CN104349670B - Fumigant and fumigating device - Google Patents
Fumigant and fumigating device Download PDFInfo
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- CN104349670B CN104349670B CN201380027726.8A CN201380027726A CN104349670B CN 104349670 B CN104349670 B CN 104349670B CN 201380027726 A CN201380027726 A CN 201380027726A CN 104349670 B CN104349670 B CN 104349670B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/18—Vapour or smoke emitting compositions with delayed or sustained release
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/20—Combustible or heat-generating compositions
Abstract
A kind of fumigant, it contains (A) composition: the medicament of argentiferous, (B) composition: organic foaming agent, (C) composition: surfactant 3～12 quality %, (D) composition: spices, (E) composition: water 0.1～5 quality %.
Description
Technical field
The present invention relates to fumigant and fumigating device.
The Patent of the application based on proposing in Japan on May 30th, 2012 advocated priority No. 2012-122922, helps at thisDraw its content.
Background technology
Fumigant and fumigant (general name fumigant) are to have mixed various incendiary agents or blowing agent etc. or the heat generation base of the twoAgent and the medicament used as the expeling harmful organism of active ingredient etc. are main component. Fumigant is in the time that sootiness is processed, to makeHeat generation base burning or decompose, by the gas that now produces and the effect of smoke particle, make medicament at short notice toEjection in air, diffusion, to carry out the good preparation of preventing and kill off of harmful organism etc., are just widely used all the time.
Fumigant produces a large amount of smoke and gas bodies while processing due to sootiness, therefore in the space as sootiness handling object (it is following,Be sometimes referred to as object space) in the residual stink from medicament and heat generation base material.
All the time, in order to reduce the stink from fumigant, various schemes have been proposed.
For example, the fumigant composition (for example, patent documentation 1) that contains argentiferous medicament and organic foaming agent has been proposed. RootAccording to the invention of patent documentation 1, by being replaced by organic medicament and using argentiferous medicament, seek to reduce the stink from medicament.
In addition, for example, the fumigant group that contains incendiary agent 1～20 % by weight and decomposition accelerating agent 30～70 % by weight has been proposedCompound (for example, patent documentation 2). According to the invention of patent documentation 2, by reduce incendiary agent content with suppress sharplySmolder, seek to reduce stink.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2011-12051 communique
Patent documentation 2: Japanese patent laid-open 11-246306 communique
Summary of the invention
Problem to be addressed by invention
Sometimes, in order to cover the stink of sootiness while processing or the stink of fumigant itself, or in order to improve after sootiness processingImplementation sense and hobby property, have the situation of allocating spices in fumigant.
, the spices of allocating in fumigant volatilizees at leisure or decomposes, and fragrance is passed and died down in time, has and can not fillDivide the problem that obtains desired screening effect and the raising of hobby property. In addition, if merely improve the proportional quantity of spices, justHave the medicament ratio (fuming rate) that can be spread in object space to reduce, the effect of medicament becomes inadequate problem.
Therefore, the object of the invention is to, provide and can give full play to the effect of medicament and can suppress well spicesFragrance deteriorated fumigant in time.
The means of dealing with problems
The present inventor studies assiduously, found that by use argentiferous medicament the surfactant that contains specified quantitative andThe water of specified quantitative, can give full play to the effect of medicament, and can suppress well in time deteriorated of fragrance, thereby completeBecome the present invention.
The present invention has following mode.
[1] fumigant, is characterized by, and contains (A) composition: the medicament of argentiferous, (B) composition: organic foaming agent,(C) composition: surfactant 3～12 quality %, (D) composition: spices, (E) composition: water 0.1～5 quality %.
[2] fumigant as described in [1], wherein, above-mentioned (A) composition is freely silver-colored simple substance, silver oxide, nitric acid of choosingThe inorganic silver salt of silver etc. or they are supported at least one in the cohort that inorganic medicament that carrier forms forms.
[3] fumigant as described in [1] or [2], wherein, above-mentioned (B) composition be select free Celogen Az,P, p '-oxo two (benzene sulfonyl hydrazide), N, the group that N '-dinitrosopentamethylene tetramine and azodiisobutyronitrile formAt least one in group.
[4] fumigant described in any one of [1]～[3], wherein, above-mentioned (C) composition is nonionic tableSurface-active agent.
[5] fumigant described in any one of [1]～[4], wherein, above-mentioned (D) composition is to contain choosing freelyγ-11 carbon lactone, γ-decalactone, ambrotone, acetyl cedrene, ambrox, damascone, jasminoleneAnd at least one the flavor compositions of fragrance component in the cohort that forms of cumarin.
[6] fumigant described in any one of [1]～[5], wherein, silver concentration is with respect to total matter of fumigantAmount is 0.001～0.5 quality %.
[7] fumigant described in any one of [1]～[6], wherein, what in above-mentioned (A) composition, comprise is silver-coloredRelative concentration is 0.01～10 quality % in the gross mass of (A) composition.
[8] fumigant described in any one of [1]～[7], wherein, the content of above-mentioned (B) composition with respect toThe gross mass of fumigant is 50～80 quality %.
[9] fumigant described in any one of [1]～[8], wherein, the content of above-mentioned (C) composition with respect toThe gross mass of fumigant is 3～12 quality %.
[10] fumigant described in any one of [1]～[9], wherein, use [quality of above-mentioned (C) composition]/[onState the quality of (D) composition] represent mass ratio be 5～100.
[11] fumigant described in any one of [1]～[10], wherein, use [quality of above-mentioned (C) composition]/[onState the quality of (E) composition] represent mass ratio be 1～80.
[12] fumigating device, is characterized by, and has and holds the holding in container and heating of [1] described fumigantState the heater of fumigant.
The effect of invention
According to fumigant of the present invention, can give full play to the effect of medicament, and the fragrance that can suppress well spices withTime deteriorated.
Brief description of the drawings
[Fig. 1] is the sectional view that relates to the fumigating device of an embodiment of the invention.
Detailed description of the invention
(fumigant)
The fumigant of first method of the present invention is to contain (A) composition: the medicament of argentiferous, (B) composition: organic foaming agent,(C) composition: surfactant, (D) composition: spices, (E) composition: the fumigant of water.
<(A) composition: the medicament of argentiferous>
(A) of the present invention composition is the medicament of argentiferous. By using (A) composition, can bring into play sterilization, antibacterial, mildew-resistantAntimicrobial effect and deodorizing effect, the insecticidal effect etc. of bacterium, antifungi etc. In addition, (A) composition with in the past at cigaretteThe IPBC of extensive use (IPBC) and 2-isopropyl-5-methylphenol (IPMP) in fumigantDeng organic medicament to compare stink few. Therefore, can reduce sootiness and process time and sootiness after treatment from fumigantStink.
(A) composition is suitably selected according to the object of fumigant. As (A) composition, for example, can enumerate as bactericide, anti-The argentiferous medicament that microbial inoculum, anti-mildew agent, antimycotic agent, deodorant, agrochemical work, wherein, preferably uses sterilizationThe argentiferous medicament of agent, antiseptic, anti-mildew agent, antimycotic agent, deodorant.
As (A) composition, for example, can enumerate as active ingredient and comprise and there is the mould proof antifungi of antibiotic and sterilizing and removeThe silver-colored simple substance of smelly effect; Silver oxide; The inorganic silver salt of silver chlorate, silver nitrate, silver sulfate, silver carbonate, sulfonic acid silver salt etc.;The composition of the silver compound of the organic silver salts of silver formate, silver acetate etc. etc.
In addition, as (A) composition, can be also by above-mentioned active ingredient be supported at zeolite, silica gel, low molecular glass,The object forming on the material (following, to be called carrier) of calcium phosphate, silicate, titanium oxide etc. (below, is sometimes referred to as and carriesHold body). As holding body, for example, can enumerate the patina that has held silver-colored simple substance, silver oxide, inorganic silver salt, organic silver salts etc.The zeolites antiseptic of compound, silica type antiseptic, titanium oxide based antiseptic, silicates antiseptic etc.
Wherein, as (A) composition, from more reducing the viewpoint consideration from the stink of (A) composition, preferred silver-colored simple substance,The inorganic silver salt of silver oxide, silver nitrate etc. or they are held to the inorganic medicament forming on carrier, has more preferably held silverThe zeolites inorganic antiseptic of compound, hold the silica alumina class inorganic antiseptic of silver compound and held patinaThe silicates inorganic antiseptic of compound, has further preferably held the zeolites antiseptic of silver compound, particularly preferably holdsThe zeolites antiseptic of inorganic silver salt of silver-colored simple substance, silver oxide, silver nitrate etc. By using inorganic medicament, can be moreReduce sootiness process time and the sootiness stink from (A) composition after treatment.
These (A) compositions can use separately a kind, also can combine two or more use.
(A) there is no particular limitation for the form of composition, can determine according to the area of object space etc. (A) particle of compositionTrickleer, fuming rate is higher, when can giving full play to the effect of (A) composition, diffuses to region widely. AnotherAspect, if (A) particle of composition is too little, becomes after diffusion and is difficult to fall, and (A) composition is aobvious below object spaceExisting effect needs the time.
For example, (A) preferably 0.01～1000 μ m of the volume average particle size of composition, more preferably 0.5～100 μ m, furtherPreferably 1～5 μ m. In fumigant of the present invention, even (A) composition of larger like this particle diameter, also can cigaretteChange diffusion. At this, so-called " fuming " refers to (A) become to be divided into the state that can diffuse in object space.
In addition, volume average particle size is by laser diffraction formula particle size distribution device at random (LA910, Co., Ltd.Hole field makes made) value of trying to achieve, can be according to following time-and-motion study. By (A) composition according to solid composition 1 quality %Be dispersed in and in distilled water, become sample. This sample is put into laser diffraction formula particle size distribution device at random, at deviceIn disperse by ultrasonic wave after, irradiate laser, measure size distribution. Be the straight of 50% (volume) by the accumulative total of volume frequencyFootpath is as average grain diameter.
In fumigant, the content of (A) composition requires according to the kind of (A) composition and the concentration of active ingredient, fumigantFunction is determined. For example, the content of (A) composition in fumigant is in the silver concentration in fumigant, with respect to fumigantGross mass is preferably the amount of 0.001～0.5 quality %, the more preferably amount of 0.05～0.1 quality %, more preferablyThe amount of 0.05～0.5 quality %. Not enough above-mentioned lower limit if, the possibility that has the effect of (A) composition to reduce, exceedesState higher limit, (A) effect of composition is saturated, likely can not seek further effect and improve.
In addition, in this manual, in the time that each composition is used in combination according to two or more, content and the concentration of each composition areRefer to its total amount.
(A) silver concentration in composition, with respect to the gross mass of (A) composition, is preferably the amount of 0.01～10 quality %, more excellentElect the amount of 0.05～5 quality % as.
<(B) composition: organic foaming agent>
(B) composition is organic foaming agent. As (B) composition, there is thermal decomposition by heating and produce a large amount of heat in useTime produce the organic foaming agent of carbonic acid gas and nitrogen etc. (following, be generically and collectively referred to as foamed gas), for example, can enumerate idolNitrogen diformamide, p, p '-oxo two (benzene sulfonyl hydrazide), N, N '-dinitrosopentamethylene tetramine, azo two isobutylsNitrile etc. Wherein, consider preferably Celogen Az from the viewpoint of the generation of decomposition temperature, foamed gas etc. These (B)Composition is by heating and (A) composition and (C) composition foaming melting, according to the effect of the thermal decomposition gas of (B) compositionCan fuming (A) composition and (C) composition.
These (B) compositions can use separately a kind, also can combine two or more use.
The content of (B) composition in fumigant can according to the kind of (B) composition and (A) particle diameter etc. of composition determine, exampleAs, with respect to the gross mass of fumigant, preferably 50～80 quality %, more preferably 60～75 quality %, further preferably 65～75 quality %. If not enough above-mentioned lower limit, just has the possibility of fuming efficiently (A) composition, if exceed above-mentioned onLimit value, the many and trend in contaminated object space of the quantitative change of dispersing of analyte that just has (B) composition.
<(C) composition: surfactant>
(C) composition is surfactant. Fumigant by and have (C) composition and (E) composition, suppress (D) compositionIn time deteriorated of fragrance, and can make sootiness process time and sootiness fragrance after treatment become good.
As (C) composition, conventionally can be set forth in the anionic surface using in washing agent purposes and food emulsification purposes and liveProperty agent, cationic surface active agent, nonionic surface active agent etc.
As anionic surfactant, for example, can enumerate alkylbenzenesulfonate, polyoxyethylene alkane ether sulfate, α-Alkene sulfonate, higher alcohol sulfate salt etc. These anionic surfactant can use separately a kind, also can groupClose two or more use.
As cationic surface active agent, for example, can enumerate alkyl trimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, alkanamineSalt etc. These cationic surface active agents can use separately a kind, also can combine two or more use.
As nonionic surface active agent, for example, can enumerate polyoxyethylene alkane ether, polyoxyethylene polyoxypropylene alkane ether,Alkanolamide etc., the nonionic surface active agent conventionally using in washing agent, or sorbitan fatty acid ester,Fatty acid glyceride, polyglyceryl fatty acid ester, sucrose fatty ester, methyl glycol fatty acid ester, glycerine alkane ether, polyoxyethyleneSorbitan fatty acid ester, polyoxyethylene fatty acid glyceride, polyoxyethylene methyl glycol fatty acid ester etc., use as foodFatty acid ester or its oxyalkylene addition product of multivalence alcohol that the emulsifying agent on way uses, wherein, preferably the fatty acid ester of multivalence alcohol orIts oxyalkylene addition product.
The fatty acid ester of multivalence alcohol is the compound that multivalence alcohol is connected with ester bond with aliphatic acid. These nonionic surface active agentCan use separately a kind, also can combine two or more use.
The alkyl of the aliphatic acid in the fatty acid ester of multivalence alcohol or its oxyalkylene addition product can be alkyl, thiazolinyl and alkynylAny.
The carbon number of the aliphatic acid in the fatty acid ester of multivalence alcohol or its oxyalkylene addition product preferably 4～22, more preferably 8～18. If in above-mentioned scope, in time deteriorated of the fragrance that just can suppress better (D) composition.
As the multivalence alcohol in fatty acid ester or its oxyalkylene addition product of multivalence alcohol, preferably sorbitan, glycerine, sucrose,Wherein, preferred sorbitan, glycerine.
The carbon number of the oxyalkylene in the oxyalkylene addition product of the fatty acid ester of multivalence alcohol preferably 2～4, more preferably 2～3,Further preferred 2 (, oxygen ethene). If in above-mentioned scope, the fragrance that just can suppress better (D) composition withTime deteriorated.
Preferably 1～30 mole of the average addition molal quantity of oxyalkylene in the oxyalkylene addition product of the fatty acid ester of multivalence alcohol, more excellentSelect 1～20 mole. If in above-mentioned scope, in time deteriorated of the fragrance that just can suppress better (D) composition.
The oxyalkylene addition product of the fatty acid ester of multivalence alcohol can be the product of a kind of oxyalkylene addition, can be also two or moreThe product of oxyalkylene addition.
As fatty acid ester or its oxyalkylene addition product of multivalence alcohol, preferably sorbitan fatty acid ester, fatty acid glyceride,Or its oxygen Addition on ethylene thing.
As sorbitan fatty acid ester, for example, monoleate, the D-sorbite of preferred sorbitan monooleate etc.The monolaurate of acid anhydride monolaurate etc.
As the oxygen Addition on ethylene thing (, polyoxyethylene sorbitan fatty acid ester) of sorbitan fatty acid ester, excellentSelect Tween-81.
As fatty acid glyceride, for example, preferably Capmul MCM C8.
(C) composition is preferably the composition of liquid (, fusing point is below 25 DEG C) 25 DEG C time. If fusing point is below 25 DEG C,Just can improve and the Combination of (D) composition, seek the homogenization of (D) composition in fumigant, suppress better (D)In time deteriorated of the fragrance of composition.
In addition,, if fusing point is below 25 DEG C, just becomes together with (A) composition and be easily attached to the sky that forms object spaceCard, wall, floor etc., the just effect of easy long-time performance (A) composition. (C) lower limit of the fusing point of composition does not haveBe particularly limited, for example, preferably more than-25 DEG C, more than more preferably-15 DEG C. Not enough above-mentioned lower limit, although easilyBe attached to the ceiling, wall, floor etc. that form object space, be difficult to but have the possibility that stops.
Consider that object space is in time deteriorated of living space etc. and the fragrance that suppresses better (D) composition, upperIn (C) composition of stating, preferably nonionic surface active agent. Wherein, as (C) composition, the preferably fat of multivalence alcoholAcid esters or its oxyalkylene addition product, more preferably fusing point is 25 DEG C of following sorbitan fatty acid ester, polyoxyethylene sorbosesAlcohol acid anhydride fatty acid ester, fatty acid glyceride or these oxygen Addition on ethylene thing.
Above-mentioned (C) composition can use separately a kind, also can combine two or more use.
The content of (C) composition in fumigant is 3～12 quality % with respect to the gross mass of fumigant, preferably 3～10 quality %,More preferably 5～8 quality %. Not enough above-mentioned lower limit, (C) composition very little, just can not fully suppress (D) compositionIn time deteriorated of fragrance, exceed above-mentioned higher limit, (A) the fuming rate of composition just becomes insufficient.
In fumigant, with mass ratio that [(A) the silver-colored quality in composition]/[(C) quality of composition] represents (following,Be sometimes referred to as A/C ratio) can determine according to the kind of (C) composition etc., for example, preferably 0.0001～0.2, more preferably 0.005～0.02. A/C is than not enough above-mentioned lower limit, and (A) composition is difficult to fuming, just have (A) composition effect reduce canCan, A/C is than exceeding above-mentioned higher limit, (C) composition very little, just have the fragrance that can not fully suppress (D) composition withThe deteriorated possibility of time.
In fumigant, (sometimes claim below, with the mass ratio that [(B) quality of composition]/[(C) quality of composition] representsFor B/C ratio) preferably 5～27, more preferably 8～15. B/C is than not enough above-mentioned lower limit, (A) the fuming rate of compositionBecome insufficient, the possibility that just has the effect of (A) composition to reduce, B/C is than exceeding above-mentioned higher limit, (C) compositionVery little, just there is the deteriorated possibility in time of fragrance that can not fully suppress (D) composition.
<(D) composition: spices>
(D) composition is spices. By containing (D) composition, can cover sootiness process time and sootiness stink after treatmentWith the stink of fumigant itself, or can give while processing with sootiness and sootiness object space after treatment fragrance arbitrarily.
As (D) composition, can enumerate fragrance component and fragrance component and be dispersed in the flavor compositions in solvent. Spices becomesThe list dividing, is recorded in various documents for example " PerfumeandFlavorChemicals ", Vol. IAnd II, SteffenArctander, AlluredPub.Co. (1994); " synthetic perfume chemistry and knowledge of goods ",Print rattan unit one work, chemical industry day newspaper office (1996); " PerfumeandFlavorMaterialsofNaturalOrigin ",SteffenArctander, AlluredPub.Co. (1994); " fragrance encyclopaedia " (fragrant り encyclopaedia), JapanFragrance association is compiled, towards storehouse bookstore (1989) and " PerfumeryMaterialPerformanceV.3.3 ", BoelensAromaChemicalInformationService (1996), and " FloweroilsandFloralCompoundsInPerfumery ", DanuteLajaujisAnonis, AlluredPub.Co. (1993) etc. Become as spicesPoint, particularly, can enumerate ambrox, anisaldehyde, acetyl cedrene, phenmethylol, citral, cumarin, rabbitAuricled Hedyotis Herb aldehyde, α-damascone, Jiale muskiness, γ-decalactone, γ-11 carbon lactone, cyclopentadecylene lactone, dihydro jasmineKetone acid methyl esters, piperonal, hexyl acetate, jasminolene, 1-Hexyl salicylate, ambrotone, ligustral, lilial, lemonLemon olein, cetone gamma, benzyl carbinol, α-(trichloromethyl) benzyl alcohol acetic acid esters, as solvent, can enumerateDPG.
In fragrance component, γ-11 carbon lactone, γ-decalactone, ambrotone, acetyl cedrene, ambrox, prominentThe excellence aspect stink screening effect in the time that sootiness is processed of ketone, jasminolene, cumarin and sootiness fragrance retention after treatment of faintingAnd by preferred. As fragrance component being dispersed in to the flavor compositions in solvent, preferably contain γ-11 carbon lactone, γ-last of the ten Heavenly stemsLactone, ambrotone, acetyl cedrene, ambrox, damascone, jasminolene, cumarin be as fragrance component,DPG is as the composition of solvent.
The kinds of content basis (D) composition of (D) composition in fumigant etc. are suitably definite, for example, and with respect to fumigantGross mass, preferably 0.1～2 quality %, more preferably 0.1～1 quality %, further preferred 0.3～1 quality %, excellent especiallySelect 0.4～0.8 quality %. Not enough above-mentioned lower limit, is preserving after fumigant, while having sootiness to process and sootiness processingAfter the fragrance of fragrance, fumigant itself become inadequate may. Exceed above-mentioned higher limit, have (A) compositionThe possibility that fuming rate reduces.
(D), when composition is flavor compositions, (D) content of the fragrance component in composition is with respect to total matter of (D) compositionPreferably 50～99 quality %, more preferably 70～95 quality % of amount.
In fumigant, (sometimes claim below, with the mass ratio that [(C) quality of composition]/[(D) quality of composition] representsFor C/D ratio) preferably 5～100, more preferably 6～80, further preferably 10～18. C/D is than not enough above-mentioned lower limit,When having sootiness to process and sootiness fragrance after treatment become fragrance insufficient or fumigant self and become inadequateMay, exceed above-mentioned higher limit, just there is the deteriorated possibility in time of fragrance that can not fully suppress (D) composition.
<(E) composition: water>
(E) composition is water. Fumigant, by containing (E) composition, can suppress the fragrance of (D) composition at any time wellBetween deteriorated.
As (E) composition, can be running water, ion exchange water and the distilled water of new allotment in manufacture method described laterDeng, can be also the water having contained in (C) composition etc.
The content of (E) composition in fumigant is 0.1～5 quality %, preferably 0.1～4 matter with respect to the gross mass of fumigantAmount %, more preferably 0.3～2 quality %. Not enough above-mentioned lower limit, can not fully suppress the fragrance of (D) composition at any timeBetween deteriorated, exceed above-mentioned higher limit, (A) the fuming rate of composition becomes insufficient.
In fumigant, (sometimes claim below, with the mass ratio that [(C) quality of composition]/[(E) quality of composition] representsFor C/E ratio) preferably 1～30, more preferably 5～30. If C/E, than in above-mentioned scope, can improve (A) moreThe fuming rate of dividing. From other situation, C/E is than preferably 1～80, and more preferably 2～80.
In fumigant, (sometimes claim below, with the mass ratio that [(D) quality of composition]/[(E) quality of composition] representsFor D/E ratio), preferably 0.05～10, more preferably 0.2～2.5. D/E, than not enough above-mentioned lower limit, has sootiness processingTime and sootiness fragrance after treatment become fragrance insufficient or fumigant self become inadequate may, exceed above-mentionedHigher limit, just has the deteriorated possibility in time of fragrance that can not fully suppress (D) composition.
In fumigant, (C) composition and (E) total amount of composition with respect to preferably 3～15 quality % of gross mass of fumigant,More preferably 5～10 quality %. Not enough above-mentioned lower limit, has in time bad of fragrance that can not fully suppress (D) compositionThe possibility of changing, exceedes above-mentioned higher limit, the possibility that has the loose rate of waving of (A) composition to reduce.
<composition arbitrarily>
Fumigant can contain (A)～(E) composition any composition in addition in the scope that does not hinder effect of the present invention.As any composition, for example, can enumerate the additive of stabilizing agent, bonding agent, excipient, spices, pigment etc. At theseArbitrarily in composition, more than preferably containing any one of stabilizing agent, bonding agent and excipient.
As stabilizing agent, can enumerate dibutyl hydroxy toluene (BHT), butylated hydroxyanisole (BHA), n-propyl gallate, epoxides (exampleAs, epoxidised soybean oil, epoxidised linseed oil etc.) etc.
As bonding agent, can enumerate methylcellulose, ethyl cellulose, carboxymethyl cellulose, hydroxypropyl methylcellulose,Hydroxypropyl cellulose, starch, dextrin, hydroxypropul starch, gelatin, polyvinyl alcohol, polyvinyl acetate, polyethylene pyrrolesAlkane ketone, Sodium Polyacrylate etc.
As excipient, can enumerate clay (, hydrated aluminium silicate), talcum, diatomite, kaolin, bentonite, whiteCarbon ink etc.
<manufacture method>
Fumigant of the present invention is modulated to the solid preparation of powdery, granular, tablet etc. As the manufacture method of fumigant, canUse known manufacture method according to object formulation. For example, while making granular preparation, can be according to extruding pelletization method, pressureThe manufacture method manufacture of the known granules such as contracting comminution granulation, stirring-granulating method, rotating granulation method, fluidized bed comminution granulation.
As according to the manufacture method of extruding pelletization method, can enumerate following method. First, each composition of fumigant is passed throughThe mixing such as kneader, obtain mixture after further adding appropriate water to mix. At this moment, be preferably pre-mixed (C)～(E)Any composition of composition and liquid is made mixed liquor, at any composition that comprises (A) composition, (B) composition and solidFor example, in the powder mixture of (, clay etc.), add mixed liquor, mix. In addition, above-mentioned mixed liquor is preferably emulsion.
The mould with any perforate footpath for the mixture obtaining, extrudes before use or laterally extruding granulator granulation. By upperState granules and cut into arbitrarily after size with cutting machine etc. further, dry.
Drying means for example can be enumerated the use heat drying method of known drying machine in the past.
Baking temperature is not particularly limited, for example, be 50～100 DEG C.
Suitably determine according to baking temperature drying time.
As fumigant of the present invention, preferably contain the fumigant of following each composition: (A) composition be choosing freely silver-colored simple substance,The inorganic silver salt of silver oxide, silver nitrate etc. or they are supported in the cohort that inorganic medicament that carrier forms forms at leastOne, (B) composition is to select free Celogen Az, p, p '-oxo two (benzene sulfonyl hydrazide), N, N '-bis-nitrousAt least one in the cohort that base pentamethylene tetramine and azodiisobutyronitrile form, (C) composition is nonionic surfaceActivating agent, (D) composition be contain select free γ-11 carbon lactone, γ-decalactone, ambrotone, acetyl cedrene,The spices group of at least one fragrance component in the cohort that ambrox, damascone, jasminolene and cumarin formCompound, (E) composition is water;
Be more preferably the fumigant that contains following each composition: (A) to be that choosing freely holds the zeolites of silver compound inorganic for compositionAntiseptic, hold the silica alumina class inorganic antiseptic of silver compound and hold the silicates inorganic antibacterial of silver compoundAt least one in the cohort that agent forms, (B) composition is Celogen Az, (C) composition be select 25 DEG C of free fusing points withUnder sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid glyceride with and oxygen ethene addAt least one in the cohort that one-tenth thing forms, (D) composition is to contain to select free ambrox, anisaldehyde, acetyl group cypressWood alkene, phenmethylol, citral, cumarin, cyclamen aldehyde, α-damascone, Jiale muskiness, γ-decalactone, γ-tenOne carbon lactone, cyclopentadecylene lactone, MDJ, piperonal, hexyl acetate, jasminolene, salicylic acidOwn ester, ambrotone, ligustral, lilial, limonene, cetone gamma, benzyl carbinol, α-(trichloromethyl)The flavor compositions of at least one fragrance component in the cohort that benzyl alcohol acetic acid esters and DPG form, (E) compositionWater;
Further preferably contain the fumigant of following each composition: (A) composition be choosing freely hold silver-colored zeolites inorganic resistMicrobial inoculum, hold silver-colored silica alumina class inorganic antiseptic and hold in the cohort that silver-colored silicates inorganic antiseptic formsAt least one, (B) composition is Celogen Az, (C) composition is to select free sorbitan monooleate, Dan XinIn the cohort that acid glyceride, Span-20 and Tween-81 form at leastOne, (D) composition be contain ambrox, anisaldehyde, acetyl cedrene, phenmethylol, citral, cumarin,Cyclamen aldehyde, α-damascone, Jiale muskiness, γ-decalactone, γ-11 carbon lactone, cyclopentadecylene lactone, dihydro jasmineJasmine ketone acid methyl esters, piperonal, hexyl acetate, jasminolene, 1-Hexyl salicylate, ambrotone, ligustral, lilial,The perfume (or spice) of limonene, cetone gamma, benzyl carbinol, α-(trichloromethyl) benzyl alcohol acetic acid esters and DPGFeed composition, (E) composition is water.
<fume smoking method>
As fume smoking method of the present invention, can enumerate known method in the past, for example, can be set forth in metal container made, potteryIn any vessel of container made etc., hold fumigant, directly or the method for indirect fumigant, wherein, preferably indirectly addThe method of heat. By indirect fumigant, can reduce the indoor pollution producing due to the burning gases of fumigant etc. AndAnd, also can make fumigating device described later, object space is implemented to sootiness processing.
As object space, be not particularly limited, for example, can enumerate bathroom, living room, closet, lavatory etc.
As the means of indirect fumigant, as long as the fumigant that do not burn, can supply with to fumigant (B) composition heatThe means of decomposing the heat energy producing, for example, can be set forth in metal container and hold fumigant, by this metalThe method of the container heating fumigant of system.
As heating means, can use known method in the past, for example, can enumerate: make with the material of water contact heating withWater contacts, and utilizes the method for its reaction heat; Mix iron powder and oxidant (ammonium chlorate etc.), or hybrid metal and with above-mentionedMetal Phase, than the less metal oxide of ionization tendency or oxidant, utilizes the method for its oxidation reaction heat etc. As with waterThe material of contact heating, can enumerate calcium oxide, magnesium chloride, aluminium chloride, calcium chloride, iron chloride etc. Wherein, from practicalityViewpoint consider, preferably make to contact with water with the material of water contact heating, utilize the method for its reaction heat, more preferably utilize oxygenChange the method for the reaction heat of calcium and water.
The use amount of fumigant is suitably set according to the volume of object space, for example, and preferred every 1m3Object space is0.1～2.4g, more preferably 0.4～2.0g.
In the sootiness processing time (from sootiness starts until remove airtight time of object space), be not particularly limited, excellentSelect more than 1 hour, more preferably more than 1.5 hours.
(fumigating device)
The fumigating device of second method of the present invention be have hold first method of the present invention fumigant hold container andThe device of the heater of the fumigant that heating is held.
Just relate to the fumigating device of an embodiment of the invention, below with reference to Fig. 1 explanation.
The fumigating device 10 of Fig. 1 is fumigating devices of indirect mode, substantially by casing 12, be arranged on casing 12 insideHeating part 20 and the fumigant portion 32 that is arranged on casing 12 inside form. Casing 12 by the main body 14 of approximate circle tubular,Bottom 16 and cap 18 form.
In casing 12, be provided with fumigant container 30 (holding container), in fumigant container 30, hold fumigant,Form fumigant portion 32.
In fumigating device 10, heating part 20 is heaters.
Cap 18 has through hole, can enumerate mesh, perforated metal, cancellate framework etc. The material of cap 18 for exampleCan enumerate metal, pottery etc.
The material of main body 14 is identical with cap 18.
Fumigant container 30 is in playing a role as the container that holds fumigant portion 32, and also conduct is to fumigant portion 32The heat transfer part that transmits the heat energy being produced by heating part 20 plays a role. As fumigant container 30, for example, can enumerate metalThe container of system etc.
Heating part 20 is determined according to the required heat of the fuming of fumigant portion 32, for example, can be to have held to contact with water to send outThe heating part of material (for example, calcium oxide etc.) of heat, also can hold and separate iron powder and oxidant with barrier materialHeating part can also be to have held to separate metal and the metal oxygen less than ionization tendency with above-mentioned Metal Phase with barrier materialThe heating part of compound or oxidant.
Wherein, preferably held and the heating part of the material of water contact heating the heating part that has more preferably held calcium oxide.
Bottom 16 can determine according to the mechanism of heating part 20, for example, heating part 20 by with the material (oxygen of water contact heatingChange calcium etc.) while forming, can use nonwoven and metal mesh etc. in bottom 16. By making bottom 16 for nonwovenOr mesh, can make water immerse from bottom 16 in heating part 20 and heat.
Describe with regard to the fume smoking method that uses fumigating device 10. First, fumigating device 10 is positioned in object space.Then, according to the mechanism of heating part 20, heating part 20 is generated heat. For example,, when heating part 20 is made up of calcium oxide, the end of byPortion 16 is immersed in water. Bottom 16 1 is immersed in water, and water just soaks into bottom 16 and contacts with calcium oxide, 20 of heating partsHeat. Heating part 20 1 heatings, heat fumigant portion 32 by fumigant container 30. The cigarette of heated fumigant portion 32The decomposition of fumigant by (B) composition produces gas, (A) composition, (C) composition and (D) gas of composition and generationFuming together, by the through hole of cap 18, diffuses to object space.
There is no particular limitation for the shape of main body, can be cylindric can be also cubic. The shape of bottom is not specialRestriction, can be that fenestra can be polygon. Particularly, be preferably the cylindric of height 6～12cm, radius 3～6cm.There is no particular limitation to hold the shape of container, can be cylindric can be also cubic. Hold the shape of container bottomThere is no particular limitation, can be that fenestra can be polygon. Particularly, be preferably height 6.0～10.0cm, radius 2.5～4.0cm's is cylindric.
In above-mentioned embodiment, as fumigating device, be illustrated as an example of the fumigating device of indirect mode example, butThat the present invention is not limited only to this. For example, can be also and Japanese Patent Laid-Open 2011-193874 communique and Japan Patent spyOpen the fumigating device of the same direct-heating type of the fumigating device described in 2002-199834 communique. The cigarette of direct-heating typeSmoked device has the firing tools that holds the fumigant portion of fumigant and the fumigant of lighting up, and firing tools is as heater.
But, make fumigant self burned flame owing to not producing, preferably the fumigating device of indirect heating type.
As mentioned above, fumigant of the present invention, owing to using (A) composition as medicament, can reduce the stink from medicament.
In addition, owing to containing (C) composition and (E) composition, in time deteriorated of the fragrance that can suppress (D) composition.
Further, due to (C) composition and (E) content of composition in specific scope, can not lose (A)The fuming rate of composition, gives full play to the effect of (A) composition.
Embodiment
Below, enumerate embodiment the present invention is described in detail, but the present invention is not limited by the following stated. In addition table,In, (A) content of composition represents silver-colored content, the content of other each composition represents pure component conversion amount.
(use raw material)
<(A) composition: argentiferous medicament>
A-1: zeolite with carrying silver class inorganic antiseptic (trade name: clean and beautiful AJ10N, volume average particle size 2.5 μ m, very closeDegree 2g/cm3(20 DEG C), bulk density 0.4g/cm3(20 DEG C), silver content 2.5 quality %, Co., Ltd.'s product combustion is clean and beautifulSystem).
A-2: year silver-colored silica alumina class inorganic antiseptic (trade name: ATOMYBALL-(UA), volume average particle size 15nm,Silver content 0.07 quality %, RiHui catalyst synthesis Co., Ltd's system).
A-3: carry silver-colored silicates inorganic antiseptic (trade name: AIS-NAZ320, volume average particle size 2 μ m, silver content1.2 quality %, RiHui catalyst synthesis Co., Ltd's system).
<(B) composition: organic foaming agent>
B-1: Celogen Az (ADCA) (trade name: DaiblowAC.2040 (C), the industrial strain formula of refining large dayCommercial firm's system).
<(C) composition: surfactant>
C-1: sorbitan monooleate (trade name: EMASOLO-10V, Kao Corp's system), fusing point: 13 DEG C.
C-2: Capmul MCM C8 (trade name: MG-80, Di-ichi Kogyo Seiyaku Co., Ltd.'s system), fusing point: 12 DEG C.
C-3: Span-20 (trade name: EMASOLL-10V, Kao Corp's system), fusing point:13℃。
C-4: Tween-81 (the average 20 moles of addition products of oxygen ethene) (trade name: EMASOLO-120V, Kao Corp's system), fusing point :-23 DEG C. In table, be denoted as POE (20) sorbitan monooleate.
<(D) composition: spices>
Flavor compositions shown in table 1.
[table 1]
| Composition name | Quality % |
| AMBROXANE (ambrox) | 0.6 |
| ANIS ALDEHYDE (anisaldehyde) | 1.0 |
| ACETYL CEDRENE (acetyl cedrene) | 2.0 |
| BENZYL ALCOHOL (phenmethylol) | 1.5 |
| CITRAL (citral) | 1.0 |
| COUMARIN (cumarin) | 1.0 |
| CYCLAMEN ALDEHYDE (cyclamen aldehyde) | 4.0 |
| DAMASCONE ALPHA (α-damascone) | 4.0 |
| GALAXOLIDE (Jiale muskiness) | 20.0 |
| GAMMA DECALACTONE (γ-decalactone) | 3.0 |
| GAMMA UNDECALACTONE (γ-11 carbon lactone) | 6.5 |
| HABANOLIDE (cyclopentadecylene lactone) | 4.5 |
| HEDION (MDJ) | 3.0 |
| HELIOTROPIN (piperonal) | 0.5 |
| HEXYL ACETATE (hexyl acetate) | 1.0 |
| HEXYL CINNAMIC ALDEHYDE (jasminolene) | 7.0 |
| HEXYL SALICYLATE (1-Hexyl salicylate) | 5.0 |
| ISO E SUPER (ambrotone) | 5.0 |
| LIGUSTRAL (ligustral) | 0.5 |
| LILIAL (lilial) | 7.5 |
| LIMONENE (limonene) | 1.0 |
| METHYL IONONE GAMMA (cetone gamma) | 0.8 |
| PHENYL ETHYL ALCOHOL (benzyl carbinol) | 1.6 |
| ROSEPHENONE (α-(trichloromethyl) benzyl alcohol acetic acid esters) | 1.0 |
| DIPROPYLENE GLYCOL (DPG) | 17.0 |
| Amount to | 100.0 |
<composition arbitrarily>
Bonding agent: hydroxypropyl methylcellulose (HPMC) (trade name: METOLOSE60SH-50, SHIN-ETSU HANTOTAI's chemical industry strainFormula commercial firm system).
Excipient: clay (trade name: NK-300, Showa Kde Co., Ltd.'s system).
(evaluation method)
<storage stability>
" fragrance of fumigant "
The fumigant 5g of each example is put into and preserves container cover lid, preserve one month at 50 DEG C, as sample. Will be eachThe fumigant 5g of example puts into and preserves container cover lid, preserves one month at 20 DEG C, as standard items. Preservation container makesWith " water In は じ め Ru バ Le サ Application [6-8 Tatami uses] (VARSAN[6-8 that water starts opens tatami area and uses])(trade name, Lion Corporation's system) " container.
Open the lid of standard items and sample, according to following evaluation criterion, use sensory evaluation. " perfume (or spice) in following evaluation criterionTaste " be the fragrance of (D) composition of allocating in fumigant.
[evaluation criterion]
A: the fragrance of sample and standard items is equal.
B: the fragrance of sample compared with the fragrance of standard items slightly a little less than, but be no problem degree.
C: the fragrance of sample compared with the fragrance of standard items, quite a little less than.
D: the fragrance of sample compared with the fragrance of standard items, obviously a little less than.
" sootiness fragrance after treatment "
Prepare the container of " water In は じ め Ru バ Le サ Application [6-8 Tatami uses] (trade name, Lion Corporation's system) ",In fumigant container in said vesse, pack the fumigant 5g of each example into, in the heating agent accommodation section in same container, pack oxygen intoChange calcium 37g, make the fumigating device same with the fumigating device 10 of Fig. 1.
The fumigating device that at 50 DEG C, preservation obtains one month, as testing arrangement. In addition, preserve one of fumigating device at 20 DEG CMonth, as standard set-up.
In the laboratory central authorities of long 3.42m × wide 3.82m × high 2.4m, the feedwater plastics that placement has packed 23ml water into holdDevice, feeds water with putting into testing arrangement or standard set-up in plastic containers at this, starts sootiness processing. Sootiness is processed and is startedAfter 2 hours, according to following evaluation criterion sensory evaluation. " fragrance " in following evaluation criterion is to allocate in fumigant(D) fragrance of composition.
[evaluation criterion]
A: implement in the laboratory of sootiness processing with testing arrangement and implement the perfume (or spice) in the laboratory of sootiness processing with standard set-upTaste is equal.
B: with the fragrance in the laboratory of testing arrangement enforcement sootiness processing and the laboratory of implementing sootiness processing with standard set-upA little less than interior fragrance is compared slightly, but it is no problem degree.
C: with the fragrance in the laboratory of testing arrangement enforcement sootiness processing and the laboratory of implementing sootiness processing with standard set-upA little less than interior fragrance is compared quite.
D: with the fragrance in the laboratory of testing arrangement enforcement sootiness processing and the laboratory of implementing sootiness processing with standard set-upA little less than interior fragrance is compared obviously.
<(A) the fuming rate of composition>
Prepare the container of " water In は じ め Ru バ Le サ Application [6-8 Tatami uses] (trade name, Lion Corporation's system) ",In fumigant container in said vesse, pack the fumigant 5g of each example into, in the heating agent accommodation section in same container, pack oxygen intoChange calcium 37g, make the fumigating device same with the fumigating device 10 of Fig. 1.
Put into fumigating device in the feedwater that has packed 23ml water in plastic containers, carry out sootiness.
After sootiness, all reclaim the residue in fumigant container, rare nitric acid of this residue being put into 5 quality % makes its strippingSilver composition, as working sample. By quantitatively this working sample of IPC luminesceence analysis, obtain not by the remnants silver of fumingAmount.
In addition, with regard to the fumigant before sootiness, similarly operate with above-mentioned residue the silver-colored amount (in fumigant 5g) of obtaining,Calculate fuming rate according to following (1) formula. The fuming rate obtaining is classified according to following evaluation criterion.
Fuming rate (quality %)=[(the silver-colored quality in the fumigant before sootiness)-(the silver-colored quality in residue)] ÷ (cigaretteSilver-colored quality in fumigant before smoked) × 100 (1)
" evaluation criterion "
A: more than fuming rate 60 quality %.
B: the above less than 60 quality % of fuming rate 40 quality %.
C: the above less than 40 quality % of fuming rate 20 quality %.
D: fuming rate less than 20 quality %.
(embodiment 1～25, comparative example 1～5)
According to composition shown in table 2～4, under the condition of 20 DEG C, with kneading machine (S5-2G type, the gloomy mountain system of Co., Ltd.)Be uniformly mixed (A) composition, (B) composition, HPMC and clay for powder composition. By (C) that be uniformly mixed in advanceComposition, (D) composition and water (with respect to (A)～(D) composition and arbitrarily total 100 Quality Mgmt Dept of composition, forThe water of 10 Quality Mgmt Dept) mixed liquor add in above-mentioned kneading machine and be mixed to get mixture.
By the mixture that obtains, with the front extruding granulator of mould with diameter 2mm perforate footpath, (EXK-1, Co., Ltd. is notTwo パ ウ ダ Le (FujiPaudal) systems) granulation obtains granules. The granules obtaining is by milling cutter (FL300, strain formulaThe only パ ウ ダ of commercial firm Le system) be cut into length 2～5mm, by being set as drying machine (RT-120HL, the ALP strain formula of 70 DEG CCommercial firm's system), adjust and become component to become (E) described in table drying time, obtain granular fumigant. Just obtainFumigant, evaluation storage stability and (A) the fuming rate of composition, it is as shown in the table for its result.
[table 2]
[table 3]
[table 4]
As shown in table 2～4, the storage stability that has been suitable for embodiments of the invention 1～25 is " B "～" A ". ,In time deteriorated of the fragrance that embodiment 1～25 has suppressed (D) composition well. In addition (A) of embodiment 1～25,The fuming rate of composition is evaluated as " B "～" A ". , can give full play to the effect of (A) composition.
On the other hand, (C) content of composition be the comparative example 1 of 2 quality % and (E) content of composition be 0.01 quality %The storage stability of comparative example 3 be " D "～" C ". (C) content of composition is the comparative example 2 of 14 quality % and (E)The content of composition is that the fuming rate of (A) composition of the comparative example 4 of 6 quality % is evaluated as " D "～" C ". Do not contain (C)The storage stability of the comparative example 5 of composition is " D ".
According to these results, judgement, by being suitable for the present invention, can be given full play to the effect of medicament, and can press down wellIn time deteriorated of the fragrance of spices processed.
The industrial possibility of utilizing
According to fumigant of the present invention, can give full play to the effect of medicament, and the fragrance that can suppress well spices withTime deteriorated.
The explanation of symbol
10 fumigating devices
20 heating parts
30 fumigant containers
32 fumigant portions
Claims (6)
1. a fumigant, is characterized by, and contains (A) composition: the medicament of argentiferous, (B) composition: organic foaming agent, (C)Composition: surfactant is 3～12 quality %, (D) composition with respect to the gross mass of fumigant: spices, (E) composition:Water 0.1～5 quality %,
Described silver concentration is 0.001～0.5 quality % with respect to the gross mass of fumigant,
The content of described (B) composition is 50～80 quality % with respect to the gross mass of fumigant,
With [quality of described (C) composition]/[quality of described (D) composition] represent mass ratio be 5～100,
With [quality of described (C) composition]/[quality of described (E) composition] represent mass ratio be 1～80.
2. fumigant as claimed in claim 1, wherein, described (A) composition is freely silver-colored simple substance, silver oxide, nothing of choosingMachine silver salt or they are supported at least one in the cohort that inorganic medicament that carrier forms forms.
3. fumigant as claimed in claim 1 or 2, wherein, described (B) composition is to select free Celogen Az, p,P '-oxo two (benzene sulfonyl hydrazide), N, in the cohort that N '-dinitrosopentamethylene tetramine and azodiisobutyronitrile formAt least one.
4. fumigant as claimed in claim 1 or 2, wherein, described (C) composition is nonionic surface active agent.
5. fumigant as claimed in claim 1 or 2, wherein, described (D) composition is to contain to select in free γ-11 carbonEster, γ-decalactone, ambrotone, acetyl cedrene, ambrox, damascone, jasminolene and cumarinThe flavor compositions of the fragrance component of at least one in the cohort forming.
6. fumigant as claimed in claim 1 or 2, wherein, the silver-colored relative concentration comprising in described (A) composition in(A) gross mass of composition is 0.01～10 quality %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-122922 | 2012-05-30 | ||
| JP2012122922A JP5903334B2 (en) | 2012-05-30 | 2012-05-30 | Smoke agent and smoke device |
| PCT/JP2013/061636 WO2013179805A1 (en) | 2012-05-30 | 2013-04-19 | Smoking agent and smoking device |
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| Publication Number | Publication Date |
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| CN104349670A CN104349670A (en) | 2015-02-11 |
| CN104349670B true CN104349670B (en) | 2016-05-25 |
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| CN201380027726.8A Active CN104349670B (en) | 2012-05-30 | 2013-04-19 | Fumigant and fumigating device |
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| Country | Link |
|---|---|
| JP (1) | JP5903334B2 (en) |
| KR (1) | KR20150027029A (en) |
| CN (1) | CN104349670B (en) |
| HK (1) | HK1205878A1 (en) |
| MY (1) | MY167067A (en) |
| SG (1) | SG11201407844SA (en) |
| TW (1) | TWI574620B (en) |
| WO (1) | WO2013179805A1 (en) |
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| JP6014423B2 (en) * | 2012-08-30 | 2016-10-25 | ライオン株式会社 | Smoke agent and smoke device |
| JP6207083B2 (en) * | 2013-04-17 | 2017-10-04 | ライオン株式会社 | Granular smoke composition |
| JP6225354B2 (en) * | 2014-06-25 | 2017-11-08 | ライオン株式会社 | Smoke agent |
| JP6559950B2 (en) * | 2014-12-11 | 2019-08-14 | 大日本除蟲菊株式会社 | Smoke agent composition and method for mitigating irritating odor after using smoke agent |
| JP6489696B2 (en) * | 2015-09-29 | 2019-03-27 | ライオン株式会社 | Indirect heating smoke composition |
| JP6741489B2 (en) * | 2016-06-27 | 2020-08-19 | ライオン株式会社 | Method for producing smoke agent composition |
| CN108669498A (en) * | 2018-05-25 | 2018-10-19 | 湖南伍子醉食品有限公司 | A kind of preparation method of matrimony vine betel nut |
| JP7341045B2 (en) | 2019-12-20 | 2023-09-08 | ライオン株式会社 | Method for suppressing dirt adhesion on hard surfaces |
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| JP3453292B2 (en) * | 1998-02-25 | 2003-10-06 | 中外製薬株式会社 | Smoking agent composition |
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| JP4420149B2 (en) * | 1999-12-22 | 2010-02-24 | ライオン株式会社 | Tablet composition |
| JP4410057B2 (en) * | 2003-08-08 | 2010-02-03 | ライオン株式会社 | Antifungal fumigating agent, apparatus, and processing method |
| JP4611722B2 (en) * | 2004-11-30 | 2011-01-12 | ライオン株式会社 | Antibacterial liquid composition and method for producing the same |
| JP5101135B2 (en) * | 2006-05-17 | 2012-12-19 | ライオン株式会社 | Antibacterial / deodorant composition and antibacterial / deodorant method using the same |
| JP2008231061A (en) * | 2007-03-22 | 2008-10-02 | Noevir Co Ltd | Cosmetic addition composition, cosmetic and their manufacturing methods |
| JP5903335B2 (en) * | 2012-05-30 | 2016-04-13 | ライオン株式会社 | Smoke agent for indirect heating method and smoke device for indirect heating method |
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2012
- 2012-05-30 JP JP2012122922A patent/JP5903334B2/en active Active
-
2013
- 2013-04-19 CN CN201380027726.8A patent/CN104349670B/en active Active
- 2013-04-19 KR KR1020147020333A patent/KR20150027029A/en not_active Application Discontinuation
- 2013-04-19 WO PCT/JP2013/061636 patent/WO2013179805A1/en active Application Filing
- 2013-04-19 MY MYPI2014703513A patent/MY167067A/en unknown
- 2013-04-19 SG SG11201407844SA patent/SG11201407844SA/en unknown
- 2013-04-24 TW TW102114587A patent/TWI574620B/en not_active IP Right Cessation
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- 2015-07-13 HK HK15106653.8A patent/HK1205878A1/en not_active IP Right Cessation
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| JP2002199834A (en) * | 2000-10-25 | 2002-07-16 | Chugai Pharmaceut Co Ltd | Fumigation device, fumigation method using the same, and method for repelling insect |
| JP2010280577A (en) * | 2009-06-02 | 2010-12-16 | Lion Corp | Fumigant composition and fumigation apparatus |
| JP2011012051A (en) * | 2009-06-02 | 2011-01-20 | Lion Corp | Fumigation agent composition, fumigation equipment and fumigation method |
| CN102187854A (en) * | 2010-02-26 | 2011-09-21 | 狮王株式会社 | Direct heating type fuming device |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201410147A (en) | 2014-03-16 |
| KR20150027029A (en) | 2015-03-11 |
| WO2013179805A1 (en) | 2013-12-05 |
| JP5903334B2 (en) | 2016-04-13 |
| HK1205878A1 (en) | 2015-12-31 |
| CN104349670A (en) | 2015-02-11 |
| JP2013249262A (en) | 2013-12-12 |
| SG11201407844SA (en) | 2014-12-30 |
| TWI574620B (en) | 2017-03-21 |
| MY167067A (en) | 2018-08-09 |
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