CN100581361C - Composition for bactericide production and process for producing organic peracid - Google Patents
Composition for bactericide production and process for producing organic peracid Download PDFInfo
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- CN100581361C CN100581361C CN200480009327A CN200480009327A CN100581361C CN 100581361 C CN100581361 C CN 100581361C CN 200480009327 A CN200480009327 A CN 200480009327A CN 200480009327 A CN200480009327 A CN 200480009327A CN 100581361 C CN100581361 C CN 100581361C
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Abstract
The invention provides a composition for production of a sterilizer having a water content of 1 to 25% by weight and comprising (A) an ester of a polyhydric alcohol and an organic acid having a hydrocarbon group which may have a hydroxyl group and (B1) hydrogen peroxide. From the composition, a sterilizer is obtained as an aqueous solution containing an organic peracid.
Description
Technical field
The present invention relates to bactericide manufacturing composition, microbicide compositions and method for disinfection.In addition, the present invention relates to the manufacture method of the organic peracid of use in bactericide, bleaching agent etc., the manufacture method of microbicide compositions.
Background technology
Now, the known various medicament that demonstrates effects such as bleaching or sterilization, sterilization, particularly mainly use hypochlorites such as clorox, mainly use hydrogen peroxide and in water, produce the SODIUM PERCARBONATE, sodium perborate etc. of hydrogen peroxide as the oxygen series bactericidal agent as the chlorine series bactericidal agent.Yet, these bactericide have various problems, and for example, hypochlorite has the problem of corroding metal etc. and because mistake is used the problem of the generation that causes chlorine, hydrogen peroxide has in order to obtain the bactericidal effect of height, need use under high concentration or the problem of Long contact time.When using hydrogen peroxide,, be used in combination, and improve countermeasure such as bactericidal effect and arise at the historic moment by producing organic peracid in use with activator in order to address these problems.As such bactericide, a kind of incomplete ester of organic acid of inorganic peroxide, polyalcohol, microbicide compositions of alkali earth metal salt of containing disclosed in JP-A6-305920.In addition, the method as using organic peracid as bactericide can list JP-A (W) 8-500843, JP-A 8-311495.In addition, in JP-A5-25497, proposed in the organic peracid generation structure, regulated the method that the pH value improves bleaching effect.In addition, disclose in WO-A 01/70030 and a kind ofly contained hydrogen peroxide, carboxylic acid and be the composition of the percarboxylic acids of special ratios with respect to hydrogen peroxide, said composition demonstrates antibacterial action to gemma and the microorganism that forms gemma.
When organic peracid for example was peracetic acid, it can be made continuously by hydrogen peroxide and acetic acid are reacted under acidity, obtains containing the equilibrium mixture of peracetic acid, acetic acid, hydrogen peroxide and water.In addition, for peracetic acid, can be in gas phase with acetaldehyde partly oxidation make; Or under catalyzer oxidizing acetaldehyde, generate intermediate acetaldehyde list peracetic acid ester, it is decomposed in solvent make again.The concentrate of the suitable sterilization that contains peracetic acid or acetic acid, hydrogen peroxide and water etc. is disclosed in JP-A 52-25034, JP-A 52-25011 in addition.
Summary of the invention
The present invention relates to a kind of bactericide manufacturing with composition (below, be called the 1st bactericide manufacturing composition), said composition contains ester that (A) is formed by polyalcohol and the organic acid with alkyl that can be hydroxyl and (B1) hydrogen peroxide, and moisture is 1～25 weight %.
In addition, the invention still further relates to a kind of bactericide manufacturing with composition (below, be called the 2nd bactericide manufacturing composition), said composition contains ester that (A) is formed by polyalcohol and the organic acid with alkyl that can be hydroxyl and (B1) hydrogen peroxide or (B2) emit the inorganic peroxide of hydrogen peroxide in water, wherein (A) and (B1) or (A) and the mol ratio of (B1) that produce by (B2) be (A)/(B1)=1/10～20/1, said composition is to use with the form of the aqueous solution, this aqueous solution is through the pH value is reached after 8～12, makes the pH value more than or equal to 1 but make less than 7 again.
In addition, the invention still further relates to a kind of bactericide manufacturing with composition (below, be called the 3rd bactericide manufacturing composition), said composition is a ester that (A) formed by polyalcohol and the organic acid with alkyl that can be hydroxyl and (B1) hydrogen peroxide or the inorganic peroxide of (B2) emitting hydrogen peroxide in water mix and obtain, and (A) and (B1) or (A) and the mol ratio of (B1) that produce by (B2) be (A)/(B1)=1/10～20/1, said composition is to use with the form of the aqueous solution, this aqueous solution is through the pH value is reached after 8～12, makes the pH value more than or equal to 1 but make less than 7 again.
In addition, the invention still further relates to a kind of microbicide compositions (below, be called the 1st microbicide compositions), said composition contains organic peracid and water, its 25 ℃ of following pH values more than or equal to 1 but less than 7, described organic peracid be ester that (A) formed by polyalcohol and the organic acid with alkyl that can be hydroxyl with (B1) hydrogen peroxide with the mol ratio of (A)/(B1)=1/10～20/1 in water and the pH value be that 8～12 times reactions obtain.
In addition, the invention still further relates to a kind of method for disinfection, wherein make the aqueous solution that contains organic peracid and contacted by germicide, the described aqueous solution obtains by following method: make ester that (A) is formed by polyalcohol and the organic acid with alkyl that can be hydroxyl and (B1) hydrogen peroxide with the mol ratio of (A)/(B1)=1/10～20/1 in water and the pH value be to react for 8～12 times, the pH value that makes this reaction system then is more than or equal to 1 but less than 7.
The invention still further relates to a kind of manufacture method of organic peracid, this method has following operation: the ester that (A) formed by polyalcohol and the organic acid with alkyl that can be hydroxyl and (B1) hydrogen peroxide with the mol ratio of (A)/(B1)=1/10～20/1 in water and the pH value be to react for 8～12 times, the pH value that makes this reaction system then is more than or equal to 1 but less than 7.
The present invention also provides a kind of manufacture method that contains the microbicide compositions of organic peracid, this method has following operation: make ester that (A) is formed by polyalcohol and the organic acid with alkyl that can be hydroxyl and (B1) hydrogen peroxide with the mol ratio of (A)/(B1)=1/10～20/1 in water and the pH value be to react for 8～12 times, the pH value that makes this reaction system then is more than or equal to 1 but less than 7.
The invention still further relates to purposes that above-mentioned any bactericide manufacturing is used with composition and the purposes that above-mentioned any microbicide compositions is used for bactericide in the bactericide manufacturing.
Embodiment
In JP-A6-305920, be not lower than the record that pH value is 7 times uses, the bactericidal effect of the higher gemma of resistance to chemical reagents, mycotic spore there is further room for improvement.JP-A (W) 8-500843, JP-A 8-311495 are to serve as basic to be used in combination dense thick peracetic acid, acetic acid and hydrogen peroxide as microbicide compositions, but because the strong impulse stink is arranged, so be difficult to use.In JP-A 5-25497, can not expect to improve sterilizing power to the higher gemma of resistance to chemical reagents, mycotic spore.In addition, WO-A 01/70030 also has the material of pungent odour equally with JP-A (W) 8-500843, JP-A8-311495, aspect usability problem is arranged.
In bactericide of employed organic peracid up to now etc., realized fully hardly: in its manufacture method, consider suitable raw material balance, and control residual amount of hydrogen peroxide.In addition, as mentioned above, when making acetic acid and hydroperoxidation, because the product that obtains is the equilibrium mixture that contains hydrogen peroxide, so the ratio of the concentration of hydrogen peroxide uprises relatively.Therefore, contain the many tendencies of quantitative change with what the organic peracid aqueous solution of existing method manufacturing had a unreacted hydrogen peroxide composition.If the concentration of per unit hydrogen peroxide uprises, therefore the concentration step-down of organic peracid then is unfavorable to the sterilization of height more.In addition, at present, the load that alleviates environment is important problem, and the bactericide etc. that contains hydrogen peroxide needs processing such as neutralization, decomposition superfluously before discharge, and its disposal cost becomes bigger burden.
The invention provides that can make can be effectively when using and stably generate the organic peracid of high concentration and demonstrate the bactericide manufacturing composition of high sterilizing power, and the microbicide compositions of the high sterilizing power of demonstration is provided.
Below, respectively to ester that (A) formed by polyalcohol and the organic acid with alkyl that can be hydroxyl as (A) composition, will (B1) hydrogen peroxide as (B1) composition, will (B2) in water, emit hydrogen peroxide inorganic peroxide as (B2) composition, (B1) composition and (B2) composition merging conduct (B) composition are described.
In addition, in (B) composition, the molal quantity of the hydrogen peroxide that is produced by (B2) composition is meant, concentration of hydrogen peroxide (weight %) in (B2) composition that will be tried to achieve by the permanganic acid titration multiply by the addition (g) of (B2) composition in the composition, the value of trying to achieve divided by the molecular weight 34 of hydrogen peroxide.
The invention provides a kind of can the manufacturing not only to common bacterium, but also the bactericide manufacturing composition of the bactericide that the high gemma of resistance to chemical reagents and mycotic spore are also demonstrated high sterilizing power.
The microbicide compositions that obtains with composition by bactericide manufacturing of the present invention or the bactericidal effect height of microbicide compositions of the present invention, and its continuation is also excellent.According to the present invention, can provide the method for disinfection that demonstrates excellent bactericidal effect the wide spectrum such from industrial sterilizations such as bakery and confectionerys to the sterilization in the family.
＜(A) composition 〉
(A) ester that forms of the polyalcohol of composition and organic acid and hydroperoxidation and generate organic peracid with alkyl that can be hydroxyl.
As the polyalcohol that constitutes (A) composition, be preferably carbon number and be 2～12 polyalcohol, can list glycerols such as glycerine, diglycerol, triglycerin, carbohydrates such as glucose, sucrose, fructose, sorbitol, pentaerythrite, alkyglycosides (alkyl polyglycoside), alkyl furan glucosides.
In addition, as the organic acid that is used for constituting (A) composition, can list acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, the sad aliphatic monocarboxylic acid that waits, oxalic acid, malonic acid, succinic acid, maleic acid, aliphatic dicarboxylic acids such as fumaric acid, citric acid, tartaric acid, malic acid etc. have the hydroxycarboxylic acid of hydroxyl etc., preferably, carbon number is 1～8 saturated or undersaturated aliphatic list or dicarboxylic acids, more preferably, carbon number is 1～8 saturated or unsaturated aliphatic monocarboxylic acid, and further preferably, carbon number is 1～8 fatty acid, particularly preferably be, carbon number is 2～8 fatty acid.(A) there is no particular limitation for the esterification degree of composition.
As concrete (A) composition, be preferably glycerine and carbon number and be the ester of 1～8 aliphatic monocarboxylic acid, wherein be preferably glycerol triacetate especially.
＜(B) composition 〉
(B) composition is the hydrogen peroxide of (B1) composition or (B2) inorganic peroxide of emitting hydrogen peroxide in water of composition, when composition when being aqueous, (B) composition is a hydrogen peroxide, when composition is solid shape such as granular, Powdered, (B) composition is preferably percarbonate, perborate, wherein is preferably SODIUM PERCARBONATE, sodium perborate especially.
＜the 1 bactericide manufacturing composition 〉
The 1st bactericide manufacturing of the present invention contains (A) composition and (B1) composition with composition, from storage, suppress (A) composition and (B1) composition reaction and keep the viewpoint of the stability of composition, moisture in the composition is preferably 1～25 weight %, more preferably 5～20 weight % are preferably 5～15 weight % especially.
The 1st bactericide manufacturing of the present invention owing to be the liquid composition that contains the one-pot type of the composition that is useful on the preparation organic peracid, is made the manufacturing of in composition and the of the present invention method for disinfection employed sterilization usefulness aqueous solution so be applicable to the 1st bactericide of the present invention for example described later with composition.The 1st bactericide manufacturing is preferably 20～90 weight % with the content of (A) composition in the composition, and more preferably 30～90 weight % are preferably 40～80 weight % especially; (B1) content of composition is preferably 1～30 weight %, and more preferably 5～25 weight % are preferably 10～25 weight % especially.In addition, (A) composition and (B1) mol ratio are preferably (A)/(B1)=1/10～20/1, and more preferably 1/10～10/1, be preferably 1/5～10/1 especially.In addition, from generating organic peracid effectively, and the viewpoint that reduces unreacted hydrogen peroxide sets out, with respect to per 1 ester group of (A) composition, (B1) mol ratio of composition be preferably 2 times of moles or below, be preferably 0.3～2 times of mole especially.
In addition, the 1st bactericide manufacturing can contain chelating agent, pH value conditioning agent, solvent etc. as required with composition.The catalyst decomposes that causes for the trace that suppresses metal ions such as Fe or Cr is sneaked into is so chelating agent is suitable.From the viewpoint of storage-stable, the 1st bactericide manufacturing is preferably 0.5～6 with the pH value (20 ℃) of the stoste of composition, and more preferably 1～5, be preferably 1～4 especially.The preferred effect that has pH value conditioning agent simultaneously and as the material of the effect of chelating agent particularly, is preferably phosphoric acid, polymer phosphate, organic phospho acid, amino carboxylic acid, hydroxycarboxylic acid or their salt.Wherein be preferably organic phospho acid or its salt especially.As solvent, be preferably polyol solvent, be preferably diol solvents such as propane diols especially.
＜the 2 bactericide manufacturing composition 〉
The 2nd bactericide manufacturing of the present invention contains (A) composition and (B) composition with composition, both ratios are preferably in (B1) composition and (A) scope that can react effectively of composition, if consider formation efficiency, bactericidal effect, preparation stability of organic peracid etc., (A) composition and (B1) mol ratio of composition be preferably (A)/(B1)=1/10～20/1, more preferably 1/10～10/1, be preferably 1/5～10/1 again.In addition, from generating organic peracid effectively and reducing the viewpoint of unreacted hydrogen peroxide, with respect to per 1 ester group of (A) composition, (B1) mol ratio of composition be preferably 2 times of moles or below, be preferably 0.3～2 times of mole especially.When using (B2) composition, also preferably add with the amount of (B1) composition of producing above-mentioned scope.
Preferably, satisfying on the basis of this mol ratio, the 2nd bactericide manufacturing of the present invention is preferably 0.1～90 weight % with the amount of (A) composition that composition contained, and more preferably 0.5～70 weight % is preferably 1～50 weight % especially; The 2nd bactericide manufacturing of the present invention with the amount of (B) composition that composition contained is, (B) composition in (B1) composition, is preferably 0.1～50 weight %, and more preferably 0.1～30 weight % is preferably 0.1～20 weight % especially.
The 2nd bactericide manufacturing of the present invention with composition in use, by the pH value being adjusted to 8～12, being preferably 9～11 (first operations), make then the pH value more than or equal to 1 but less than 7, be preferably 1～6, more preferably 1～5 (second operation), thereby preparation is as the aqueous solution of microbicide compositions.Preferably in first operation, use alkaline pH value conditioning agent, in second operation, use the acid ph value conditioning agent.PH value when this pH value can be to use preferably satisfies above-mentioned pH value under 25 ℃.In addition, also can use the 1st bactericide manufacturing composition of the invention described above equally.
As alkaline pH value conditioning agent, can list alkali metal hydroxide or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, slaked lime, barium hydroxide, silicate base such as sodium silicate, silicon potash fertilizer slaine, tertiary sodium phosphates etc. are the phosphoric acid alkali metal salt of alkalescence, carbonic acid such as sodium carbonate, potash alkali metal salt, but from basicity and water miscible viewpoint, be preferably alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonic acid alkali metal salts such as phosphoric acid alkali metal salt, sodium carbonate and potash such as tertiary sodium phosphate and tripotassium phosphate.In addition, as the acid ph value conditioning agent, can list inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids such as formic acid, acetic acid, citric acid, succinic acid, gluconic acid, from acidity and water miscible viewpoint, be preferably liquid mineral acid such as sulfuric acid and phosphoric acid, and citric acid and the contour water-soluble organic acid of acetic acid.They can use separately, also can be used in combination two or more.In addition, these pH value conditioning agents can directly be present in the 2nd bactericide manufacturing of the present invention with in the composition.In addition, the 1st bactericide manufacturing of the invention described above also can have these pH value conditioning agents with composition.
The 2nd bactericide manufacturing of the present invention except containing (A) composition, (B) composition, can also contain surfactant, inorganic or organic salt, chelating agent, spices, pigment, dyestuff etc. with composition.In addition, the 1st bactericide manufacturing of the invention described above is with also having these compositions in the composition.
As surfactant, can list nonionic surfactant, anionic surfactant, cationic surfactant and amphoteric surfactant.As nonionic surfactant can list polyoxyethylene (below, be called POE) 1 yuan of 01 derivatives type nonionic surfactant such as alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene (block or random) alkyl ether, polyoxyethylene aryl phenyl ether, polyoxyethylene styrene phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyol derivative type nonionic surfactants such as (gathering) fatty glyceride, fatty acid cane sugar ester, sorbitan fatty acid esters, alkyglycosides etc.Can list lignosulfonates, alkylbenzenesulfonate, alkylsulfonate, POE alkylsulfonate, POE alkyl phenyl ether sulfonate, POE alkyl phenyl ether phosphate salt, POE aryl phenyl ether sulfonate, POE aryl phenyl ether phosphate salt, naphthalene sulfonate, naphthalene sulfonic acid-formaldehyde condensation product, POE tribenzyl phenyl ether sulfonate, POE tribenzyl phenyl ether phosphate salt etc. as the anionic surfactant.As cationic surfactant, can list single-long-chain alkyl (carbon number is 8～18) trimethyl ammonium chloride, two chain alkyls (carbon number is 8～18) alkyl dimethyl ammonium chloride, zephiran, Benzethonium Chloride etc.As amphoteric surfactant, can list alkyl amino trimethylglycine, alkyl dimethyl amine oxide and alkyl diamino ethyl glycine hydrochloride etc.They can use separately, also can be used in combination two or more.As surfactant, be preferably nonionic surfactant, more preferably polyol derivative type nonionic surfactant.In addition, preferably contain 0～20 weight % in composition, more preferably contain the surfactant of 0～10 weight % in the 2nd bactericide manufacturing of the present invention.
Salt is except using as pH value conditioning agent, use mainly as the purpose that makes the bactericide stabilisation, particularly, can list organic salts such as carboxylic metallic salt such as succinic acid, malonic acid, citric acid, gluconic acid, glutaric acid, phosphate cpd slaines such as tripolyphosphate, hexa metaphosphoric acid, phosphoric acid, mineral salt such as sulphate such as sodium sulphate, potassium sulphate.They can use separately, also can be used in combination two or more.
As chelating agent, can list ethylenediamine tetra-acetic acid, triacetamide, tripolyphosphate, poly-hydroxy acrylic acid, organic phospho acid etc. or their salt.
The 2nd bactericide manufacturing of the present invention can form various forms with composition, when being aqueous, preferably has high fluidity, also can be the slurry with flowability beyond the aqueous solution, gel, pasty state etc.In addition, for solid shape the time, can list shapes such as granular, Powdered, graininess, sheet.
For the 2nd bactericide manufacturing composition of the present invention, all blending constituents can be compiled back packing and form, from the viewpoint of stability, preferably will (A) composition pack the multi-form of formation respectively with (B) composition.For example, can form to be useful on and at last pH value is adjusted to more than or equal to 1 but less than the bactericide manufacturing composition of three formulations of package body (3) formation of the composition of 7 pH value conditioning agent acid ph value conditioning agents such as () citric acids by the package body (1) of the composition that contains (A) composition, the package body (2) and containing that contains the composition of (B) composition.At this moment, preferably add alkaline agent in package body (2), it is 8～12 that the mixture of package body (1) and package body (2) is adjusted to the pH value.In addition, particularly when being powder composition, (A) composition and (B) composition also can co-exist in 1 package body, for example, can form by contain with (A) composition and (B) composition to be adjusted to pH value be that the package body (I) and containing of the composition of 8～12 alkaline agent is useful on the last pH value is adjusted to more than or equal to 1 but less than the package body (II) of the composition of 7 pH value conditioning agent acid ph value conditioning agents such as () citric acids.
The 2nd bactericide manufacturing of the present invention is regulated the pH value by formerly first operation, second operation with composition in use, then can be prepared into the aqueous solution of the microbicide compositions that contains organic peracid.The concentration of the organic peracid in this aqueous solution is 10～20,000ppm (weight ratio, below identical), more preferably 10～10,000ppm.In addition, aspect bactericidal effect, preferably the content of the hydrogen peroxide in this aqueous solution is 0.5 weight % or following, and more preferably 0.3 weight % or following is preferably 0.2 weight % or following especially.These opinions also are same for the 1st bactericide manufacturing of the invention described above with composition.
＜the 3 bactericide manufacturing composition 〉
The 3rd bactericide manufacturing composition of the present invention by the invention described above (A) composition and (B) composition mix and to obtain, the same with the 2nd bactericide manufacturing with composition, with (A) composition with from the mol ratio of (B1) composition of (B) composition is (A)/(B1)=1/10～20/1, said composition is to use with the form of the aqueous solution, this aqueous solution reaches after 8～12 through making the pH value, makes the pH value more than or equal to 1 but make less than 7 again.(A) mol ratio of the concrete compound of composition, (B) composition and preferred (A)/(B1) is also identical with composition with the 2nd bactericide manufacturing.In addition, the 3rd bactericide manufacturing also can contain aforementioned surfactants, inorganic or organic salt, chelating agent, spices, pigment, dyestuff etc. with composition, and the scheme of packing also can be identical.
＜the 1 microbicide compositions 〉
The 1st microbicide compositions of the present invention contains organic peracid and water, and the pH value under 25 ℃ is more than or equal to 1 but less than 7, described organic peracid be make (A) composition and (B1) composition be that 8～12 times reactions obtain with the mol ratio of (A)/(B1)=1/10～20/1 in water and in the pH value.The 1st microbicide compositions of the present invention is, as mentioned above, make (A) composition and (B1) composition in water, be to react for 8～12 times with specific mol ratio and pH value, be adjusted to the pH value then more than or equal to 1 but less than 7, be preferably 1～6, more preferably 1～5 and form.(A) mol ratio of the particular compound of composition, (B) composition and preferred (A)/(B1) is identical with composition with the 2nd bactericide manufacturing of the invention described above.In addition, the 1st microbicide compositions also can contain aforesaid surfactant, inorganic or organic salt, chelating agent, spices, pigment, dyestuff etc.The content of water is preferably more than in composition and equals 50 weight % but less than 100 weight %, more preferably more than or equal to 60 weight % but less than 100 weight %, is preferably more than especially and equals 70 weight % but less than 100 weight %.With the same with the aqueous solution that composition obtains by the bactericide manufacturing of the invention described above, the 1st microbicide compositions of the present invention is the aqueous solution that contains organic peracid, and the concentration of the organic peracid in this aqueous solution is preferably 10～20,000ppm, more preferably 10～10,000ppm.In addition, aspect bactericidal effect, the content of the hydrogen peroxide of the 1st microbicide compositions of the present invention is 0.5 weight % or following, and more preferably 0.3 weight % or following is preferably 0.2 weight % or following especially.Preferably, after the preparation of said composition, reach the content of this hydrogen peroxide soon, more preferably, reach the content of this hydrogen peroxide in use.
＜method for disinfection 〉
Method for disinfection of the present invention be make the aqueous solution that contains organic peracid (below, be called the sterilization aqueous solution) with the method that is contacted by bactericide, wherein said organic peracid be make (A) composition and (B1) composition with the mol ratio of (A)/(B1)=1/10～20/1, in water, and the pH value is 8～12 times reactions, then the pH value is adjusted to more than or equal to 1 but less than 7, preferred pH value is 1～6, more preferably the pH value is 1～5 to obtain, preferred therein the use by the above-mentioned microbicide compositions of the present invention or the aqueous solution that made with composition by bactericide manufacturing of the present invention.
Method for disinfection of the present invention can comprise:
(I) make (A) composition and (B1) composition with the mol ratio of (A)/(B1)=1/10～20/1 in water and pH value be the operation of reacting the aqueous solution that obtains containing organic peracid for 8～12 times;
(II) make this pH value of aqueous solution more than or equal to 1 but less than 7 then, be preferably 1～6, more preferably 1～5, thus obtain the operation of bactericidal aqueous solution;
(III) make sterilization with the aqueous solution and the operation that is contacted by germicide.
The operation of above-mentioned (I), for example, can add a certain amount of (A) composition, (B1) composition in 5～50 ℃ water, give the pH value is 8～12 pH value conditioning agent (alkaline agent), make (A) composition and (B1) composition react.The operation of above-mentioned (II) can be added in this hybrid system and given the pH value more than or equal to 1 but less than 7 pH value conditioning agent (sour agent) and carry out.
As making sterilization, can list methods such as this aqueous solution distribution, dipping, filling, coatings with the aqueous solution and the method that is contacted by germicide.When scattering, be preferably spraying.In addition, appropriate carriers is contained be dipped in this aqueous solution, then the wiping object thing.Time of contact is unqualified, for germicide, even 30 seconds with interior, also can obtain enough effects in making 10 seconds with interior such short time especially.In addition, the temperature of this aqueous solution during contact is also unqualified, is preferably 10～90 ℃, more preferably 15～80 ℃.
Microbicide compositions of the present invention or the bactericide (the sterilization aqueous solution) that is made with composition by the bactericide manufacturing and method for disinfection be owing to have a high bactericidal effect, thus can with have various microorganisms various by germicide as sterilization object.For example, for the bacterium class, can list pathogene such as food poisonings such as Escherichia coli, salmonella, staphylococcus aureus, green dense bacterium and hospital-acquired infection, Mycophyta such as aspergillus niger, Candida, and bactericide is had fungal spores such as the bacterial spore such as hay bacillus of strong patience and aspergillus niger.Wherein, described bacterial spore is meant, the rest cell of making in the environment that is not suitable for breeding with durability, the shell that the bacterium colony outside has multiple stratiform.This bacterial spore is very high to the durability of medicament and heat etc., and common sterilization is difficult to kill fully.But, also can obtain enough bactericidal effects to this bacterial spore according to microbicide compositions of the present invention and method for disinfection.
So, microbicide compositions of the present invention or the bactericide (the sterilization aqueous solution) and the fungicidal spectrum of method for disinfection that are made with composition by the bactericide manufacturing are wide, not only to bacterium class but also also high, so be applicable to sterilization in the wide spectrum to the effect of Mycophyta and gemma.For example, can be used for the sterilization of the utensil, standby and the goods that wall, bed, window etc. in hospital, maintenance facility, food processing factory, clean facilities, kitchen etc. or they use with (for example, beverage with) container etc.
＜bactericide kit (kit) 〉
Be used to prepare microbicide compositions of the present invention suitable bactericide kit can by contain microbicide compositions of the present invention, cause (A) composition that said composition had and (B1) reaction initiator of the reaction of composition (below, be called (C) composition), pH value conditioning agent (below, be called (D) composition) constitutes.In addition, the bactericide kit also can contain (A) composition, (B) composition, (C) composition and (D) composition and constituting.
Consider the simplicity when organic peracid is made, the bactericide kit that is used to prepare microbicide compositions of the present invention can be the one-pack type that all adding ingredients is compiled the back packing; Stability when considering storage, it also can be with (A) composition, (B) composition, (C) composition and the multi-form after (D) composition is packed respectively.Consider the simplicity when organic peracid is made and make these two viewpoints of storage-stable that the formulation of preferred bactericide kit is to contain multi-forms such as 2 formulations of the package body of having packed the composition that contains two or more compositions in (A)～(D) composition or 3 formulations with composition.
(A) composition and (B1) composition in water, alkali condition (suitable water temperature is 5～50 ℃) down reaction generate organic peracid, so, can use the composition that can give such pH value as (C) composition.Particularly, as alkaline pH value conditioning agent, can list alkali metal hydroxide or alkaline earth metal hydroxides such as illustrative sodium hydroxide, potassium hydroxide, slaked lime, barium hydroxide, silicate base such as sodium silicate, silicon potash fertilizer slaine, tertiary sodium phosphates etc. are the phosphoric acid alkali metal salt of alkalescence, carbonic acid such as sodium carbonate, potash alkali metal salt, from basicity and water miscible viewpoint, be preferably carbonic acid alkali metal salts such as phosphoric acid alkali metal salt, sodium carbonate and potash such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, tertiary sodium phosphate and tripotassium phosphate.
On the other hand, aspect bactericidal effect, the bactericide that preferably contains organic peracid is for acid,, so (D) composition can use the pH value that is in alkaline range owing to (C) composition to reach the composition of acid range.Particularly, can list inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid as the acid ph value conditioning agent, organic acids such as formic acid, acetic acid, citric acid, succinic acid, gluconic acid, from acidity and water miscible viewpoint, be preferably liquid organic acid and citric acid and the contour water-soluble organic acids of acetic acid such as sulfuric acid and phosphoric acid.
Concrete formulation as the bactericide kit can list:
(I) contain following 3 kinds or the formulation of more kinds of forms: contain (A) composition and (B) composition the bactericide manufacturing with the package body (X1) of composition, contain the composition of (C) composition package body (X2), contain the package body (X3) of the composition of (D) composition;
(II) contain following 3 kinds or the formulation of more kinds of forms: contain the composition of (A) composition package body (Y1), contain (B) composition and (C) package body of the composition of composition (Y2), contain the package body (X3) of the composition of (D) composition;
(III) contain following 2 kinds or or the formulation of more kinds of forms: contain (A) composition, (B) composition and (C) package body of the composition of composition (Z1) and contain (Z2) of package body of the composition of (D) composition.
For the formulation of (I), the form of microbicide compositions can be Powdered a, solid, shaped, aqueous etc., but is not limited to this, and is from the viewpoint of simplicity, more preferably aqueous.When choosing aqueous form, for (A) composition in suppressing to preserve and (B) composition reaction and keep stability, the moisture in this liquid composition is preferably 1～25 weight %, more preferably 5～20 weight %, more preferably 5～15 weight %.In addition, as required, can in this liquid composition, add chelating agent, solvent.In order to suppress the decomposition of the catalyzer that metal ions such as Fe that trace sneaks into and Cr cause, preferably add chelating agent.In addition, the stoste pH value of this liquid composition (20 ℃) is relevant with storage-stable, and therefore preferred pH value is 0.5～6, and more preferably the pH value is 1～5, and further preferred pH value is 1～4.As previously mentioned, preferred use has simultaneously as pH value modulator effect with as the composition of chelating agent effect, particularly, is preferably phosphoric acid, polymer phosphate, organic phospho acid, amino carboxylic acid, hydroxycarboxylic acid or their salt.Wherein, be preferably organic phospho acid or its salt especially.Be preferably polyol solvent as solvent, be preferably diol solvents such as propane diols especially.
In addition, in the formulation of (I), when bactericide manufacturing composition is the form of Powdered, solid, shaped, preferably use SODIUM PERCARBONATE and sodium perborate etc. as (B) composition.Similarly, concerning the formulation of (II) and formulation (III), the viewpoint from storage-stable, the composition that contains (B) composition is preferably and uses SODIUM PERCARBONATE and sodium perborate etc. as the powder of (B) composition, the form of solid shape.
For the content of (A)～(D) composition in these each formulations,, can select suitable scope respectively according to the usage of aforementioned the of the present invention the 1st～the 3rd bactericide manufacturing with composition.In addition, the composition beyond (A)～(D) composition wherein can be added in the arbitrary package body that contains these (A)～(D) compositions, also can add in other package body.
The invention provides a kind of method that can make organic peracid under the situation of excessively not using hydrogen peroxide, it is suitable organic peracid as bactericide etc. that this organic peracid demonstrates high stability and sterilizing power and its.Below, manufacture method is described.
According to the present invention, can use hydrogen peroxide not superfluously and make organic peracid efficiently effectively as bactericide etc.Thereby the low organic peracid aqueous solution of the content that can obtain hydrogen peroxide, so for example when using, can also alleviate draining burden to environment as bactericide.
＜(A) composition 〉
Can similarly use with (A) of above-mentioned composition.
＜(B) composition 〉
(B) composition is hydrogen peroxide (B1), uses after also the inorganic peroxide of emitting hydrogen peroxide in water can being dissolved in water.As this inorganic peroxide, wherein preferred percarbonate, perborate are preferably SODIUM PERCARBONATE, sodium perborate especially.
＜manufacture method 〉
Manufacture method of the present invention is that when making (A) composition and (B1) composition reacts, making both mol ratios is special ratios, and makes the pH value of reaction system divide the two-stage to change.Manufacture method of the present invention is different with the existing method that makes acetic acid and hydroperoxidation, (A) composition and (B1) reaction of composition be irreversible reaction, so in system, do not accumulate hydrogen peroxide, when manufacturing contains the aqueous solution of organic peracid of desired concn, be favourable.Just, according to the present invention, the method of making the aqueous solution that contains organic peracid can be provided, this method has following operation: make (A) composition and (B1) composition be to react for 8～12 times with above-mentioned specific mol ratio pH value in water, then, make the pH value of this reaction system more than or equal to 1 but less than 7.
From the viewpoint of the production rate of organic peracid and stability, (A) composition and (B1) mol ratio of composition be (A)/(B1)=1/10～20/1, be preferably 1/10～10/1, be preferably 1/5～10/1 especially.In addition, from generating organic peracid effectively and reducing the viewpoint of unreacted hydrogen peroxide, with respect to per 1 ester group of (A) composition, (B1) mol ratio of composition be preferably 2 times of moles or below, be preferably 0.3～2 times of mole especially.
In addition, (A) ratio of composition, (B1) composition and water, is preferably [(A)+(B1)]/water=1/10000～1/1 in weight ratio, is preferably 1/1000～1/2.
On the basis of satisfying above-mentioned mol ratio and weight ratio, in reaction system, to be preferably 0.1～90 weight %, 0.5～70 weight % more preferably, the amount that is preferably 1～50 weight % is especially added (A) composition; To be preferably 0.1～50 weight %, 0.1～30 weight % more preferably is preferably (B1) composition that the amount of 0.1～20 weight % is added especially.
In manufacture method of the present invention, preferred use contains (A) composition and (B1) composition and moisture are the liquid composition of 1～25 weight %.Just, in manufacture method of the present invention, (A) composition and (B1) composition be preferably formed and contain (A) composition and (B1) composition and moisture are the liquid composition of 1～25 weight %.The content of (A) composition in this liquid composition is preferably 20～90 weight %, 30～90 weight % more preferably, is preferably 40～80 weight % especially; (B1) content of composition is preferably 1～30 weight %, and more preferably 5～25 weight % are preferably 10～25 weight % especially.In addition, (A) composition and (B1) mol ratio of composition be preferably (A)/(B1)=1/10～20/1, more preferably 1/10～10/1, be preferably 1/5～10/1 especially.In addition, from generating organic peracid effectively and reducing the viewpoint of unreacted hydrogen peroxide, with respect to per 1 ester group of (A) composition, (B1) mol ratio of composition be preferably 2 times of moles or below, be preferably 0.3～2 times of mole especially.
In addition, this liquid composition can contain chelating agent, pH value conditioning agent, solvent etc. as required.For the catalyst decomposes that suppresses metal ions such as Fe that trace sneaks into and Cr and cause, so chelating agent is suitable.From the viewpoint of storage-stable, the pH value of the stoste of this liquid composition (20 ℃) is preferably 0.5～6, and more preferably 1～5, be preferably 1～4 especially.Preferred have pH value modulator effect simultaneously and as the material of the effect of chelating agent, particularly, be preferably phosphoric acid, polymer phosphate, organic phospho acid, amino carboxylic acid, hydroxycarboxylic acid or their salt.Wherein will be preferably organic phospho acid or its salt.Be preferably polyol solvent as solvent, be preferably diol solvents such as propane diols especially.
In addition, (B) composition also can use the inorganic peroxide of emitting hydrogen peroxide in water, for example, and by the composition of the solid forms such as granular, Powdered that contains percarbonate, perborate, particularly SODIUM PERCARBONATE, sodium perborate and obtain peroxide.
In the present invention, after with (A) composition and (B) composition mixed, making the pH value of reaction system was 8～12, is preferably 9～11 (first operations), then, makes the pH value more than or equal to 1 but less than 7, is preferably 1～6, more preferably 1～5 (second operation).In first operation, preferably use alkaline pH value conditioning agent; In second operation, preferably use the acid ph value conditioning agent.PH value when this pH value is reaction, but preferably, reacted end product satisfies the pH value of above-mentioned second operation under 25 ℃.
Above-mentioned first operation is the operation that is used to produce organic peracid, and the time is unqualified; Preferably till 50% the organic peracid that produces theoretical value, the pH value is being remained on 8～12.The preferred reaction time of first operation is 1～120 minute.In addition, the reaction temperature of first operation is preferably 5～50 ℃.
In addition, second operation is the operation that makes the organic peracid stabilisation of generation, is basically to make the pH value more than or equal to 1 but carry out less than 7 pH value conditioning agent by adding in reaction system.Just, when the pH value reached regulation numerical value, second operation finished.Reaction temperature in second operation is preferably 5～50 ℃.
Manufacturing method according to the invention can obtain with the form that organic peracid is present in the aqueous solution, accumulate the viewpoint with the stability of organic peracid from preventing hydrogen peroxide, the concentration of the residual hydrogen peroxide in this aqueous solution is preferably 60 weight % or following of the initial stage addition of hydrogen peroxide, more preferably 50 weight % or following are preferably 0.1～50 weight % especially.
Alkaline pH value conditioning agent can similarly use with above-mentioned composition.PH value conditioning agent can directly be present in the aqueous solution of the organic peracid that contains manufacturing in the present invention.
In the present invention, except (A) composition, (B) composition, can also in reaction system, add surfactant, inorganic or organic salt, chelating agent, spices, pigment, dyestuff etc.Thus, can easily obtain bactericide and bleaching agent etc.
Surfactant can similarly use with above-mentioned composition.Surfactant is preferably and contains 0～20 weight % in reaction system of the present invention, more preferably contains 0～10 weight %.
Salt and chelating agent also similarly use with above-mentioned composition.
The aqueous solution that contains by the organic peracid of the present invention preparation can when aqueous, preferably have high fluidity for various forms, also can be to have mobile slurry, gel, a pasty state etc. beyond the aqueous solution.
For the aqueous solution that contains the organic peracid of being made by the present invention, the concentration of organic peracid is preferably 10～100,000ppm (weight ratio, below identical), more preferably 10～50,000ppm.
For example, when being bactericide, by adopting adding ingredient, can obtain the organic peracid of necessary concentration easily, in use so be suitable according to implementing manufacture method of the present invention.
In addition, when being bactericide, can directly use the aqueous solution of the organic peracid that contains the present invention's manufacturing, but from the viewpoint of economy, preferably use suitable water dilution, the concentration that forms organic peracid is 10～20,000ppm is preferably 10～10, the aqueous solution of 000ppm and using.
When the organic peracid that manufacture method of the present invention is obtained uses as bactericide, make the aqueous solution that contains organic peracid (below, be called the sterilization aqueous solution) and contacted by germicide.
Make sterilization also identical with the method that is contacted by germicide with above-mentioned composition with the aqueous solution.
Such sterilization aqueous solution is microbicide compositions, and the content of the hydrogen peroxide in the said composition is preferably 0.5 weight % or following, and more preferably 0.3 weight % or following is preferably 0.2 weight % or following especially.
Organic peracid constructed in accordance has high bactericidal effect, thus can be the same with above-mentioned composition, with have various microorganisms various by germicide as sterilization object.
Like this, the organic peracid that the present invention makes is identical with above-mentioned composition, and fungicidal spectrum is wider, is not only the bacterium class, and also higher to the effect of Mycophyta and gemma, so be applicable to sterilization in wide spectrum.
Embodiment
Embodiment 1
(A) composition, (B) composition, 50g ion exchange water and an amount of alkaline pH value conditioning agent (sodium carbonate) of the amount shown in table 1～5 were mixed in the beaker of 200mL 20 minutes.Make the pH value of this moment reach 8～12.Afterwards, re-use the pH value that acid ph value conditioning agent (citric acid) is adjusted to target, make microbicide compositions.Measure the passing in time of concentration of organic peracid of this moment and situation about changing.The concentration of organic peracid is measured by the following method.The result is shown in table 1～5.
(1) assay method of the concentration of organic peracid
(1-1) hydrogen peroxide is quantitative
In the conical flask of 200mL, accurate weighing w
1Gram microbicide compositions (in the scope of 1～50 gram), add 20% the aqueous sulfuric acid of 10mL and 2～3 borneols with cooling solution, drip 1～2 saturated manganese sulfate solution as catalyzer after, with 0.1mol/L (1/2 equivalent) potassium permanganate solution titration.When solution is presented 1～10 second pale pink, as terminal point.Concentration of hydrogen peroxide is calculated by following formula (1-1).
T
1: the titration requirement (mL) of 0.1mol/L potassium permanganate solution
F
1: the coefficient of 0.1mol/L potassium permanganate solution
w
1: the weight of microbicide compositions (g)
(1-2) organic peracid is quantitative
In the conical flask of 300mL with public stopper, accurate weighing w
2Gram microbicide compositions (in the scope of 1～50 gram) adds behind 20% aqueous sulfuric acid, 20mL pure water and the saturated potassium iodide aqueous solution of 2mL of 10mL behind the airtight stopper, and flask slightly vibrates.It after dark cold place leaves standstill 5 minutes, is used 0.2mol/L (1/5 equivalent) sodium thiosulfate solution titration.Solution is presented when faint yellow, drip several 2% amidins and continue titration.When the blue-violet color disappearance of solution as terminal point.The concentration of organic peracid is calculated according to following formula (1-2).
T
2: the needed amount of the titration of the sodium thiosulfate solution of 0.2mol/L (mL)
F
2: the coefficient of the sodium thiosulfate solution of 0.2mol/L
H:(1-1) the formula concentration of hydrogen peroxide (weight %) of trying to achieve
w
2: the weight of microbicide compositions (g)
Numerical value in () of (notes) adding ingredient is molal quantity, and (B) molal quantity in () of composition is the amount (following identical) of hydrogen peroxide.(A)/(B) mol ratio is the mol ratio (following identical) of (A) composition and hydrogen peroxide.In addition, the organic peracid residual rate is by (the pH value is regulated the concentration of the organic peracid after just having finished)/(the pH value is regulated the concentration of the organic peracid after 120 minutes) * 100 values of calculating (following identical).In addition, (A) in the composition, the fatty acid of fatty glyceride (trade name: HOMOTEX PT, Kao Corp's manufacturing) is that carbon number is 8 fatty acid (following identical).In addition, SODIUM PERCARBONATE contains the hydrogen peroxide of 22 weight %, and sodium perborate contains the hydrogen peroxide of 20 weight %.
Embodiment 2
(A) composition, (B) composition, 50g ion exchange water and an amount of alkaline pH value conditioning agent (sodium carbonate) with amount shown in table 6～9 mixed in the beaker of 200mL 20 minutes.Make the pH value of this moment reach 8～12.Afterwards, re-use the pH value that acid ph value conditioning agent (citric acid) is adjusted to target, make microbicide compositions.Use the microbicide compositions of gained, measure bactericidal effect according to following method.The result is shown in table 6～9.
(1) killing effect of bacterial spore
Will as the hay bacillus of the bacterium that forms gemma (
Bacillus Subtilis Var.niger) and Bacillus circulans (
Bacillus CirculansIFO3967) respectively in SCD agar medium (Japanese pharmacy (strain) manufacturing), 30 ℃ down pre-cultivate about 4 weeks after, obtain in right amount in bacterium colony that forms on the agar medium and outstanding turbid sterilization water at 1mL, confirm the formation of bacterial spore (below, be called gemma) with microscope lens.Behind this suspension centrifuge washing 2 times, be adjusted to about 10 with an amount of sterilization water
8～10
9The bacteria concentration of cell/mL (gemma liquid 1).This gemma liquid of 0.1mL is inoculated in the microbicide compositions of 2mL table 6～9, acts on 120 seconds down at 25 ℃.Afterwards, immediately 0.1mL is contained the microbicide compositions of gemma liquid 1, add in the SCDLP medium (Japanese pharmacy (strain)) that has added 1.0% sodium thiosulfate, make microbicide compositions deactivation (gemma liquid 2).0.2mL gemma liquid 2 is applied in the standard agar medium that diameter is 9cm, cultivated 36 hours down,, confirm residual bacterium number by calculating the clump count that on medium, forms at 35 ℃.
(2) killing effect of mycotic spore
With aspergillus niger (
Aspergillus NigerIFO6341) in potato glucose medium (Japanese pharmacy (strain)), 25 ℃ of down pre-cultivations about 4 weeks.It is also outstanding turbid in 5mL sterilization water to read the bacterium colony that produces on the medium, uses the glass homogenizer to make outstanding turbid bacterium liquid homogenising.Behind this suspension centrifuge washing 2 times, be to be adjusted to about 10 with concentration adjustment with an amount of sterilization water with an amount of sterilization water
8～10
9The bacteria concentration of cell/mL (spore liquid 1).This spore liquid 1 of 0.1mL is inoculated in the microbicide compositions of 2mL table 6～9, acts on 120 seconds down at 25 ℃.Afterwards, immediately 0.1mL is contained the microbicide compositions of spore liquid 1, add in the SCDLP medium (Japanese pharmacy (strain)) that has added 1.0% sodium thiosulfate, make microbicide compositions deactivation (spore liquid 2).0.2mL spore liquid 2 is applied in the potato glucose medium of diameter 9cm, cultivated 3～4 days down,, confirm residual bacterium number by calculating the clump count that on medium, forms at 25 ℃.
Embodiment 3
(A) composition of weight shown in the table 10, (B) composition, organic phospho acid (trade name: デ
イNetwork エ ス ト 2010 (ソ Le one シ ア ジ
ヤパ Application (strain) manufacturing) and in the alkaline pH value conditioning agent add ion exchange water, making gross weight is 100g.It was mixed in the beaker of 200mL about 10 minutes.Make the pH value of this moment reach 8～12.Afterwards, use the pH value of the acid ph value conditioning agent quick adjustment of the weight shown in the table 10 as target rapidly, adding ion exchange water again, to make total amount be 110g.Measuring the concentration and the concentration of hydrogen peroxide of the organic peracid of this moment (just after the preparation), will be 3000ppm with the concentration that the aqueous solution is adjusted to organic peracid from stirring the sterilization that begins after about 30 minutes simultaneously, the affirmation bactericidal effect.In addition, although being assay method according to the concentration of the organic peracid of embodiment 1, the assay method of the concentration of concentration of hydrogen peroxide and organic peracid carries out.In addition, the sterilization experiment method is according to the killing effect of the bacterial spore of embodiment 2, but in this example, sterilization with the aqueous solution and bacterium contact temperature and be 60 ℃ of following 20 seconds time of contact, use as object bacteria
Bacillus Cereus IFO13494 Hes
Bacillus Subtilis Var.nigerThe result is as shown in table 10.
Embodiment 4
The bactericide manufacturing composition of forming shown in the preparation table 11 is estimated storage-stable according to following method.The result is as shown in table 11.
＜storage-stable experimental technique 〉
The manufacturing of 150mL bactericide is filled in the vial that capacity is 200mL (water white transparency) with composition, and cover lid is preserved down at 50 ℃.After 4 weeks, measure concentration of hydrogen peroxide in the composition according to the assay method of the concentration of the organic peracid of embodiment 1, as the concentration of hydrogen peroxide after preserving.Try to achieve the residual peroxide rate according to following formula, as the index of storage-stable.In addition, the concentration of hydrogen peroxide after just having adjusted can adopt based on the concentration in the composition of the addition of hydrogen peroxide.
Residual peroxide rate (%)=[(concentration of hydrogen peroxide after the preservation) ÷ (concentration of hydrogen peroxide after the preparation just)] * 100
Embodiment 5 and comparative example 5
Except (A) composition, (B) composition and the ion exchange water [in the table, indicating (C) label] that use the amount shown in table 12～17 and an amount of alkaline pH value conditioning agent (sodium carbonate) in addition, manufacturing similarly to Example 1.The result is shown in table 12～17.
In addition, (A) composition, (B) composition and ion exchange water [in the table, indicating (C) label] and an amount of acid ph value conditioning agent (citric acid) with the amount shown in the table 18 mixed in the beaker of 200mL 20 minutes.Make that the pH value of this moment is 3～5.Measure the concentration of the organic peracid of this moment, but confirm not have the generation of organic peracid.In addition, this example is equivalent to the example that pH value with first operation is set at 3～5, second operation is not set especially.The result is shown in table 18.
(1) in the assay method of organic peracid, (1-1) quantitatively and (1-2) quantitatively the carrying out similarly to Example 1 of organic peracid of hydrogen peroxide.Wherein, w
1Be the weight (g) of the aqueous solution that contains organic peracid after second operation, w
2Be the weight (g) of the aqueous solution that contains organic peracid after second operation.
Numerical value in () of (notes) adding ingredient is molal quantity, and (B) molal quantity in () of composition is the amount (following identical) of hydrogen peroxide.In addition, (A)/(B1) mol ratio is the mol ratio (following identical) of (A) composition and hydrogen peroxide.In addition, described second operation in the concentration of organic peracid is meant after just having finished, the pH value of system has just reached after the certain value, and the residual rate of organic peracid is according to [(concentration of the organic peracid after second operation)/(concentration of the organic peracid after 60 minutes of second operation)] * 100 (following identical) of calculating.In addition, the residual peroxide rate is after in the past formula (1-1) concentration of hydrogen peroxide of calculating is tried to achieve whole hydrogen peroxide weight in the system, (following identical) that its whole hydrogen peroxide weight that drop into divided by the initial stage are calculated.In addition, (A) in the composition, fatty glyceride (trade name: ホ モ テ
StarThe manufacturing of Network ス PT Kao Corp) fatty acid in is that carbon number is 8 fatty acid (following identical).In addition, SODIUM PERCARBONATE contains the hydrogen peroxide of 22 weight %, and sodium perborate contains the hydrogen peroxide of 20 weight %.
Embodiment 5a and comparative example 5a
Contain the organic peracid of embodiment 5 and comparative example 5 manufacturings with the concentration shown in table 19～22, preparation has the sterilization aqueous solution of the pH value of table 19～22, according to following method mensuration bactericidal effect.The result is shown in table 19～22.
(1) killing effect of bacterial spore
Will as the hay bacillus of the bacterium that forms gemma (
Bacillus Subtilis Var.niger) and Bacillus circulans (
Bacillus CirculansIFO3967) respectively in SCD agar medium (Japanese pharmacy (strain) manufacturing), 30 ℃ down pre-cultivate about 4 weeks after, obtain in right amount in bacterium colony that forms on the agar medium and outstanding turbid sterilization water at 1mL, confirm the formation of bacterial spore (below, be called gemma) with microscope lens.Behind this suspension centrifuge washing 2 times, be adjusted to about 10 with an amount of sterilization water
8～10
9The bacteria concentration of cell/mL (gemma liquid 1).The sterilization that this gemma liquid 1 of 0.1mL is inoculated into 2mL table 19～22 acts on 120 seconds with in the aqueous solution down at 25 ℃.Afterwards, the sterilization that immediately 0.1mL contained gemma liquid 1 is added in the SCDLP medium (Japanese pharmacy (strain)) that has added 1.0% sodium thiosulfate with the aqueous solution, makes sterilization with aqueous solution deactivation (gemma liquid 2).0.2mL gemma liquid 2 is applied in the standard agar medium of diameter 9cm, cultivated 36 hours down,, confirm residual bacterium number by calculating the clump count that on medium, forms at 35 ℃.
(2) killing effect of mycotic spore
With aspergillus niger (
Aspergillus NigerIFO6341) in potato glucose medium (Japanese pharmacy (strain)), 25 ℃ of down pre-cultivations about 4 weeks.It is also outstanding turbid in 5mL sterilization water to obtain the bacterium colony that produces on the medium, uses the glass homogenizer to make outstanding turbid bacterium liquid homogenising.Behind this suspension centrifuge washing 2 times, be about 10 with concentration adjustment with an amount of sterilization water
8～10
9The bacteria concentration of cell/mL (spore liquid 1).The sterilization that this spore liquid 1 of 0.1mL is inoculated into 2mL table 8～11 acts on 120 seconds with in the aqueous solution down at 25 ℃.Afterwards, the sterilization that immediately 0.1mL contained spore liquid 1 is added in the SCDLP medium (Japanese pharmacy (strain)) that has added 1.0% sodium thiosulfate with the aqueous solution, makes sterilization with aqueous solution deactivation (spore liquid 2).0.2mL spore liquid 2 is applied in the potato glucose medium of diameter 9cm, cultivated 3～4 days down,, confirm residual bacterium number by calculating the clump count that on medium, forms at 25 ℃.
Embodiment 6
(A) composition of weight shown in the table 23, (B) composition, organic phospho acid (trade name: デ
イNetwork エ ス ト 2010 (ソ Le one シ ア ジ
ヤパ Application (strain) manufacturing) and in the alkaline pH value conditioning agent add ion exchange water, making gross weight is 100g (first operation).It was mixed in the beaker of 200mL about 10 minutes.Make that the pH value of this moment is 8～12.Afterwards, the acid ph value conditioning agent of the weight shown in the use table 21 is adjusted to the pH value of target immediately, and adding ion exchange water again, to make total amount be 110g (second operation).Measure the concentration and the concentration of hydrogen peroxide of the organic peracid of this moment (after just having made), measure simultaneously organic peracid concentration through the time change (after 30 minutes after just making, after 60 minutes, after 120 minutes).To be 3000ppm with the concentration that the aqueous solution is adjusted to organic peracid through sterilization after 120 minutes, confirm bactericidal effect.In addition, the assay method of the concentration of concentration of hydrogen peroxide and organic peracid carries out according to the assay method of the concentration of the organic peracid of embodiment 5.In addition, the sterilization experiment method is the killing effect according to the bacterial spore of embodiment 5a, but in this example, sterilization with the aqueous solution and bacterium contact temperature and be 60 ℃ of following 20 seconds time of contact, as object bacteria, provide
Bacillus Cereus IFO13494 Hes
Bacillus CirculansIFO 3967.
Embodiment 7
The liquid composition of forming shown in the preparation table 24 is according to the generation stability of following method evaluation organic peracid.The result is shown in table 24.
The stability experiment method that＜organic peracid generates 〉
Liquid composition, 0.1 gram organic phospho acid, 2 at X gram table 24 restrain among the NaOH, add ion exchange water, and making total amount is 100g, prepares in the 100mL beaker.After mixing 5 minutes, measure the concentration (%) (organic peracid after just having made generates concentration) of the organic peracid that generates according to the assay method of the concentration of the organic peracid of embodiment 5.Here, embodiment 7-1～7-3 is X=7.5 (g), and embodiment 7-4～7-9, comparative example 7-1～7-2 are X=10 (g).
In addition, the liquid composition of 150mL table 24 is filled in the vial (water white transparency) of capacity 200mL, cover lid is preserved down at 50 ℃.After 4 weeks, with the above-mentioned generation of similarly carrying out organic peracid, the organic peracid of similarly measuring after preserving generates concentration (%).The generation coefficient of stabilization of organic peracid is tried to achieve according to following formula.
Organic peracid generates coefficient of stabilization (%)=[(organic peracid after the preservation generates concentration) ÷ has just made organic peracid afterwards and generated concentration] * 100
Claims (11)
1. bactericide manufacturing composition, it is that 2～12 polyalcohol and hydroxyl or not hydroxyl carbon number are ester 20～90 weight % that form of 1～8 saturated or unsaturated aliphatic list or dicarboxylic acids and (B1) hydrogen peroxide 1～30 weight % by carbon number that said composition contains (A), and moisture is 1～25 weight %.
2. microbicide compositions, it contains the organic peracid of 10～20000ppm and more than or equal to 50 weight % but less than the water of 100 weight %, its 25 ℃ of following pH values more than or equal to 1 but less than 7, described organic peracid with (A) by carbon number be 2～12 polyalcohol and hydroxyl or not hydroxyl carbon number be the ester that forms of 1～8 saturated or unsaturated aliphatic list or dicarboxylic acids and (B1) hydrogen peroxide mol ratio and pH value with (A)/(B1)=1/10～20/1 in water be that 8～12 times reactions obtain.
3. the microbicide compositions of putting down in writing according to claim 2, wherein the content of hydrogen peroxide is 0.5 weight % or following.
4. method for disinfection, wherein make contain more than or equal to 50 weight % but less than the aqueous solution of the water of 100 weight % and organic peracid 10～20000ppm with contacted by germicide, the described aqueous solution obtains by following method: make with (A) by carbon number be 2～12 polyalcohol and hydroxyl or not hydroxyl carbon number be the ester that forms of 1～8 saturated or unsaturated aliphatic list or dicarboxylic acids and (B1) hydrogen peroxide with the mol ratio of (A)/(B1)=1/10～20/1 in water and pH value be to react 1～120 minute for 8～12 times, the pH value that makes this reaction system then is more than or equal to 1 but less than 7.
5. the method for disinfection of putting down in writing according to claim 4, the content of the hydrogen peroxide in the wherein said aqueous solution is 0.5 weight % or following.
6. the manufacture method of the microbicide compositions of a claim 2 record, this method has following operation: with (A) by carbon number be 2～12 polyalcohol with have hydroxyl or not hydroxyl carbon number be the ester that forms of 1～8 saturated or unsaturated aliphatic list or dicarboxylic acids and (B1) hydrogen peroxide with the mol ratio of (A)/(B1)=1/10～20/1 in water and the pH value be to react 1～120 minute for 8～12 times, the pH value that makes this reaction system then is more than or equal to 1 but less than 7.
7. the manufacture method of putting down in writing according to claim 6, wherein (A) and (B1) be formed contain (A) and (B1) and moisture be the liquid composition of 1～25 weight %.
8. according to claim 6 or 7 manufacture methods of being put down in writing, wherein the content of the hydrogen peroxide in the microbicide compositions is 0.5 weight % or following.
9. according to claim 7 or 8 manufacture methods of being put down in writing, wherein (A) and the reaction (B1) carried out in water are carried out under 5～50 ℃.
10. the bactericide manufacturing of 1 of claim record is used to make the purposes of bactericide with composition.
11. the microbicide compositions of 2 records of claim is used to make the purposes of bactericide.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107530457A (en) * | 2014-12-18 | 2018-01-02 | 艺康美国股份有限公司 | Peroxyformic acid is produced by polyalcohol formic acid esters |
| JP2020523088A (en) * | 2017-06-22 | 2020-08-06 | エコラボ ユーエスエー インコーポレイティド | Chlorine bleaching after peracid treatment |
| US11771673B2 (en) | 2018-06-15 | 2023-10-03 | Ecolab Usa Inc. | On site generated performic acid compositions for teat treatment |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011079079A1 (en) * | 2009-12-21 | 2011-06-30 | Fresh Express Incorporated | Peracid and 2-hydroxy organic acid compositions and methods for treating items |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4541944A (en) * | 1983-04-14 | 1985-09-17 | Interox Chemicals Limited | Compositions and processes employing activators for the generation of peroxyacids |
-
2004
- 2004-04-01 CN CN200480009327A patent/CN100581361C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4541944A (en) * | 1983-04-14 | 1985-09-17 | Interox Chemicals Limited | Compositions and processes employing activators for the generation of peroxyacids |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107530457A (en) * | 2014-12-18 | 2018-01-02 | 艺康美国股份有限公司 | Peroxyformic acid is produced by polyalcohol formic acid esters |
| US11684067B2 (en) | 2014-12-18 | 2023-06-27 | Ecolab Usa Inc. | Generation of peroxyformic acid through polyhydric alcohol formate |
| JP2020523088A (en) * | 2017-06-22 | 2020-08-06 | エコラボ ユーエスエー インコーポレイティド | Chlorine bleaching after peracid treatment |
| JP7060626B2 (en) | 2017-06-22 | 2022-04-26 | エコラボ ユーエスエー インコーポレイティド | Chlorine bleaching after peracid treatment |
| US11771673B2 (en) | 2018-06-15 | 2023-10-03 | Ecolab Usa Inc. | On site generated performic acid compositions for teat treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1770977A (en) | 2006-05-10 |
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