyethylene alkyl ether sulfate salt, higher alcohol sulfate salt, lauryl sodium sulfate, sodium lauroyl sarcosine,Stearyl dimethyl benzyl ammonium chloride, benzalkonium chloride, benzethonium chloride, alkyl diaminoethyl glycine hydrochloride and alkyl gather ammoniaMore than one in ethyl glycine hydrochloride.

Preferably, the concentration of the surfactant except nonionic surface active agent is 20～100ppm.

Preferably, in the disinfection solution that this method is used, also contain and be selected from sorbic acid, sorbate, benzoic acid, benzeneMore than one in formates and p-hydroxybenzoate.

Preferably, the concentration of sorbic acid, sorbate, benzoic acid, benzoate and p-hydroxybenzoate be 50～100ppm。

Preferably, the disinfection solution pH that this method is used is adjusted into 2.5～4.0.

The beneficial effect of the invention: this disinfection solution is almost non-toxic harmless to humans and animals, and cause of disease to wide scopeMicroorganism shows very high sterilizing power, and the continuation excellence of bactericidal action.

Detailed description of the invention

Since ancient times, silver and the antibiotic property of copper are with regard to being known to experience, in history always at tableware, currency, ornament etc.In daily life, make full use of, but expose with organic disinfectant as antiseptic, except a part of goods, almost do not haveAt present and look back the visible fact. In this case, the inventor of patent documentation 1 is at the disinfection solution of patent documentation 1Middle adopted toxicity lower, can be used as food additives and use and show the ferric ion (Fe of antibacterial action³⁺) doFor main component.

Such mineral-type antiseptic is discussed it for the present, and at short notice whether acumen is strong, but possesses basic antimicrobial spectrumExtensively, there is the excellent speciality such as stability, keeping quality. Be not limited to above-mentioned Fe³⁺Ion, from taking in the necessary mineral of body tissueIn matter, attempt having carried out studying again result, choosing for the mineral matter (the atomic effect of metal) that shows antibacterial action with traceSelect and adopt zinc ion (Zn²⁺), copper ion (Cu²⁺), cobalt ions (Co²⁺), nickel ion (Ni²⁺), ferrous ion (Fe²⁺) and from ancient timesSince have the silver ion (Ag of real result⁺), the ion concentration of these mineral matters of close examination etc. and the relevant pass of antibacterial activitySystem, is categorized as a) bacterial multiplication inhibitory action, b) bacteriostasis and c) 3 stages of bactericidal action are carried out close examination that is.

In addition, in the data in described later description etc., by unified to " mineral ion " be denoted as common-use words " metal fromSon ".

1) in the situation of adding each metal ion species in culture medium for propagation

Standard viable count shown in following is measured with in culture medium, changes concentration and adds each metal ion, then inoculates 1% by weight is for the suspension (1 × 10 of examination bacterium⁹Cell/ml drink raw water) after, according to conventional method through time measure viable count, rootObserve the dependency relation of each metal ion and antibacterial activity according to its growth and decline, in the 1st table, gather.

Zero for trying bacterium: as the representative S.aureus209P of gram-positive bacteria

As the representative E.coliO-157 of Gram-negative bacteria

Zero standard viable count mensuration culture medium: yeast extract 2.5g, peptone 5g, glucose 1g, agar 15g,pH7.2

[table 1]

The antibacterial activity of the 1st table (1) metal ion

To S.aureus209P

The the 1st (2)

To E.coliO-157

Add metal ion culture of bacteria in culture medium time, the known inhibited proliferation being produced by concentration of metal ionsNot obvious with the line of demarcation of bacteriostasis, but can roughly obviously distinguish bacteriostasis and bactericidal action.

For example,, at Cu²⁺Situation under, in the scope of 10～50ppm, bring into play inhibited proliferation, 40～150ppm'sIn scope, performance bacteriostasis, if more than reaching 150ppm, brings into play bactericidal action.

In addition, in upper table, only record the representative compound of each metal ion species, but for forming in water solubleFor other compound of ion, for example, with Fe³⁺Relevant iron chloride, ferric nitrate hexahydrate, ferric nitrate nonahydrate,Ferric nitrate n hydrate, ferric phosphate n hydrate, ironic citrate n hydrate etc., with Fe²⁺Relevant frerrous chloride tetrahydrate, PortugalSaccharic acid ferrous iron, ferrous citrate, ferrous oxalate etc., with Zn²⁺Relevant zinc citrate dihydrate, ZnG etc., with Cu²⁺Relevant copper chloride dihydrate, chlorination two ammonium copper dihydrates, copper nitrate trihydrate compound etc., with Co²⁺Relevant gluconic acid cobaltTrihydrate, cobalt hydroxide, citric acid cobalt etc., with Ni²⁺Relevant nickel nitrate etc. and and Ag⁺Relevant silver sulfate, silver orthophosphate etc.,Also shown similar achievement.

Incidentally, there is the promotion showing growing in the appropriateness of metal ion (mineral matter). (2) according to the 1st table (1),(2) result, then adds 1 % by weight for trying bacterium suspension being dissolved with in the aqueous solution of each metal ion (28 DEG C of Purified Waters)(1×10⁹Cell/1ml water), make it contact, take 0.2ml through time ground at every turn, measure viable count according to conventional method immediately, meterSurvey the death rate, infer thus the dependency relation of concentration of metal ions and antibacterial activity. In addition, as for examination bacterium, adoptedStaphylococcusaureus209P and EscherichiacoliO-157, because this 2 strain all shows similar achievement,So, in the 2nd following table, represent its mean value.

[table 2]

The antibacterial activity of the metal ion in the 2nd table Purified Water

In the Purified Water of metal ion not, the death rate of 60 minutes is 2%, and the death rate during through 120 minutes is3% left and right (self-dissolving), in addition, in the Purified Water that is added with metal ion, its ion concentration and the death rate are proportional, but canWhile knowing the short-time contact about 10～15 minutes, little by the difference of the death rate of the deep or light generation of concentration, and known, evenConcentration is extremely low, as long as extend contact time, although effect is not sharp, but bacterium also can accelerate death gradually.

Can infer according to the relevant test data of metal ion in above-mentioned the 1st table, the 2nd table:

<1>in culture medium, add metal ion, if the propagation of bacterium is suppressed, the way of bactericidal action under this concentrationFootpath also continues.

<2>in the time expecting with short-time contact sterilization, the concentration obviously manifesting from bacterial multiplication inhibitory action is to antibacterial workIn concentration range with obvious appearance, be sufficient concentration.

<3>, even to show that the concentration of bactericidal action makes bacterium contact, can not expect great kill capability.

<4>therefore, security is also investigated, is made concentration in<2>shown in concentration range in, and make up it notFully part, the method for drawing to greatest extent thus more powerful bactericidal action is reasonable.

(2) imported sulfo group amorphous carbon checking and study again

1) in this embodiment, be used as the Euglena (euglena) of the Euglena in Euglenophyta, protozoa,Propagation has imported the amorphous carbon of sulfo group with interpolation in culture medium, studies the bactericidal effect that each carbon is solid acid A～C, in table 3:

Table 3

As known from Table 3, by imported sulfo group amorphous carbon kind produce antibacterial activity there is no difference, all showPowerful bactericidal properties.

2) while adding the amorphous carbon that has imported sulfo group in Purified Water, produce through time the death rate, in table 4

Table 4

In Purified Water, add while having imported the amorphous carbon of sulfo group, than not adding the amorphous carbon that has imported sulfo groupPurified Water, its death rate uprises.

Then, attempt checking about and with both, that is, and with metal ion the effect when having imported the amorphous carbon of sulfo groupReally, add metal ion and imported the amorphous carbon of sulfo group in Purified Water, its death rate is in table 5:

Table 5:

In Purified Water, add metal ion and while having imported the amorphous carbon of sulfo group, than only add metal ion orImported the Purified Water of the amorphous carbon of sulfo group, its death rate uprises.

As the material that contains the amorphous carbon that has imported sulfo group, can use for example following carbon is solid acid A～C.

Be that solid acid A is by by by organic compound and the sulfur trioxide of not exclusively carbonization or contain sulfur trioxideThereby sulfonating agent carries out heat treated carrys out the solid acid that condensation and sulfonation obtain. Be that solid acid A was former in Japan about this carbonBe applied (No. 2009-134096, Japanese Patent Application).

Here, as organic compound, can be culled wood, sawdust, preferably uses and is selected from benzene, anthracene, perylene, coronene or itSulfur-containing compound (ス Le ホ compound) in the Ppolynuclear aromatic hydro carbons of at least a kind. In addition, can also use and comprise virtueThe heavy oil of fragrant family hydro carbons, pitch (pitch), tar, asphalt (asphalt) etc. Above organic compound can be independentUsing can be also two or more multiple mixtures. Referred to by comprising by the organic compound of not exclusively (midway) carbonizationThe amorphous carbon that the Ppolynuclear aromatic hydrocarbon of 10～20 aromatic series 6 rings forms, as an example, for having arranged 10～20 benzeneThe state of ring. For example, by by organic compound at 200～600 DEG C, preferably 300～500 DEG C heating 0.5～20 hour, excellentSelect and within 1～10 hour, obtain by the organic compound of incomplete carbonization. By by the not exclusively organic compound sulfonation of carbonizationBe because, in such organic compound, the key of carbon and hydrogen is residual in a large number, in the time of sulfonation, sulfo group is incorporated into the key of this carbon and hydrogenPart, therefore obtain the solid acid that sulfo group density is higher. Therefore, be desirably in by large in the organic compound of not exclusively carbonizationThe key that amount comprises carbon and hydrogen, in other words, comprises hydrogen in a large number. By the hydrogen amount in the organic compound of not exclusively carbonization with hydrogenIn situation about representing than (H/C atomic ratio) with the element of carbon, be preferably 0.3～1.5, more preferably 0.5～1.1.

The chemical formula of sulfur oxide is SO₃, be also referred to as sulfuric anhydride. Make by the organic compound and three of incomplete carbonizationIn the situation of sulfur oxide contact, under the non-active gas such as nitrogen, argon gas air-flow or carry out for system under dry air air-flowIt is important making the solid acid that sulfo group density is high.

For the sulfonating agent that contains sulfur trioxide can illustrate oleum.

Carbon is that solid acid B is at least 1 in the Ppolynuclear aromatic hydrocarbon by free choosing 2～7 aromatic rings condensations are formedThereby kind in the concentrated sulfuric acid or oleum, carry out heat treated and carry out the solid acid that condensation and sulfonation obtain. Be solid about this carbonAcid B had been applied and had become patent (No. 40414909, Japanese Patent) in Japan in the past. Be the character of solid acid B about this carbon,Autofrettages etc. are recorded in No. 40414909, this patent gazette.

Here, as Ppolynuclear aromatic hydrocarbon, there are naphthalene, En, perylene and coronene etc., as long as at least 2 above aromatic rings condensationsThe synthesis material that can be just solid acid B as carbon uses. Known aromatic hydrocarbon basedly carry out in the concentrated sulfuric acid or oleumPolycondensation, the amorphous materials of the complicated Ppolynuclear aromatic hydrocarbon of condensation has been carried out in formation, along with the increase of aromatic rings number, its propertyQualitative change must with graphite approach etc. In addition, carbon of the present invention is that solid acid comprises by Ppolynuclear aromatic hydrocarbon particularly being selected to free 2At least a kind in the Ppolynuclear aromatic hydrocarbon that～7 aromatic rings condensations form is carried out heat treated in the concentrated sulfuric acid or oleumBy the condensation of Ppolynuclear aromatic hydrocarbon, sulfonation and stable chemical constitution.

Come sulfonation, polycondensation by Ppolynuclear aromatic hydrocarbon being carried out in the concentrated sulfuric acid or oleum to heat treated, thereby obtainObtain the sulfonation Ppolynuclear aromatic hydrocarbon that a large amount of aromatic rings polycondensations form. But the treatment temperature in the concentrated sulfuric acid or oleum is lowIn the situation of 100 DEG C, the polycondensation of Ppolynuclear aromatic hydrocarbon is not fully carried out, and can not form the many cyclophanes perfume (or spice) that comprises a large amount of aromatic ringsFamily's hydrocarbon, therefore can not get in polar solvent is insoluble solid acid. On the other hand, in the time that treatment temperature exceedes 450 DEG C, send outThe thermal decomposition of raw sulfo group, therefore can not get the insoluble amorphous hydrocarbon that sufficient sulfo group exists. Preferred treatment temperatureIt is 200 DEG C～350 DEG C. Solid acid catalyst of the present invention not only can be using single Ppolynuclear aromatic hydrocarbon as raw material, andMultiple Ppolynuclear aromatic hydrocarbon can be synthesized as raw material. In addition, can also multiple Ppolynuclear aromatic hydrocarbon and saturated will be comprisedPitch, the tar etc. of hydrocarbon, unsaturated hydrocarbons synthesize as raw material.

Be that solid acid C is for to import sulfo group by organic compound being carried out in the concentrated sulfuric acid or oleum to heat treatedAnd the solid acid obtaining. Be solid acid C about this carbon, the former international application (WO2005/029508) that carried out. About this carbon systemThe character of solid acid C, autofrettage etc. are recorded in International Publication communique WO2005/029508.

Here, as organic compound, can use aromatic hydrocarbon basedly, but also can use organising in additionCompound, for example, glucose, granulated sugar (sucrose), the such such synthetic high score of carbohydrate, polyethylene, polyacrylamide of celluloseSub-compound. Aromatic hydrocarbon based can be Ppolynuclear aromatic hydro carbons, can be also monocyclic aromatic hydro carbons, for example can use,Benzene, naphthalene, En, perylene, coronene etc., preferably, can use naphthalene etc. Organic compound can only use one, also can be by two kindsMore than be used in combination. In addition, not necessarily need to use purified organic compound, can use, for example, comprise aromatic hydrocarbonThe heavy oil of class, pitch, tar, asphalt etc.

Using the carbohydrate such as glucose, cellulose, synthetic macromolecular compound during as raw material, preferably at the concentrated sulfuric acid or be fumingBefore carrying out heat treated in sulfuric acid, these raw materials are heated in non-active gas air-flow, make it partially carbonized. NowHeating-up temperature be generally 200～600 DEG C, the processing time is generally 0.5～20 hour. Partially carbonized state is preferably and is addingIn the x-ray diffractogram of powder case of heat treatment thing, detect that half-peak breadth (2 θ) is the such shape of diffraction maximum of (002) face of 30 °State.

Using aromatic hydrocarbon based or comprise the feelings as raw material such as aromatic hydrocarbon based heavy oil, pitch, tar, asphaltUnder condition, preferably in the concentrated sulfuric acid or oleum, after heat treated, product is carried out to heating in vacuum. Thus, by superfluous sulphurAcid remove and promote product carbonization, solidify, make product yield increase. Vacuum exhaust is preferably used exhaust velocity 10L/ to divideClock is above, the following exhaust apparatus of limiting pressure 100 holder. Preferred heating-up temperature is 140～300 DEG C, and preferred temperature is200～280 DEG C. The time of vacuum exhaust when this temperature is generally 2～20 hours.

This carbon is the characteristic that solid acid C possesses following (1)～(3):

(1) exist¹³Condensation aromatic series carbon 6 rings and the condensation aromatic series that is combined with sulfo group in C NMR spectrum, detectedThe chemical shift of carbon 6 rings;

(2) in powder x-ray diffraction, at least detect that half-peak breadth (2 θ) is the diffraction maximum of carbon (002) face of 5～30 °,In addition, the diffraction maximum detecting can have the diffraction maximum except (002) face, the diffraction maximum of (002) face preferably only detected;

(3) show proton-conducting. In this case, proton conductivity is had no particular limits, be preferably 0.01～0.2Scm^-1, more preferably 0.08～0.11Scm^-1(above-mentioned proton conductivity is under the condition of 80 DEG C of humidity 100% of temperature,Measure the value obtaining by AC impedence method).

Make to contain the side that the thimerosal of the material of the amorphous carbon that has imported sulfo group contacts with the microorganism on thing to be sterilizedThere is no particular limitation for method, can illustrate following methods: for example can thing to be sterilized be soaked into contain imported sulfo group without fixedIn the thimerosal of the material of shape carbon.

In the present invention, microorganism refers to the material that is commonly referred to as microorganism, for example, and bacterium, archeobacteria, primary lifeThing, Mycophyta etc., but also comprise the such tool of Euglena unicellular Eukaryotic Algae amphitrichous, in addition, also comprise virus.

There is the mechanism of action of the bactericidal effect of the material of the amorphous carbon that has imported sulfo group to illustrate not yet in detail at present, but shouldMaterial has the sulfo group that becomes the strong acid position of working as with sulfuric acid phase. Therefore think by microorganism is contacted with this sulfo group, therebyPerformance bactericidal effect. In addition think, this material is owing to being carbonaceous, thereby has the adsorptivity to microorganism, by this adsorptivityAssemble the microorganism on article to be sterilized, thereby effectively make microorganism contact sulfo group.

Embodiment

Next, illustrate the bactericidal effect of the amorphous carbon that has imported sulfo group by embodiment.

Embodiment 1

In this embodiment, having studied the carbon of being made by following method is that solid acid A～C is to colibacillary bactericidal effect.

(1) carbon is the making of solid acid A

As organic compound, be used as the microcrystalline cellulose of commercially available product. This cellulose 20g is joined to there-necked flaskIn, under stream of nitrogen gas, 450 DEG C of heating 5 hours, the not exclusively material of carbonization that obtains 9g (was claimed " not complete below,Full carbide "). Guarantee the incomplete carbide of predetermined weight by repeating this operation. By the incomplete carbonization obtaining like thisThing 20.2g joins in 1L capacity eggplant type flask, is installed on rotary evaporator ROTAVAPORRE120 (PVC ュッヒ-ラボテクニック society (BUCHILabortechnikAG) (Switzerland) system) upper, eggplant type flask is heated to 60 DEG C and rotation, simultaneously logicalCross vavuum pump by degassed in evaporimeter (0.5kPa), carry out airtight. On the other hand, measure sulfur trioxide (day Cao's metallochemistryThe goods name of (strain) " day Cao サ Le Off ア Application ") 6.1g to gasification with in there-necked flask. This sulfur trioxide is steamed from being positioned at rotationThe injection cock on the condenser top of hair device imports in evaporimeter lentamente. After having imported sulfur trioxide, make eggplant on one sideThe rotation of type flask is reacted 2 hours at 60 DEG C on one side. After reaction, disconnect sulfur trioxide gas and import pipeline, in evaporimeterSulfur trioxide gas nitrogen replacement. Eggplant type flask is taken off from evaporimeter, in this eggplant type flask, add the steaming of about 500mLHeat up in a steamer water and stir 10 minutes. Temperature remains below 30 DEG C. Then, use hydrophily PTFE filter (ミリ Port ァ system, ォ systemニ Port ァ, aperture 10 μ m) suction filtration go out solid constituent. As water washing, solid constituent is suspended in again to the distilled water of about 500mLIn, stir 10 minutes, and then filter. Repeat this operation until the pH of filtrate becomes almost constant, then at 80 DEG CSolid constituent is dried to 1 day. Then,, as hot wash, solid constituent is washed with the distilled water 500mL of approximately 100 DEG CWash. Repeat this operation until the pH of filtrate becomes almost constant. After hot wash, at 80 DEG C, solid constituent is dried to 1 dayObtain solid acid 20.9g. Above carbon is that the sulfur content of solid acid A is 0.94 % by weight. Be that solid acid A grinds again by the carbon obtainingMake powder.

(2) carbon is the making of solid acid B

Be that solid acid B makes according to the record of the embodiment 1 of No. 4041409 communique of Japanese Patent. Institute specific as followsState. As Ppolynuclear aromatic hydrocarbon, be used as the coronene (C of commercially available product₂₄H₁₂). This coronene 1g is joined to the concentrated sulfuric acid of 100mL(96%), in and 200 DEG C of heating 8 hours, then, by removing the superfluous concentrated sulfuric acid the decompression distillation of 250 DEG C, obtain blackThe pressed powder of look. This pressed powder is washed with the ethanol of 300mL, repeat this operation until washing after ethanol inSulfuric acid be the detection limit of elementary analysis following till. The carbon of gained is that solid acid B is black powder, at X-ray diffraction patternIn can't be confirmed to be what kind of structure, and known be amorphous. In addition, above carbon is that the sulfur content of solid acid B is 4 weightsAmount %. Be that solid acid B is developed into powder again by the carbon obtaining.

(3) carbon is the making of solid acid C

Be that solid acid C makes according to the record of the embodiment of the description of International Publication: WO2005/029508 4. SpecificallyAs described below. As organic compound, be used as the naphthalene of commercially available product. This naphthalene 20g is joined to 96% concentrated sulfuric acid of 300mLIn, be blown into nitrogen on one side 250 DEG C of heating 15 hours to this mixture with 30ml/ minute on one side, thereby obtain the liquid of black.This liquid is adopted to exhaust velocity 50L/ minute, limiting pressure 1 × 10 on one side^-2The following high vacuum rotary pump of holder carries out vacuum rowGas, on one side 250 DEG C of heating 5 hours, thereby carries out removing and the promotion of carbonization of the superfluous concentrated sulfuric acid, obtains black powder.In nonactive air-flow, 180 DEG C of heating 12 hours, then adopt the distilled water of 300mL to wash this black powder, heavyMultiple this operation has been used the elementary analysis meter of flash of light burning to enter until the sulfuric acid in the distilled water after washing reaches above-mentioned passing throughTill below the detection limit of the elementary analysis of row, thereby obtain the amorphous carbon that has imported sulfo group, carbon is solid acid. This carbonBe solid acid,¹³In C NMR spectrum, if according to¹³The determination method of CMAS NMR spectrum is measured, and existsNear 130ppm, there is the chemical shift being caused by condensation aromatic series carbon 6 rings, near 140ppm, occur by being combined with sulfo groupThe chemical shift that causes of condensation aromatic series carbon 6 rings. This displacement is for adopting¹³The mensuration characteristic of CMAS NMR spectrumThe spinning side band observing, instead of derive from carbon kind. In addition, in the mensuration of being undertaken by x-ray analysis equipment, as powderEnd X-ray diffraction pattern, has confirmed the diffraction maximum of carbon (002) face and (004) face. (002) half-peak breadth of the diffraction maximum of face (2 θ)It is 11 °. In addition, above carbon is that the sulfur content of solid acid C is 9 % by weight. Be that solid acid C is developed into powder again by the carbon obtainingEnd.

(4) carbon is that solid acid A～C is to colibacillary bactericidal effect.

(a) Escherichia coli are used the Escherichia coli that obtain from independent administrative legal person's products assessment technique basal disc organization(Escherichiacoli) NBRC3972. And, about test organisms liquid, above-mentioned Escherichia coli are utilized to nutrient agar panel trainingTo support base (day a water pharmacy (strain) system) and cultivate 1 day at 30 DEG C, the thalline of gained is suspended in aqua sterilisa, bacterium number is adjusted into approximately 2 ×10⁷Cfu/ml (cfu is CFU).

(b), as bacterium number mensuration culture medium, in SCDLP culture medium " ダィ go " (Japanese pharmacy (strain) system), add1.5% agar is made multiple Agar Platings and is used.

(c) instrumentation operation is as described below. The pulverous carbon that takes 0.1g is that solid acid A is extremely with sillicon rubber blocking (シリコセ Application) bottle in, 121 DEG C of steam sterilizings 15 minutes. After this sterilization treatment, in bottle, add above-mentioned test organisms liquid 2ml,30 DEG C are rotated vibration (140rpm). After 10 minutes, (carbon is solid acid A+ test organisms to the treatment fluid in the bottle of sampling 200 μ lLiquid), carry out stepwise dilution (10～10 with aqua sterilisa immediately⁴Doubly dilution). Then, 50 μ l of each dilution bacterium liquid are spread upon respectivelyOn above-mentioned SCDLP Agar Plating. After smearing, leave standstill and cultivate 1～2 day at 30 DEG C, then utilize colony counting method to surveyDetermine viable count. In addition be that solid acid B, C also carry out similarly instrumentation for carbon.

(d) in addition, experiment, also carries out following such experiment in contrast. After steam sterilizing with sillicon rubber blockingBottle in add above-mentioned test organisms liquid 2ml, at 30 DEG C of rotational oscillations (140rpm). After 10 minutes, the examination in the bottle of sampling 200 μ lTest bacterium liquid, carry out stepwise dilution (10～10 with aqua sterilisa immediately⁴Doubly dilution). Then, 50 μ l of each dilution bacterium liquid are coated with respectivelyBe put on above-mentioned SCDLP Agar Plating. Then, leave standstill and cultivate after 1～2 day at 30 DEG C, utilize colony counting method to surveyDetermine viable count.

Table 6 shows its result. In addition, do not carry out the rotational oscillation processing of 10 minutes, and utilize colony counting method to measure examinationTest the viable count of bacterium liquid, the viable count during using this bacterium number as processing beginning is shown in Table 6. Viable count in table 6 is every 1ml placeManage the value of liquid, show the mean value of the viable count that carries out each processing experiment twice and obtain.

Table 6

Embodiment 2

In this embodiment, be used as Euglenophyta, the Euglena (euglena) of the Euglena in protozoa, withUnder lower condition, study the bactericidal effect that each carbon is solid acid A～C (cell membrane execution).

(1) carbon is that the making of solid acid A～C is made similarly to Example 1.

(2) carbon is the cell membrane execution of solid acid A～C to Euglena.

(a) test organisms uses the Euglena (powder) obtaining from (strain) ュ mono-ゲレ Na. The confirmation of this cell membrane executionUtilize and be present in the phenomenon that the intracellular glucose of Euglena is detected along with the destruction of Euglena.

(b) test method is as described below. The carbon that takes 3g is that the above-mentioned Euglena of solid acid A, 1.5g, the water of 2.5ml extremely burnIn cup, 30 DEG C of stirrings (400rpm) 1 hour. Then, judge bactericidal effect by the glucose of measuring in this aqueous solution. DoFor comparative example, replace carbon be solid acid and use strong-acid ion exchange resin (Aldrich society system, Amberlyst-15) come withSample ground is implemented. In addition be that solid acid B, C test similarly to carbon.

From above test, using carbon is in the situation of solid acid A, and glucose is 53mg, and using carbon is solid acid BSituation under, glucose is 20mg, use carbon be in the situation of solid acid C, glucose is 25mg. On the other hand, use strong acidIn the situation of property ion exchange resin, glucose do not detected.

(embodiment 3)

In this embodiment, the carbon that research is made by following method is the bactericidal effect of solid acid D to various microorganisms.

(1) carbon is the making of solid acid D

In 500mL capacity there-necked flask, add above-mentioned incomplete carbide 4g, 96% concentrated sulfuric acid 100mL and 30% is fumingSulfuric acid 100mL, under stream of nitrogen gas, 80 DEG C of heating 10 hours. After 10 hours, return to room temperature and add distilled water 200mL,Use glass fiber filter paper, suction filtration goes out solid constituent, and solid constituent is reclaimed and be suspended in the distilled water 400mL of approximately 100 DEG CIn, add thermal agitation 30 minutes, then suction filtration goes out solid constituent. Repeat this operation until the pH of filtrate becomes almost constant,Then at 80 DEG C, solid constituent is dried to 1 day. After dry, with the above-mentioned similarly distilled water with approximately 100 DEG C by solid constituent400mL carries out hot wash, repeats this operation until the pH of filtrate becomes almost constant. After hot wash, will at 80 DEG CDry 1 day of solid constituent, obtains solid acid. The sulfur content of solid acid D is 5.1 % by weight. The solid acid D obtaining is developed into powderEnd.

(2) carbon is the bactericidal effect of solid acid D to various microorganisms

(a), as test organisms, use the false unit cell of the stench obtaining from independent administrative legal person's products assessment technique basal disc organizationBacterium (Pseudomonasputida) NBRC14164, Staphylococcus aureus (StaphylococcusaureusSubsp.aureus) NBRC12732, atrophy bacillus (Bacillusatrophaeus) NBRC13721. About test organismsLiquid, utilizes the agar plate that is added with 1.5% agar in each SCDLP culture medium " ダィ go " (Japanese pharmacy (strain) system)Culture medium, cultivates various microorganisms 1 day 30 DEG C (being 37 DEG C in the situation that of staphylococcus microorganism belonging to genus), by the bacterium of gainedBody is suspended in aqua sterilisa, and bacterium number is adjusted into 10⁵～10⁷Cfu/ml (cfu is CFU).

(b), as bacterium number mensuration culture medium, similarly modulate multiple SCDLP Agar Platings and use.

(c) instrumentation operation is as described below. The pulverous carbon that takes 0.1g is that solid acid D is to the bottle with sillicon rubber blockingIn, 121 DEG C of steam sterilizings 15 minutes. After this sterilization treatment, in bottle, add respectively above-mentioned various test organisms liquid 2ml,Be rotated vibration (140rpm) at 30 DEG C. After 10 minutes, the treatment fluid in the bottle of sampling 100 μ l, carries out with aqua sterilisa immediatelyStepwise dilution (10～10⁴Doubly dilution). Then, 50 μ l of each dilution bacterium liquid are spread upon respectively to above-mentioned SCDLP agar plate trainingSupport on base. After smearing, leave standstill and cultivate 1～2 day 30 DEG C (being 37 DEG C in the situation that of staphylococcus microorganism belonging to genus), utilize bacterium colony meterNumber method is measured viable count.

(d) in addition, experiment in contrast, adds respectively above-mentioned each in the bottle with sillicon rubber blocking after steam sterilizingKind of test organisms liquid 2ml at 30 DEG C of rotational oscillations (140rpm), after 10 minutes, the test organisms liquid in the bottle of sampling 100 μ l, with upperState and similarly utilize colony counting method to measure viable count.

Table 7 shows its result. In addition, do not carry out the rotational oscillation processing of 10 minutes, and it is each to utilize colony counting method to measurePlant the viable count of test organisms liquid, the viable count during using this bacterium number as processing beginning is shown in Table 7. Viable count in table 7 is everyThe value of 1ml treatment fluid, show carry out each processing experiment twice and the mean value of viable count.

Table 7

Embodiment 4

In this embodiment, use Escherichia coli to study under the following conditions the bactericidal effect that carbon is solid acid D.

(1) carbon is the making of solid acid D: carbon is that solid acid D makes similarly to Example 3.

(2) carbon is that solid acid D is to colibacillary bactericidal effect

(a) Escherichia coli are used Escherichia coli similarly to Example 1.

(b), as bacterium number mensuration culture medium, use tryptose soya agar culture medium day water pharmacy (strain) system.

(c) instrumentation operation is as described below. The pulverous carbon that takes 0.5g be solid acid D to after steam sterilizing with siliconIn the bottle of rubber stopper. In this bottle, add above-mentioned Escherichia coli liquid 10ml, be rotated vibration (140rpm) at 25 DEG C.

After 3 hours, the treatment fluid in the bottle of sampling 100 μ l, carries out stepwise dilution (10～10 with aqua sterilisa immediately³Doubly rareRelease). Then, 50 μ l of each dilution bacterium liquid are spread upon respectively on above-mentioned tryptose soya agar plating medium. After smearing,Leave standstill and cultivate 1 day at 30 DEG C, utilize colony counting method to measure viable count.

(d) in addition, experiment in contrast, adds above-mentioned large intestine in the bottle with sillicon rubber blocking after steam sterilizingBacillus liquid 10ml at 25 DEG C of rotational oscillations (140rpm), after 3 hours, the Escherichia coli liquid in the bottle of sampling 100 μ l, with above-mentionedSimilarly utilize colony counting method to measure viable count.

Table 8 shows its result. In addition, do not carry out the rotational oscillation processing of 3 hours, and utilize colony counting method determination testThe viable count of bacterium liquid, the viable count during using this bacterium number as processing beginning is shown in Table 8. Viable count in table 8 is that every 1ml processesThe value of liquid, show carry out each processing experiment twice and the mean value of viable count. In addition in bracket, show, the pH of each liquid.

Table 8

Above-described embodiment is illustrating or explaining of invention technical scheme, and should not be construed as the technology of the present invention sideThe restriction of case, obviously, those skilled in the art can carry out various modifications and variations and not depart from essence of the present invention the present inventionGod and scope. If within these amendments and modification belong to the scope of the claims in the present invention and equivalent technologies thereof, the present inventionWithin being also contained in protection domain of the present invention.

Claims

1. a disinfection solution, this disinfection solution is anti-bad to have the metal ion of antibacterial action and Cys and L-Hematic acid is main component, contains the surfactant except nonionic surface active agent, its feature in this main componentBe: the dusty material that contains the amorphous carbon that has imported sulfo group in this disinfection solution.

2. disinfection solution as claimed in claim 1, is characterized in that: the amorphous carbon that has imported sulfo group can use carbon systemSolid acid A, carbon are that solid acid B and carbon are solid acid C, and carbon is that solid acid A is by by by the incomplete organic compound of carbonizationThereby thing and sulfur trioxide or the sulfonating agent that contains sulfur trioxide carry out heat treated carrys out the solid acid that condensation and sulfonation obtain; CarbonBe solid acid B be by by least a kind in the choosing Ppolynuclear aromatic hydrocarbon that freely 2～7 aromatic rings condensations form at the concentrated sulfuric acidThereby or in oleum, carry out heat treated and carry out the solid acid that condensation and sulfonation obtain; Carbon is solid acid C for by by organicCompound carries out the solid acid that heat treated imports sulfo group and obtain in the concentrated sulfuric acid or oleum.

3. disinfection solution as claimed in claim 1, is characterized in that: live in the surface except nonionic surface active agentProperty agent is the iron ion (Fe of trivalent³⁺), the iron ion (Fe of divalence²⁺), zinc ion (Zn²⁺), copper ion (Cu²⁺), cobalt ions (Co² ⁺), nickel ion (Ni²⁺) or silver ion (Ag⁺)。

4. disinfection solution as claimed in claim 3, is characterized in that: have the concentration of metal ion of antibacterial action threeIn the situation of the iron ion of valency, be 50～200ppm, in the case of the iron ion of divalence, be 110～400ppm, at zinc ionIn situation, be 7.5～125ppm, the in the situation that of copper ion, be 15～60ppm, the in the situation that of cobalt ions, be 180～300ppm, the in the situation that of nickel ion, be 85～175ppm, the in the situation that of silver ion, be 1～3ppm.

5. disinfection solution as claimed in claim 1, is characterized in that: the concentration of Cys is 100～1000ppm,The concentration of L-AA is 100～500ppm.

6. disinfection solution as claimed in claim 1, is characterized in that: live in the surface except nonionic surface active agentProperty agent be selected from alkylbenzenesulfonate, linear alkylbenzene sulfonate (LAS), polyoxyethylene alkyl ether sulfate salt, higher alcohol sulfate salt,Lauryl sodium sulfate, sodium lauroyl sarcosine, stearyl dimethyl benzyl ammonium chloride, benzalkonium chloride, benzethonium chloride, alkylMore than one in the poly-aminoethyl glycine hydrochloride of diaminoethyl glycine hydrochloride and alkyl.

7. the disinfection solution as described in any one in claim 1-6, is characterized in that: except nonionic surface active agent withThe concentration of outer surfactant is 20～100ppm.