Note: Descriptions are shown in the official language in which they were submitted.
1100099
This invention relatestoamethod of fumigating
the interior of rooms and other confined spaces for
controlling vermin and for fungicidal and incensing purposes,
and an apparatus therefor, and more particularly to fumi-
gating method and apparatus which are capable of concent-
rically producing such effects within a short period of
time e.g.a few minutes or ten-odd minutes. The present
method and apparatus are especially useful for controlling
noxious insects, such as mosquitoes, flies and ~ockroaches,
which are detrimental to man and also other insects, such
as plant lice, green house whiteflies and caterpillers,
which are harmful to agricultural plants.
As a method of controlling noxious insects,
fumigation is known in which compositions of an active
chemical and a combustible material are used, such that
the combustible material, when burned, gives off heat and
smoke,the heat causing the active ingredient to concentrically
vaporize within a short time and the smoke assisting the
volatilization of the ingredient. In order to quickly
volatilize a great amount of active ingredient, the combus-
tible materials useful for fumigating compositions are those
capable of evolving a large quantity of smoke. The large
quantity of smoke emitted by such combustible material
generally has a pungent odor and high toxicity is harmful
to the human body and might possibly be mistaken for a fire.
Q9~
Soot and the like contained in the smoke tend to soil
household furniture and walls in rooms. The combustible
material involves a fire hazard. Fumigators must therefore
be handled with care. The known fumigators further have
the serious drawback that the heat of combustion of the
combustible material decomposes part of the active ingredient
and results in a loss of the active ingredient, consequently
affording a lower volatilization efficiency,namely lower
effective fugacity rate and reduced efficacy. Measurements
in the above method using various insecticides lead to
effective fugacity rates lower than.10~. Thus the fumigators
heretofore known are not usable with safety and convenience
and are unsatisfactory in effectiveness.
An object of this invention is to provide a
fumigating method which can be practiced with high safety
substantially free of attendant smoke and without involving
combustion and an apparatus therefor.
Another object of this invention is to provide
a fumigating method and an apparatus therefor capable of
effectively quickly giving off the vapor of an active
ingredient without entailing a loss of the active ingredient
due to the thermal decomposition ther of.
Still another object of this invention is to
provide a fumigating method and an apparatus therefor
capable of giving off the vapor of an active ingredient
uniformly throughout a confined space within a short period
of time to produce greatly improved insect-controlling effects.
1100099
These and other objects of this invention will
become apparent from the following description.
This invention provides a fumigating method
comprising heating a mixture of an active ingredient and
a blowing agent indirectly with a heating element to ther-
mally decompose the blowing agent without entailing combus-
tion and to volatilize the active ingredient.
Further this invention provides a fumigating
apparatus for practicing the method of this invention com-
prising a container which has at least one compartment
accomodating a mixture of an active ingredient and a
blowing agent and at least one further compartment provided
ad~acent to said compartment and accommodating a heating
element, the interior of the container being divided with
a partition into said compartments, the partition providing
a surface for transferring the heat evolved from said heating
element to the mixture.
Throughout the specification and claims, the
term "indirect heating" refers to heating of a mixture of
an active ingredient and a blowing agent with the heat given
off from a heating element through a heat transfer surface
or a partition provided in a container.
We have found that when a mixture of an active
ingredient and a blowing agent is heated with a heating
element indirectly to thermally decompose the blowing
agent to a gas, the active ingredient can be vol~tilized
with a greatly improved efficiency substantially free o
thermal decomposition.
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ilOOQ99
According to the fumigating method of this
invention, a large quantity of the vapor of an active
ingredient can be emitted and diffuse~i through a confined
space without involving combustion or producing smoke which
would have a pungent odor and toxicity and without involving
any loss of the active ingredient due to the thermal decom-
position.
The active ingredient useful in this invention
are various and include those heretofore used for insecticidal,
fugicidal and incensing purposes. Typical of useful examples
are as follows.
1. Insecticide
(1) 3-allyl-2-methylcyclopenta-2~ene-4-one-1-yl dl-cis/
trans-chrysanthemate(available under the trademark
"Pynamin", product of SUMITOMO CHEMICAL CO.,LTD.,Japan,
hereinafter referred to as "allethrin A");
(2) 3-allyl-2-methylcyclopenta-2-ene-4-one-1-yl d-cis/
trans-chrysanthemate (available under the trademark
"Pynamin-forte", product of SUMITOMO CHEMICAL CO.,LTD.,
Japan, hereinafter referred to as "allethrin B");
(3) d-3-allyl-2-methylcyclopenta-2-ene-4-one-1 yl d-trans-
chrysanthemate(available under the trademark "Exlin",
product of SUMITOMO CHEMICAL CO.,LTD.,Japan);
(4) 3-allyl-2-methylcyclopenta-2-ene-4-one-1-yl d-trans-
chrysanthemate ;
(5) N-(3,4,5,6-tetrahydrophtha]imide)-methyl dl-cis/trans-
chrysanthemate(available under the trademark "Neo-
pynamin", product of SUMITOMO CHEMICAL CO.,LTD.,Japan,
hereinafter referred to as "phthalthrin");
- 1100099
(6) 5-benzyl-3-rurylmethyl d-cis~trans-chrysanthemate
(available under the trademark "Chrysron-forte", product
of SUMITOMO CHEMICAL CO., LTD.,Japan, hereinafter
referred to as "resmethrin") ;
(7) 5-propargyl-3-furylmethyl chrysanthemate ;
(8) 3-phenoxybenzyl-2,2-dimethyl-3-(2', 2'-dichloro)
vinylcyclopropane-carboxylate (available under the
trademark "Eksmin", product of SUMITOMO CHEMICAL CO.,
LTD.,Japan, hereinafter referred to as "permethrin");
(9) 3-phenoxybenzyl d-cis/trans-chrysanthemate (available
under the tradem~rk "Sumithrin", product of SUMITOMO
CHEMICAL CO., LTD., Japan, hereinafter referred to as
"phenothrin");
(10) 0,0-dimethyl 0-~2,2-dichloro) vinylphosphate (hereinafter
referred to as "DDVP") ;
(11) o-isopropoxyphenyl methylcarbamate ;
(12) 0,0-dimethyl 0-(3-methyl-4-nitrophenyl)phosphorothioate;
(13) 0,0-diethyl 0-2-isopropyl-4-methyl-pyrimidyl-(6)-thio-
phosphate ;
(14) 0,0-dimethyl S-(1,2-dicarboethoxyethyl)-dithiopho~;phate;
Among those insecticides,allethrin ~allethrin B,
phthalthrin, resmethrin, permethrin, phenothrin and
DDVP are most preferable.
2. Industrial fungicide
(1) 2,4,4'-tr~chloro-2'-hydroxydiphenyl ether (hereinafter
referred to as "IF-l");
(2) 2,3,5,6-tetrachloro-4-(methylsulfonyl)-pyridine
(hereinafter referred to as "IF-2") ;
1100099
(3) alkylbenzyl dimethylammonium chloride (to be referred
to as "IF-3") ;
(4) benzyldimethyl ~2-[2-(p-1,1,3,3-tetramethyl-butylphenoxy)
ethoxy] ethyl} ammonium chloride (to be referred to as
"IF-4") ;
(5) N,N-dimethyl-N-phenyl-N'-(fluorodichloro methylthio)
sulfonamide (hereinafter referred to as "IF-5") ;
(6) 2-(4'-thiazolyl3benzimidazole (hereinafter referred to
as"IF-6") ;
0 (7) N-(fluorodichloromethylthio)-phthalimide (hereinafter
referred to as "IF-7") ;
(8) 6-acetoxy-2,4-dimethyl-m-dioxine (hereinafter referred
to as "IF-8");
(9) salicylic acid ;
(10) formalin ;
(11) 4-isopropyltropolone ;
(12) p-chloro-m-xylenol ;
(13) zinc bis (2-pyridinethiol-1-oxide);
(14) sodium-2-pyridinethiol-1-oxide ;
(15) diiodo methyl-p-tolyl-sulfone ;
(16) p-chlorophenyl-diiodomethyl sulfone ;
(17) 2,4-hexadienoic acid ;
(18) N-trichloromethylthio-4-cyclohexene-1,2-di.carboximide;
~19) 2,4,5,6-tetrachloro-isophthalonitrile ;
(20) butyl-p-hydroxybenzoate;
-- 6 --
llOl~lQ99
(21) 3-trifluoromethyl-4,4'-dichlorocarbanilide ;
(22) 2,2'-methylenebis[3,4,6-trichlorophenol];
(23) 2-hydroxyethyl-disulfide ;
(24) ~-phenoxyethylalcohol ;
(25) 1,3-benzenediol ;
(26) 1-dodecyl-2-methyl-3-benzyl-imidazolium chloride ;
(27) alkyl-diaminoethylene glucine HCQ ;
(28) polymeric biguanide HCQ ;
(29) polyoctyl polyamino ethylglycine ;
(30) hexahydro-1,3,5-tris-(2-hydroxyethyl)-S-triazine ;
(31) polyhexamethylene b;guanide HCQ ;
(32) poly [oxyethylene (dimethylimino) ethylene dichloride];
(33)alkylbetaine type S.A.A.;
(34) bis-(p-chlorophenyldiguanide)-hexanegluconate ;
(35) S-bromo-S-nitro-1,3-dioxane ;
(36) A mixture of 1,2-benzoisothiazoline-3-one, quartenary
ammonium salt and propylene glycol ;
(37) allcyldi-(aminoethyl)glycine;
(38) alkylisoquinolinium bromide ;
(39) 3,4,4'-trichlorocarbanilide ;
(40) decamethylene-bis-(4-aminoquinaldinium chloride);
(41) sodiurn dehydroxyacetate ;
(42) 1-oxy-3-methyl-4-isopropylbenzene ;
(43) 2~bromo-2-nitropropane-1,3-diol ;
~O~Q99
(44) sodium p-toluenesulfon chloramide;
(45) l-hexadecylpyridinium chloride ;
(46) hexadecyltrimethylammonium brom~:1e ;
Among those industrial fungicides, IF-l to
IF-8 are preferable.
3. Antiseptic
(1) ~ -bromo-cinnamaldehyde ;
(2) N,N-dimethyl-N-phenyl-N'-(fluorodichloromethylthio)-
sulfamide ;
4. Agricultural fungicide
(1) A mixture of bis (dimethylthiocarbamoyl) disulfide, zinc
dimethyldithiocarbamate and methylarsenic dimethyldithio-
carbamate ;
(2) S-benzyl diisopropyl phosphorothioate
(3) 0-ethyl diphenyl phosphorodithioate ;
(4) diethyl 4,4'-o-phenylenebis (3-thioallophanate);
(5) dimethyl 4,4'-o-phenylenebis (3-thioallophanate);
(6) N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide;
(7) N-(1,1,2,2-tetrachloroethylthio)-4-cyclohexene-1,2-di-
carboximide ;
(8) S,S-6-methylquinoxaline-2,3-diyldithiocarbonate ;
(9) pentachloronitrobenzene;
(10) methyl 1-(butylcarbamoyl)-2-benzimidazol carbamate;
(11) 2,4-dichloro-6-(o-chloroanilino)-1,3,5-triazine;
llOOQ99
(12) 2,3-dicyano-1,4-dithia-1,4-dihydroanthraquinone:
(13) 3-hydroxy-5-methylisoxazole ;
(14) streptomycin ;
(15) polyoxin :
(16) blasticidin S :
(17) kasugamycin :
(18) validamycin ;
(19) 4,5,6,7-tetrachlorophthalide ;
(20) N-(dichlorofluoromethylth~o)-N',N'-dimethyl-N-phenyl-
sulfamide:
(21) tetrachloroisophthalonitrile :
(22) 2,4-dichloro-6-(o-chloroanilino)-1,3,5-triazine :
(23) ethyl p,p'-dichlorobenzylate :
(24) zinc ethylenebis (dithiocarbamate);
(25) manganese ethylenebis(dithiocarbamate);
(26) complex of zinc and manganese ethylenebis(dithiocarba-
mate);
(27) dizinc bis(dimethyldithiocarbamate)ethylene
bis(dlthiocarbamate);
(28) bis(dimethyl-thiocarbamoyl)disulfide:
(29) isomeric reaction mixture of 2,6-dinitro-4-octyl-
phenyl crotonate;
Among the above fungicides,those numbered
(21)-(29) are preferable.
5. Plant growth regulant
(1) 4-chlorophenoxy acetic acid;
_ 9 ~
llOOQ99
(2) gibberellin ;
(3) N-(dimethylamino) succinamide;
(4) ~ -naphthylacetamide;
6. Herbicide
(1) 2,4-D sodium salt;
(2) 3,4-dichloropropionanilide;
7. Repellent
(1) 2,3,4,5-bis ( 2 -butylene)-tetrahydrofulfural;
(2) di-n-butyl-succinate;
Among the above active ingredients, insecticides
are more suited for use in the apparatus of this invention.
These active ingredients can be used con~ointly with any
of synergists, fugacity rate improving agents, deodorants,
perfumes, etc. which are usually used. Preferable examples
of the synergists are piperonyl butoxide, N-propyl isome,
"MGK-264" (product of MCLAUGHLIN GORMLEY KING CO.,U.S.A.,
"Cynepirin-222" (product of YOSHITOMI PHARMACEUTICAL INDUST-
RIES LTD., Japan), "Cynepirin-500" (product of YOSHITOMI
PHARMACEUTICAL INDUSTRIES LTD., Japan), "Lethane 384"
2Q (product of ROHM AND HAAS COMPANY, U.S.A.), "IBTA" (product
of NIPPON FINE CHEMICAL CO.,LTD, Japan), "S-421" (product
of SANYO CHEMICAL INDUSTRIES, LTD.,Japan). Preferable
fugacity rate improving agents includ~ phenethylisothio-
cyanate, dimethylester of himic acid, etc. Preferred deo-
dorants are lauryl methacrylate (LMA), etc. Citral and
citronellal are preferably usable as perfumes.
_ 10 --
llO~Q99
The blowing agent to be used conjointly with the
: active ingredient and, when desired, with various additives
can be any of those generally used and capable of mainly
evolving nitrogen gas on thermal decomposition. It is
preferable to use compounds which will give off a gas at
(~ O
a temperature of between about 7U C and about 300 C. The
compounds having blowing temperatures far lower than 70 C
tend to decompose by themselves during storage The compounds
with blowing temperatures much higher than 300 C are likely
not to decompose when subjected to heat evolved from
the heating element. Accordingly such compounds are
s~
'~ not preferable. Examples of typical blowing agents are
listed in Table 1 below.
:
. .
1100~99
Table 1
No. Blowin~ a~ent Abbreviation Blowing temp.(~)
1. azodicarbonamide AC 200 - 210
2. benzenesulfonylhydrazide BSH 100 - 160
3. p-toluensulfonylhydrazide TSH 110
4. p,p'-oxybis(benzensulfonyl- OSH 140 - 160
hydrazide)
5. dinitrosopentamethylene- DPT19C - 205
tetramine
6. N,N'- dinitro~o-N,N'-di- DDTP90 -- 105
methylterephtalamide
7. trihydrazinotriazine THT235 - 290
8. azo~isisobutyronitrile AIBN95 - 105
9. 4,4'-azobiscyano~aleric ACVA 120
acid
10. t-butylazoformamide BAFA147 - 149
11. 2,4-bis-(azosulfonyl) 2,4-TSH108 - 109
toluene
12. 2,2'-azobisisobutylo- AZ-A 92
amide
13. methy~2,2'-azobisiso- AZ-~ 85
butyrate
14. 2-(carbamoylazo)iso- CIB 105
butyronitrile
15. l,l'-azobiscyclohexane ACHC 115
-1- carbonitrile
110~
Among the blowing agents listed in Table 1, AC,
OSH, DPT, AIBN and ACHC are preferable because they con-
tribute to the increase in fugacity rate of an active in-
gredient. AC in particular remarkably enhances the fugacity
rate thereof~Produces a gas free of toxicity and pungent odor,
and is therefore especially useful.
A blowing agent may be used with additives to reduce
the blowing temperature. Preferable examples of the addltives
are as followæ: "~yhos"(product of NATIONAL LEAD CO., LTD.,
U.S.A.), "Tribase"(product of NATIONAL LEAD CO., LTD.,U.S.A.),
"~F-14"(product of ADECA ARGUS CO., LTD., U.S.A.), "OF-15"
(product of ADECA ARGUS CO., LTD., U.S.A.), "KV-68A-l"(product
of KYODO YAKUHIN CO., LTD., Japan), "Mark-553"(product of
ARGUS CHEMI. CO., LTD., U.S.A.), "Sicostab 60"(product of
G. Siegle & Cv., U.S.A.), "Sicostab 61"(product of G.Siegle
& Co., U.S.A.), Cd-stearate, Ca-stearate, Zn-stearate, Zn-
octate, ZnO, Sn-maleate, ZnC03, urea, chrome yellow, carbon
black, etc.
According to this invention, the amount of the
blowing agent relative to the active ingredient can be
determined suitably depending on the use of the resulting
composition. Usually it is preferable to use at least about
one part by weight of the blowing agent per part by weight ~f
the active ingredient The effective fugacity rate progressive-
ly increases with increasing proportion of the blowing agent,
~lOQ~99
but the use of too great an amount of the blowing agent
will not produce significantly improved results. Prefer-
ably about one to about 20 parts by weight of the blowing
agent is used per part by weight of the active ingredient.
The active ingredient and the blowing agent are merely mixed
together to prepare a fumigating mixture of this invention
but, to ensure efficient production and ease of use, it is
desirable to prepare the mixture in the form of powder
granules, pellets, otherwise shaped pieces, paste or the like
or to enclose the mixture in a bag of meltable and incom-
bustible resin. The mixture may also be enclosed in an
openable bag made of aluminum.
According to this invention, the mixture of an
active ingredient and a blowing agent is heated indirectly
with a heating element to thermally decompose the blowing
agent without burning the mixture. In this invention, any
of heating elements is useful ~nsofar as it is capable
of indirectly heating the mixture to such a temperature
at which the blowing agen~ can be decomposed toa gas
without burning the mixture. Preferred heating elements
are i) an exothermic substance capable of evolving heat
by contact with water, ii) that capable of evolving heat
by CQntact wi'h air and iii) means capable of evolving
heat by application of an electric current.
Examples of typical exothermic substances using
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1100~99
water are calcium oxide, magnesium chloride, alumin~m
chlorlde, calcium chloride and ferric chloride, among
which calcium oxide is most preferable since this compound
gives off heat enough to elevate the temperature up to about
400~C without producing any harmful substances due to hydro-
lysis thereof and the corrosion of a container accommodating
this compound. For the most efficient heat generation, it
is desirable that calcium oxide be in the form of about
1- to about 20-mesh pieces or grains. Preferably the reac-
tion between calcium oxide and water is initiated not immedi-
ately after the addition of the latter to the former but
after the water added thereto has uniformly and satisfactori-
ly permeated into the calcium oxide.
To retard the initiation of the exothermic reac-
tion when calcium oxide comes into contact with water, the
pieces or grains of calcium oxide can be coated with at
least one of mineral oils, vegetable oils and fats, higher
alcohols, polyhydric alcohols, higher fatty acids and deriv-
atives thereof. The amount of water to be used is prefer-
ably about 0.2 to about 3 times the stoichiometric amount,
and is, for example, about 0.2 to about 3 moles per mole of
calcium oxide. When blowing agents which will evolve a gas
at lower temperatures are used, diatomaceous earth, acid clay,
zeolite or like clay can be added to the exothermic substance
so as to regulate the heating time and temperature to be given
by the heat evolved from the substance.
- 15 -
Q99
Examples of exothermic substances using air
are compounds which evolve heat on oxidation with the
oxygen contained in air. More specific examples include
a mixture of sodium sulfide and iron carbide and/or
carbon black. Among them, a mixture of the above three
substances is preferable. Preferably the mixture con-
tains 40 to 60% by weight of sodium sulfide.
Examples of useful heating elements using an
electric current are heating wires such as usual nichrome
wires, heating carbon elements such as those produced by
MATSUSHITA ELECTRIC INDUSTRIAL C0., LTD., Japan, semicon-
ductors such as positive temperature coefficient thermistors,
etc.
According to this invention, the mixture of an
active ingredient and a blowing agent is indirectly heated
by the heating element, preferably any of the above heating
element~ iii). To heat the mixture indirectly, the
mixture is contained in a suitable container, and the heat-
ing element is disposed outside the container. Preferably
the mixture and the heating element are accommodated in a
container as separated from each other by a partition pro-
viding a heat transfer surface. The container is made of
heat resistant material such as an iron plate. The mixture
and the heating element can be contained in the container in
any desired arrangement within the container. The arrange-
ments can be divided into three general types:
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110~099
(i) Arrangement in which the mixture is positioned above
the heating element with a substantially horizontal
partition interposed therebetween.
(ii) Arrangement in which the mixture and the heating
element are separated from each other by a substan-
tially vertical partition.
(iii) Arrangement in which the mixture and the heating
element are separated from each other substantially
horizontally and vertically.
In the arrangements (ii) and (iii), it i8 prefer-
able to arrange the two components concentrically when seen
in a plan view, with either one of the two positioned out-
side the other. In the case of concentric arrangement, the
mixture may be accommodated in a plurality of separate com-
partments. Several kinds of mixtures having varying effica-
cies can be accommodated in the compartment6 respectivelyO
The mixture accommodating compartment has an open
upper end which may be kept sealed until the apparatus i8
put into use. When a material such as polyethylene, poly-
propylene, polyamide or the like which is meltable but is
not burned with the heat evolved from the heating element
is used for sealing the compartment, there is no need to
remove the seal by hand when using theapparatus, nor any
likehood of hand coming into contact with the mixture,
hence convenient and safe.
llOOQ99
The meltable seal can be covered with another film
or sheet for reinforcing the seal. The covering film or
sheet has a number of perforatlons and may be made from metal
such as iron, aluminum or alloy thereof,synthetic resin or paper.
The heating element is a~commodated in a compart-
ment provided ad~acent to the compartment containing the
mixture of active ingredient and blowing agent. The com-
partment for accommodating the heating element may be option-
ally closed or opened, but is usually closed to eliminate
heat losses. Preferably the container has an outer wall of
heat in~ulated construction to minimize the heat loss and
assure safety in handling.
When using the exothermic substance a~ the heating
element, the clo~ed compartment is provided with means for
supplying water to the exothermic substance. For instance,
the water supplying mean~ i~ in the form of at least one
water inlet aperture formed in an upper portion and/or
lower portion of the closed compartment or comprises a
water reservoir which can be opened from outside.
2~ The water reservoir is made from a film of easily
breakable material such as an aluminum foil or synthetic
re~in filmO
Examples of means for opening the water reservoir
from outside, although not particularly limited, are pre-
ferably as follows:
110~99
(i) A thread attached to the water reservoir and adapted
to be pulled from outside to break the portion of the
reservoir where the thread is attached.
(ii) A needle adapted to puncture the water reservoir
when pushed into the container from outside.
(iii) ~ cutter provided within the container and dis-
placeable from outside to cut the water reservoir.
(iv) One of the means (i) to (iii) which is so arranged
as to cause the exothermic substance to contact paJt
~f the water contained in the reservoir, permitting
the resulting heat to melt and break the meltable film
which forms the water reservoir. The sealing materlals
exemplified above are usable for the meltable film.'
When the means (ii) or (iii) is u~ed, the closed
compartment ls provided with suitable means for restraining
~he needle or cutter from inadvertent displacement.
Preferably water can be applied to the exothermic
substance in such a manner that water placed in the bottom of
the container i6 introduced through water inlet apertures in
a lower part of the container into a water permeable layer
provided ln the closed compartment from which the water
comes into contact with the exothermic substance. The water-
permeable layer, when employed, allows water to be applied
to the exothermic substance uniformly over an increased area
for efficient heat generation. The seeping rate of the water
-- 19 --
l~OQQ99
through the layer is suitably adjustable by varying the
density, material and thickness of the layer. When such a
water-permea~e layer forms the bottom wall of the closed
compartment, water can be supplied to the exothermic sub-
stance without the necessity of forming water inlet aper-
tures in the bottom wall. Alternatively a water-permeable
layer impregnated with water and sealed with a meltable
film may ~e provided within the closed compartment, prefer-
ably in combination with one of the opening means (i) to
(iii) as already stated.
The water-permeable layer has numerous minute
spaces as in open-cellular foamed materials and mats of
fibrous material. The layer can be made from any water-
permeable material. Examples of useful materials are
woven an~ nonwoven fabrics of polyethylene, polypropylene,
polyvinylidene chloride or like synthetic fibers, or of
a blend of such synthetic fiber~ and cotton, mats of glass
wool, asbestos, rock wool or like inorganic fibers, filter
paper or like paper made of pulp, etc.
The exothermic substance filling the clo~ed
compartment expands on application of water and also raises
the internal temperature of the compartment owing to the re-
sulting heat generation, so that the internal pressure of
the container will build up to a very high level. According-
2~ ly an opening for maintaining the internal pressure in balance
with the atmospheric pressure can be formed in the wall defi-
ning the closed compartment~
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11~99
Electric heating elements, when used, are pro-
vided preferably in ~uch manner that the heat evolving
portion of the element will be in direct contact with part
or whole of the partition providing a heat transfer surface,
namely of the container wall accommodating the mixture, or
will fit to the wall with a heat releasing plate interposed
between that portion and the wall. The electric heating
element has the advantage of giving a suitable amount of
heat with ease at any time desired merely by being connected
to an appropriate power æupply. Accordingly the electric
heating element ls u~able repeatedly for fumigation in
combination with a replaceable cartridge which contains
the mixture to be thereby heated and which may be service-
able also as the container for the mixture.
When heating elements which evolve heat on con-
tact with air are used, the element is usable in the form
of particles to grains, a sheet or plate or in some other
suitable form as contained in an apprnpriate portion of the
apparatu~. The heating element mu6t be held out of con-
tact with air, namely in a hermetic state or in an inert
gas atmosphere, before the use of the apparatus and must
further be maintained in contact with air during use.
This can be done easily by encloslng the heating element
in a bag of material, such as an aluminum foil, which is
impervious to air but readily openable, or by accommodating
99
the heating element in an open compartment of the apparatuS
and sealing the opening as with an aluminum film. In the
latter case, it is preferable to place the heating element
into the compartment in a nitrogen gas or like inert gas
atmosphere. The heating element thus enclosed can be ex-
posed to air by opening the bag or the seal covering the
opening of the compartment.
When the heating element evolves heat, the heat
indirectly heats the mixture containing the active ingre -
dient through the partition, thereby decomposing the blow-
ing agent and vigorously volatilizing the active ingre-
dient. According to this invention, the active ingredient
can be very eff~ctively volatilized in a large quantity
within a short period of time, e.g. a few minutes or ten-
odd minutes, presumably because the blowing agent mixed
with the active ingredient gives off a gas on decomposi-
tion, forcing the active ingredient to volatilize prompt-
ly from the interior of the mixture and because the active
agent per se remainæ free of decomposition due to combus-
tion. The method of this invention, which is capable of
very efficientiy quickly releasing large quantities of
vapors of active ingredients, is useful in controlling
noxious insects, ~uch as flies, mosquitoes, fleas, bed
bugs, house ticks and cockroaches, which are detrimental
to man, as well as plant lice, green house whiteflies,
caterpillars and other insects which are harmful to
- 22 -
110~9~
agricultural plants, and is also servlceable for fungi-
cidal and incensing purposes. Additionally ~he present
method is usable for these applications with high safety
and great convenience æubstantially without involving
combusition which would produce smoke with toxicity or
a pungent odor.
110~99
This invention will be described below in greater
detail with reference to apparatus suitable for practicing
the present method ~d shown in the accompanying drawings,
in which:
Figs. 1-45 each show preferred embodiments of
the present apparatus utilizing as the heating element an
exothermic substance which evolves heat on contact with
water;
Fig. 1 is a view in vertical section showing an
, 10 embodiment ol` the invention in which the bottom wall of
a container is formed with water inlet apertures;
Fig. 2 is a bottom view showing the water inlet
apertures of the container shown in Fig. l;
Figs.3 and 4, Figs. 5 and 5A, Figs. 6 and 7,
Figs.8 and 9, Figs. 10 and 11, and Figs. 12 and 12A are
plan views and vertical sections respectively taken on
lines III - ~Is V - V, Vl - VI, VIII - VIII, X - X, and
XII - XII which show embodiments of this invention compris-
ing a container having the same water supplying means as
in the embodiment of Figs. 1 and 2;
Figs. 13 and 14, and Figs. 15 and 16 are plan
views and vertical sections respectively taken on lines
XIII - XI~ and XV - XV which show embodiments of this
invention comprising a container with at least one water
inlet aperture formed in its upper portion;
- 24 -
Q99
Fig. 17 and Fig. 18 are vertical sections show-
ing modifications of the embodiment illustrated in Figs.
15 and 16;
Figs. 19 and 20, Figs~ 21 and 22, and Figs. 23
and 24 are plan views and vertical sections taken on lines
XIX - XIX, XXI - XXI and XXIII - XXIII which show embodi-
ments of this invention comprising a container having its
top portion a water inlet aperture provided with a water
inlet tube;
Fig. 25, Fig. 26, Fig. 27 and Fig. 28 are views
in vertical section each showing an embodiment of this
invention in which a container incorporates a water
reservoir;
Fig. 29, Fig. 30, Fig. 31, Pig. 32, Fig. 33
and Fig. 34 are views in vertical section each showing an
embodiment of this invention in which water is supplied
to an exothermic substance through a water-permeable layer;
Fig~, 35 and 36 are a plan view and a view in
vertical section taken on lines XXXV - XXXV which show an
embodiment of this invention in which a container is provided
with means for attaching the apparatus to a wall;
Fig. 37 is a view in vertical section showing
an embodiment of this invention in which a compartment
accommodating a mixture of active ingredient and blowing
agent is sealed with a meltable film;
- 25 -
1~0~99
Figs.38 and 39 are a view in vertical section
and a plan view showing a preferred case for enclosing
the apparatus of this invention;
Fig. 40 is a view in vertical section showing
another preferred case for enclosing the apparatus of
this invention;
Fig. 41 is a plan view in develop~ent showing
the case;
Fig. 42 is a view in vertical section showing
the case during use;
Fig. 43, Fig. 44 and Fig. 45 are views in
vertical section each showing an embodiment of this
invention provided with means for supplying a specified
amount of water;
Fig. 46, Fig. 47 and Fig. 48 are views in vertical
section respectively showing preferred embodiments of the
apparatus of this invention utilizing an electric heating
element; and
Fig. 49, Fig. 50, Fig. 51 and Fig. 52 show embodi-
ments each incorporating a heating element which evolves
heat on contact with air.
Figs.1 and 2, Figs. 3 and 4, Figs. 5 and 5A,
F'igs. 6 and 7, Figs. 8 and 9, Figs. 10 and 11, and Figs.
12 and 12A respectively show embodiments of this inverltio
each comprising a container 1 with water inlet apertllres 5
- 26 -
Q99
formed in its bottom wall la. The heating element is
formed of an exothermic substance which evolves heat on
contact with water.
The container 1 of Figs. 1 and 2 accommodates
a mixture B of an active ingredient and a blowing agent
in its upper open compartment 2 and an exothermic substance
C in its lower closed compartment 3 separated from the
mixture B by a partition 4. In Figs. 3 and 4 and Figs.
5 and 5A, the mixture B and the substance C contained in
the container 1 are separated from each other by a vertical
partition. The mixture B and the exothermic substance C
shown in Figs. 6 and 7, and Figs. ~ and 9 are accommodated
in the container 1 as vertically and horizontally separated
from each other, with the mixture B placed at an upper
position of the substance C.
In Figs. 10 and 11, and Figs. 12 and 12A, the
mixture B is accommodated in the open compartment 2 of
the container 1 as divided into a plurality of small
portions, in which case the portions need not always be
of the same kind, but several kinds of mixtures B of vary-
ing compositions and efficacies may be contained separately.
When the bottom of the container 1 is placed in
water a in use of the apparatus shown in Figs. 1-12A, the
water enters the closed compartment 3 through the water
inlet apertures 5 in the bottom wall la of the closed
- 27 -
llO~Q99
; compartment 3 of the container 1 and comes into contact
with the exothermic substance C contained in the closed
compartment 3, causing the substance to evolve heat.
The heat indirectly heats the mixture B in the open
compartment 2 of the container 1 through the partition
4, thereby decomposing the blowing agent in the mixture
B and vigorously volatilizing the active in~redient.
On absorbtion of water, the exothermic substance
C expands and gives off heat, increasing the internal
pressure of the closed compartment 3 and impeding smooth
ingress of the water through the inlet apertures 5.
Uneven heat generation will then result. It is therefore
desirable that the container 1 be formed~ in its side wall
lb or top wall lc, with a balance opening 6 for maintain-
ing the interior of the closed compartment 3 in communi-
cation with the atmosphere.
As seen in Figs. 1 and 4, the bottom wall la
of the container 1 is preferably detachable for use with
a refill of the exothermic substance.
Fig. 9 shows water inlet apertures 5 formed in
the bottom wall la and lower portion of the side wall l_
of the container 1.
Figs. 13 and 14, and Figs. 15 and 16 respectively
show other embodiments of this invention each comprising
a container 1 with at least one water inlet aperture 5
- 28 -
11~0~99
formed in the upper portion of its enclosed compartment 3.
These embodiments need not be provided with the
above-mentioned balance opening, since the water inlet
aperture 5 is serviceable also as such.
As shown in Figs. 14 and 16, preferably a water
receptacle 7 is provided in the upper portion of the
containerand the water inlet aperture 5 is formed in the
bottom of the water receptacle 7.
Figs. 17 and 18 show modifications of the embodi-
ment illustrated in Fig. 15. The modifications of Figs.
17 and 18 are substantiallythe same as the embodiment of
Fig. 15 except that the partition of Fig. 17 has a curved
lower part, while that of Fig. 18 has inclined side parts.
Figs. 19 and 20, Figs. 21 and 22, and Figs. 23
and 24 respectively show other embodiments cr this inven-
tion each comprising a container 1 having in its top
portion a water inlet aperture 5 provided with a water
inlet tube 8.
The water inlet tube ~ extends almost to the
bottom of the container 1 to supply water to a bottom
portion of an exothermic substance C filling a closed com-
partment 3 of the container 1. This arrangement enables
the exothermic substance C to start heat generation at
the bottom portion. For example, when water is supplied
according to the embodiment of Figs. 13 and 14 to the
- 29 -
llO~Q99
exothermic substance C through the water inlet aperture
5 in the upper part of the container 1, heat generation
is initiated at the upper part of the exothermic substance
C, and the water thus heated is partly vaporized, thereby
involving a loss of water. Consequently the lower part
of the éxothermic substance mi~ht possibly remain with-
out evolving heat. The use of the water inlet tube 8
prevents such undesirable loss of water, thus ensuring
complete consumption of the substance for heat generation
without any waste.
Figs. 25 to 28 respectively show other embodi-
ments of this invention in each of which a water reservoir
9 is incorporated in a closed compartment 3 of a container
1. The water reservoir 9 contains a sufficient amount of
water required for the heat generation of an exothermic
substance C.
The embodiments of Figs. 25 and 26 have a thread
10 which can be pulled from outside to break the water
reservoir 9 when so desired, and those of Figs. 27 and
28 have a needle 11 for puncturing the water reservoir
9 a~d a pin 12 for retaining the needle 11 in posltion.
The pin 12 is removably inserted in the hole ~not shown)
of the needle 11. When the pin 12 is removed, the need~e
11 is freely movable upward or downward.
Fig. 26 shows a balance opening 6 formed in
- 30 -
110~99
an upper end peripheral curled portion of the container 1.
Figs. 29 to 34 respectively show other embodi-
ments of this invention which are so adapted that water
is supplied to an exothermic substance C through a water-
permeable layer 13.
With the embodiments of Figs. 29 to 31, the
water supplied through water inlet apertures 5 seeps
through the water-permeable layer 13 and comes into con-
tact with the exothermic substance C to cause the substance
C to evolve heat. Since the water seeps through the
layer 13 over the entire surface area thereof, this
arrangement assures very efficient heat generation.
When the water inlet apertures 5 are formed in
the bottom wall la or lower portion of the side wall lb
f the container 1 as shown in Figs. 29 and 31, the water-
permeable layer 13 separates the exothermic substance C
from the water inlet apertures 5, preventing the substance
C from falling through the apertures 5, so that the water
inlet apertures 5 can be of relatively large diameter.
Figs. 32 to 34 show embodiments of the type in
which water is supplied from a water reservoir 9 to a
water-permeable layer 13. With the embodiment of Fig. 32,
the main body of a container-l is depressed, with retain-
ing pins 12 removed, to break the water reservoir 9 for
the application of water to the layer 13. With the embodi-
- 31 -
.~,
1104~Q99
ments of Figs.33 and 34, a thread 10 is pulled to break
the reservoir 9.
Figs. 35 and 36 show another embodiment of
this invention including a container 1 which is mountable
on a vertical wall, column, ceiling and others. The
container 1 has a lug 15 pro~ecting from its upper end
periphery and having a hole 14. A hook (not shown) on a
wall, column, ceiling or the like is engageable in the
hole 14 to support the container.
Fig. 37 shows another embodiment of this inven-
tion in which a compartment accommodating a mixture B
has an open end which is sealed with a meltable film 16.
The film 16 is removable by being melted with the heat
evolved from an exothermic substance C and the heat of
the gas released from an active ingredient with that heat.
The apparatus of this type is convenient to use since the
seal over the mixture accommodating compartment need not
be separated before use.
Figs. 38 and 39, and Figs. 40 to 42 respectively
show preferred cases for enclosing an apparatus A accord-
ing to this invention of the type in which water inlet
apertures 5 are formed in the bottom wall la of a container
1. When opened, the case 17 (23) is usable as a container
for water.
With reference to Figs. 38 and 39~ a cover 1
~10~99
is detachable from the case 17. The cover 18 is detached
from the case when water is introduced into the case.
The cover 18 is refixed to the case 17 after the supply
of water. The cover 18 has an opening 19 serving as a
passage for the vapor given off from the mixture B in
the open compartment 2.
The case 17 and the apparatus A enclosed therein
define an annular space 20 which serves as a heat insulat-
ing portion for protecting the case 17 from the heat
evolved from the exothermic substance C.
The case 17 has projections 22 of small width
provided on its bottom and extending radially from the
center thereof. The proJections 22 support the apparatus
A thereon and form spaces 21 beneath the apparatus A,
the spaces 21 serving to accommodate the water to be
supplied to the apparatus A through the water inlet
apertures 5 in the bottom of the apparatus. The pro-
jections 22 each have an upwardly outwardly sloping top
face 22a, rendering the apparatus accurately positionable
within the case 17 concentrically therewith.
The case 23 shown in Figs. 40 to 42 is of the
same construction as the case 17 except that the case 23
comprises an outer case member 23a of the knockdown type
and a plastics inner case member 23b disposed within the
outer case member 23a concentrically therewith.
ll~gg
Fig. 41 is a development showing the outer
case member 23a. The top cover portion thereof comprises
cover pieces 25, 25 extending from the upper ends of the
opposite side walls 23a', 23a' of the outer case member
23a with folds 24, 24 formed therebetween. One of the
cover pieces 25 further extends outward intoan attaching
piece 27 with a perforated fold 26 formed at the outer
end of the cover piece.
When the present apparatus is to be used, the
cover pieces 25, 25 are unfolded to a semi-open position
as shown in Fig. 42. In this state, openings 28, 28 are
formed on the opposite sides of the cover pieces 25, 25.
The vapor released from the apparatus is diffused into the
outside atmosphere through the openings 28, 28. To ensure
more efficient diffusion, one of the cover pieces 25 can
be formed with holes 29 (see Fig. 41). To retain the
cover pieces 25 in a semi-open position, one of the
opposed ends of the cover pieces has a tongue-like insert
piece 30 and the other end a cutout 31 for receiving the
insert piece 30.
As seen in Fig. 40, the inner case member 23b
has a seal 32 closing its open upper end. The seal 32
is removed when the apparat~s is put to use.
Fig. 43, Fig. 44 and Fig. 45 are views in
vertical section each showing an embodiment of this inven-
- 34 -
ll~OQ99 '
tion provided with means for supplying a specified amount
of water.
With reference to Fig. 43, a container 1 is
provided on one side thereof with a water receptacle 33.
An overflow opening 34 is formed in the outer wall 33a
of the receptacle 33 at a suitable level. The lower
end of the receptacle 33 communicates with a slit 35
provided beneath the bottom of the container 1. The
bottom of the container 1 has water inlet aperture 5
opened to the slit 35. The portion where the lower end
of the water receptacle 33 communicates with the slit
35 is provided with a seal 36 which is opened after water
has been placed into the receptacle 33. When made of
water-soluble material, the seal 36 is openable without
being opened by hand.
When the level of the water placed into the
receptacle rises beyond the overflow opening 34, excess
water ~lows out from the opening 34, with the result that
a predetermined amount of the water remains in the receptacle
33. The seal 36 is thereafter removed, permitting the
water to enter the slit 35 from the lower end of the
receptacle 33 and to flow into the container 1 via the
water inlet apertures 5 opened to the slit 35.
When a water-permeable layer 13 of suitably
selected material is provided on the bottom of a container
1100Q99
1 as seen in Fig. 44, the layer 13 also has substantially
the same function as the seal 36 shown in Fig. 43, thus
ellminating the necessity of providing a seal between the
water receptacle 33 and the slit 35.
Fig. 45 shows a container 1 having in its top
portion a water receptacle 7 the side wall of which is
formed with an overflow opening 34 for ensuring the
supply of a specified amount of water. The receptacle
7 has a water inlet aperture 5 which is closed with a
seal 37. The seal 37 is removed after the specified
amount Or water has been placed into the receptacle 7.
Throughout Fig. 1 to Fig. 45, like numerals
indicate like members. A supply of water to the exothermic
substance in the closed compartment according to the
embodiments of Figs. 13 to 45 achieves substantially
the same results as with the embodiments of Flgs. 1 to 12A.
Figs. 46 to 48 show apparatus each uti]izing an
electric heating element. With the apparatus of Fig. 46,
a mixture of an active ingredient and a blowing agent
and the heating element are separated from each other
vertically and horizontally, whereas Figs. 47 and 48 each
show an apparatus in which the mixture is positioned above
and separated from the heating elemrnt. The heating
elements used in these apparatus are a heating wire
(Fig. 46), a heating carbon element (Fig. 47) and a
- 36 -
llOQO99
thermistor of positive temperature coefficient (Fig. 48).
Each of these heating elements 101 evolves heat upon
application of an electric current by being connected to
a suitable power supply outside the apparatus. This
connection is effected for example via a terminal 103
provided-within a compartment 102 of the container
accommodating the heating element 101 and a cord 104
extending outward from the wall of the compartment 102
as seen in Fig. 46, or by way of a plug 105 fixed to the
wall of the compartment 102 as seen in Fig. 48. In view
of safety, the heating element 101 can be surrounded by
an insulating plate 106. A heat releasing plate 107 can
be interposed between another compartment 108 of the con-
tainer accommodating the mixture of active ingredient and
blowing agent, i.e. mixture B as seen in Fig. 47 and the
heating el~ment 101 to achieve an improved thermal effi-
ciency. With the apparatus of Fig. 46 and Fig. 47, the
compartment 108 containing the mixture B is fitted in
the upper portion of the compartment 102 accommodating the
heating element 101 and serving as the main body, in
whlch case the mixture B is replaceable as desired along
with the compartment 108. The main body of the apparatus
is therefore advant~geous in that it is usable repeatedly
for the same purpose or for different applications. The
apparatus of Fig. 48 includes a compartment 108 accommodat-
llOOQ9g
lng the mixture B and secured to the upper portion of
the compartment 102 containing the heating element 101,
in which case the walls Or compartment 108 areserviceable also
as a heat releasing plate. This apparatus is repeatedly
usable by replacing the mixture B only. The compartment
108 for ~he mixture B may have an open upper end, but
the opening is preferably kept sealed until the apparatus
is put into use, for example, with a meltable film 111
as seen in Fig. 47. The seal is convenient in that it
is spontaneously removable with the heat emitted from
the heating element 101. It is desirable that the outer
wall of each of the foregoing apparatus, especially the
outer wall of the compartment containing the heating
element 101, be of heat insulated construction.
Figs. 49 to 52 show embodiments each incorpo-
rating a heating element which evolves heat on contact
with air. The heating element 101 shown in Fig. 49 is
in the form of a molded sheet and accommodated in a
compartment 102. A container forming a compartment 108
containing the mixture B is fitted ln the upper portion
of the compartment 102 in intimate contact therewith.
The heating element 101 shown in Fig. 50 is in the form
of grains and placed in a hollow cylindrical compartment
102 which is formed in a compartment 108. The outer com-
partment 108 concentric with the inner compartment 102
- 38 -
llOQQ99
contains the mixture B. With the apparatus of Fig. 51
comprising a hollow cylindrical container of the double
wall structure, the heating element 101 is shaped in the
form of a hollow cylinder and conversely fits around an
inner compartment 108 containing the mixture B. With
the apparatus shown in Fig. 52, the heating element 101
is intimately fitted over the side and bottom walls of
a compartment 108 containing the mixture B and is thereby
separated from the mixture B.
With the apparatus of Fig. 49 to 52, the com-
partment 102 containing the heating element 101 is
sealed with a film 109 which is impervious to air and
easily openable. When the heating element 101 is dis-
posed in a lower portion or in lower and side portions
f the apparatus as sho~n in Fig. 49 or Fig. 52, the
bottom of the compartment 102 containing the heatlng
element 101 is formed with air apertures 110, and the
bottom is covered with the film 109 from outside. In
the case of concentric arrangement as shown in Figs.
50 and 51, the upper end of the compartment 102 is sealed
with the film 109. The heating element 101 evolves heat
when the seal portion is opened to expose the element
101 to air, thus indirectly heating the mixture B con-
tained in the compartment 108 through the partition
providing a heat transfer surface, namely the bottom or
- 39 -
~lOQ~gg
side wall of the compartment. The apparatus utilizing
the heating elements which evolve heat on contact with
air are all very simple in construction and easy to use
and require no power supply.
Throughout Fig. 46 to Fig.52, like numerals
indicate like members.
This invention will be described below in
greater detail with reference to examples, in which the
effective fugacity rates of active ingredients are
determined by volatilizing the ingredient within a
closed container, passing the air within the container
through a solvent which completely disolves the active
ingredients, such as benzene, acetone, water, chloroform
or dichloromethane to cause the solvent to absorb the
vaporized ingredient in the air, concentrating the solvent
and sub~ecting the concentrate to gas chromatography.
The fugacity rate is expressed in terms of the ratio in
percent of the quantity of the active ingredient to the
quantity of the ingredient initially admixed with a blow-
ing agent.
- 4~ -
llOOQ99 '
Example 1
A mixture of an insecticide and a blowing agent
as listed in Table 2 is placed into an apparatus of this
invention utilizing 100g of calcium oxide (l-to 5-mesh
pieces) and shown in Fig. 29. The apparatus is brought to
contact with water and 40 g of water enters into a com-
partment accommodating calcium oxide via inlet apertures in
its bottom wall to heat the mixture to a temperature of
up to about 300 to about 350C with the resulting heat,
whereby the blowing agent ls thermally decomposed to
volatilize the insecticide. The effective fugacity rate
of the insecticide is determined.
The results are shown in Tables 2.
Table 2
effective
Specimen blowing fugacity
No. insecticide (g) a~ent (g) rate(%)
1 allethrin B 1 AIBN 5 69.4
2. DDVP 1 TSH 10 61.1
3. " 1 2,4-TSH 10 63.o
4. " 1 OSH 10 74.2
5. allethrin A 1 AZ-A 10 69.1
1 AZ-B 10 65.6
7. '! 1 CIB 10 61.6
8. " 1 ACHC 10 63.2
9 allethrin B 1 AC 1 65.3
10. " 1 AC 3 74.9
11. " 1 AC 5 86.7
12. allethrin A 1 AZ-B 10 63.0
13. DDVP 1 OSH 10 70.1
- 41 -
llOOQ99
effective
Specimen blowing used fugacity
No. insecticide used(g) agent (g) rate(%)
14 allethrin A 1 CIB 10 60.5
allethrin B 1 AC 1 60.8
16 l~ 1 AC 3 72.9
17 resmethrin 1 AC 5 83.4
i 18 ~ 0.5 AC 2 75.0
i 19 " 0.5 AC 4 84.0
; 20 " 0'5 AC 5 82.3
1 21 0 5 AC 10 79.8
j 22 " 0.5 DPT 1.5 80.8
23 phthalthrin 0.5 AC 5 63.0
24 phenothrin 0.5 AC 5 75.5
permethrin 0.5 AC 5 78.1
26 DDVP 0.5 AC 4 78.2
27 resmethrin1 / AC 65.2
AZ-B
28 allethrin B 1 AC 68.1
! ( AIBN
Comparative Example 1
The same procedure as in Example 1 is repeated
without using any blowing agent. Table 3 shows the results.
Table 3 effective
Specimen blowing fugacity
No. insecticide (g) agent ~g) rate (%)
29 resmethrin 1 - - 0.3
allethrin B 1 - - 0.7
Comparative Example 2
To a cylindrical container with a single compart-
ment accomodating 100 g of calcium oxide con~ointly with an
insecticide only or with an
- 42 -
~lOQQ99
insecticide and a blowing agent listed in Table 4 is
supplied 40 g of water in the same manner as in Example 1
to determine the effective fugacity rate achieved. Table 4
shows the results.
Table 4
effective
Specimen blowing fugacity
_ No. insecticide (g) agent (g) rate (%)
31 resmethrin 1 0.2
32 allethrin B 1 0.3
33 resmethrin 1 AC 5 4.2
34 allethrin B 1 AC 5 5.1
Comparative Example 3
The mixtures listed in Table 5 each composed of
an insecticide and a comsubtible material as in known
fumigants, were burned for fumigation. Table 5 also shows
15 the effective fugacity rates achieved.
Table 5
effective
Specimen combustible fugacity
_ No. insecticide (g) material (g) rate (%)
resmethrin 0.5 nitrocellulose 3 6.3
(30%)
36 allethrin B 0.5 " 3 1.7
37 phthalthrin 0.5 " 3 7.2
38 phenothrin 0.5 " 30 8.1
39 permethrin 0.5 " 30 8.6
Tables 2 to 5 show that the method of this inven-
tion using present apparatus can achieve remarkably improved
effective fugacity rate.
- 43 -
110~99
Example 2
The same procedure as used in Example 1 is repeated
with the exception that a blowing agent containing an
additive is used as shown in Table 6.
The results are als~ given in Table 6.
_able 6
effective
Specimen blowing fugacit~ rate
No. insecticlde (g) agent (g) (~0)
resmethrin 1 CELLMIC 5 86.8
CAP*
41 ' 0.5 CE*L*LMIC 5 87.5
* "CELLMlC CAP" is an AC-type blowing agent
manufactured by SANKYO KASEI CO.,LTD.,Japan
** "CELLMIC AN" is a blowing agent manufactured by
the same company and containing a mixture of
50% DPT and 50% urea as an additive.
Table 6 reveals that the use of the additive with
the blowing agent achieves the results as excellent as
those shown in Table 2.
Example 3
The same procedure as used in Example 1 is repea-
ted except that to the active ingredient is added a syner-
gist (for Specimens No. 42 to No. 46), a deodorant or
perfume (for Specimens Nos. 47 and 48) or a fugacity rate
improving agent (for Specimens Nos. 49 and 50) as shown in
- 44 -
llO~Q99
Table 7, which also shows the results.
Table 7
effective
Specimen blowing fugacity
No. insecticide (g) additive (g) agent (g) rate(%)
42 resmethrin 1 S-421 2 AC 3 79.4
43 " 1 ~iperonyl 3 l 5 85.8
butoxide
44 " 1 Lethane 384 3 " 5 85.5
" 1 Cynepirine- 3 " 5 87.7
222
46 " 1 Cynepirine- 3 " 5 86.2
500
47 " 0.5 citral 0.1 " 2 82.4
48 ' 0.5 LMA 0.1 " 1 78.1
49 ~ 0.5 ph~nethYl- 1 CELLMIC 5 90.3
isothiocya- AN
nate
5o ~' 0.5 dimethyl
ester of 1 CELLMIC 5 89.6
himic acid AN
Table 7 shows that the use of the additiVe with
the active ingredient achieves the results as excellent as
those shown in Table 2.
Example 4
The same procedure as used in Example 1 is repea-
ted except that a heat generation regulating agent listed
in Table 8 is added to the calcium oxide. Table 8 also shows
the results.
- 45 -
~lOOQ99
Table 8
heat
generation effective
Specimen blowing regulating fugacity
No. insecticide (g) agent (g) agent (g) rate (%)
-
51 resmethrin 1 AC 5 zeolite 5 87.4
52 " 1 " 5 acid clay 10 88.5
53 " 1 " 5 diatoma- 10 88.2
ceous earth
Apparatus of the invention are tested for the
quantity of smoke evolved, toxicity and insecticidal effect.
Quantity of smoke (turbidity)
An apparatus of this invention accommodating the
same mixture as Specimen No. 20 is used in a chamber 90 cm x
90 cm x 90 cm to volatilize the active ingredient. For com-
parison, a fumigating compositions composed of 30g of a
combustible material and 1.5 g of DDVP is burned in the same
chamber as above.
The chamber is transparrent in the upper part and
is lit up with a fluorescent light (20w) provided in the
upper center of the chamber. A marking plate is horizontally
disposed in vertically movable manner in the chamber. The
marking plate is a white disc made of plastic with a diameter
of 35 mm. On the disc are drawn four black lines 0.5mm in
width such that two pairs of lines are intersected at a right
angle in the center of the disc, two lines of each pair being
spaced in parallel with a distance of l.Omm. The above disc
- 46 -
.~
110~99
ls vertically moved to measure a distance (h) between the
top of the chamber and the disc when the four lines on the
disc ar~ clearly seen with unaided eyes. In this way, a
turbidity within the chamber is calcul~ted by the followlng
equation:
turbidity (%) = h (cm) ~ 100
90(cm)
The same procedure is repeated five times for each specimen,
glving the following average data shown in Table 9.
Table 9
distance(cm) turbidity(%)
present invention: 67 74.4
Comparison : 16 17.8
The results indicate that the ~uantity of smoke
emitted from the apparatus of this invention is substantially
negligible.
Toxici~ (determined by exposure to fumigatlng vapor)
A toxicity test is conducted under the following
conditions.
(1) Apparatus
A: Apparatus accommodating specimen No. 18 Or this invention.
B: Apparatus accommodating specimen No.20 of this invention.
(2) Device
Chambers, lm x lm x lm (i.e. lm3).
(3) Animals
Five-week-old mice JCL: ICR
(4) Method
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Five male mice or five female mice are placed
lnto a chamber, the interior of the chamber is
fumigated with one or two apparatus and the
animals are left confined in the chamber for 2 hours.
The animals are thereafter placed into an ordinary
cage and given a diet and water.
(5) Results
Tables 10 and 11 show the results.
Table 10
Test. number of deaths
No. Apparatus immediately one day ~ two days
after the after the after the
fumigation fumigation fumigation
M. F. M. F. M. F.
1 A (one) 0 0 0 0 0 0
2 B (one` 0 0 0 0 0 0
3 B ( two) 0 0 0 0 0 0
Specimens No.18 and No.20 used in the toxicity test
produce no toxicity, and the test animals are alive 10 days
after the fumigation. As shown in Table 10, high safety
is ensured when using the present apparatus in a chamber
having a concentration of the volatilized active ingredi-
ent over 30 times the concentration thereof at which a
satisfactory insecticidal effect is achieved.
Table 11 shows the changes in the body weight of
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the animals surviving the test.
Table 11
Test animal's changes in the body weight of the animals
No. sex (average ~)
before 1 day 2 days 4 days 6 days 8 days lOday
test after after after after after after
1 M. 26.2 27.3 26.2 29.6 29.4 29.6 31.4
F. 22.2 22.4 21.6 23.0 23.4 22.4 23.2
2 M. 24.8 26.2 25.6 28.4 27.0 28.4 29.8
F. 22.4 22.6 21.8 24.0 23.8 24.4 24.6
3 M. 25.4 28.4 28.2 31.0 31.4 31.8 34.0
F. 22.0 22.0 21.4 22.8 23.4 23.6 24.4
Table 11 reveals that the specimens of the invention
show substantially no harmful effect on the increasing rate
of body weight of the tested an~mals and that they are sub-
stantial]y free from toxicity. The amounts of food taken
by the animals is slightly reduced only on the first day
after the test but thereafter no change is observed.
Insecticidal effect
1. Specimens of this invention are tested for insecticidal
effect under the following conditions.
(1) Test insects
Adults of german cockroaches.
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(2) Method
A laboratory dish (24 cm in inside diameter and
6.5 cm in height) containing 25 test insects is placed
in each corner of a closed room, 3 m x 4 m x 3 m
(height), i.e. 36 m3, and the interior of the r~om
is fumigated with a specimen placed in the center of
the room. Knockdown is determined at a specified time
interval after the initiation of fumigation. Two
hours after the fumigation, the test insects are
transferred to a rearing chamber, and mortality (%)
is determined in 24 hours and 48 hours. In the rearing
chamber, the insects are given a diet and water. Table
12 shows the results.
Table 12
~ecimens No. I 11 24 25 20
¦ 30 min. 55 51 46 53
Knockdown 1 60 min. 99 96 84 100
(%)90 min. 100 98 95 100
' 120 min. 100 100 100100
24 hr. 78 66 97 80
Mortality I
(%) , 48 hr. 100 100 100100
Table 12 shows that the use of the present apparatus
in a closed room leads to effective extermination of
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099
noxious vermin.
2. Specimens of this invention are further tested for
insecticidal effect in a simulated living room.
(1) Test insects
Adults of german cockroaches and adults of american
cockroaches.
(2) Method
A 76-cm-high desk having four drawers in layers
is placed in one corner of a room, 3m in width, 4 m
in length and 3 m in height, i.e. 36 m3. A wood ~ox
(45 cm x 41 cm x 37 cm) is placed in another corner
of the room as spaced apart by 2 cm from the wall, with
its opening opposed to the wall. A closed box
(measuring 30 cm x 30 cm x 30 cm and having 8 holes
of 7 mm in diameter in its top side) is placed on a
150-cm-high shelf in the center of one of the longi-
tudinal walls of the room, the box being positioned
close to the wall.
Laboratory dishes (24 cm in inside diameter and
6.5 cm in height) each containing 20 adults of german
cockroaches and 10 adults of american cockroaches are
placed in various locations within the room. The
interior of the room is fumigated with a specimen
placed in the center of the room, and the insects
are left conf1ned in the room for one hour. The
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insects are thereafter placed into a rearing case and
given a diet and water. Mortality (%) is determined
24 hours and 48 hours after the start of the experiment.
The dishes are placed in the following locations:
Pl: In the open box.
P2: In the closed box.
P3: In the uppermost closed drawer of the desk.
P4: In the second highest drawer of the desk as
withdrawn by 1 cm.
P5: In the lowermost drawer of the desk as withdrawn
by 2 cm.
(3) Specimens
Specimen No. 20.
(4) Results
Table 13 shows the results achieved with the german
cockroaches, and Table 14 those with american cock-
roaches.
Table 13
Place
Pl P2 P3 P4 P5
Mortality(%) 24 hr. 50 35 50 40 35
48 hr. 100 95 100 100 100
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Table 14
Place
Pl P2 P3 P4 P5
Mortality(%)24 hr. 10 20 3 10 20
48 hr. 90 60 100 80 100
~5 Tables 13 and 14 show that the apparatus of this
invention is very effective at various locations.
Example 5
The procedure of Example 1 is repeated using
the same apparatus as used therein, the apparatus containing
a fungicide and a blowing agent listed in Table 15, which
also shows the results.
Table 15
Specimen fungicide blowing effective
No. (g) agent (g) fugacity rate(%)
54 IF-2 0.5 AIBN 5 60.1
" 0.5 AC 5 71.3
56 ~ 0.5 AZ-A 10 66-7
57 IF-8 0.5 AZ-B 10 6~.8
58 ~ 0.5 AIBN 5 68.4
59 " 0.5 ACHC 5 57.~
IF-7 0.5 AZ-B 5 57.9
61 " 0.5 AC 5 70.8
62 " 0.5 CIB 5 54.0
63 IF-6 0.5 DPT 1.5 6~.ll
64 IF-3 0.5 AZ-A 3 88.8
IF-2 0.5 AIBN 10 71.3
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Specimen fugicide blowing effective
No. (g) agent(g) fugacity rate(%)
66 IF-l0.5 AIBN 5 71.5
67 IF-40.5 AIBN 5 54.0
68 IF-31 ( AZ-A 2 56.4
AZ-B 2
Comparative Example 4
The procedure of Example 5 is repeated using an
fungicide listed ln Table 16 but without using any blowing
agent. Table 16 also shows the results.
Table 16
Specimen fungicide effective
No. (g) fugacitY rate (%)
69 IF-5 l 6.5
IF-8 l 8.9
71 IF-7 1 18
72 IF-2 1 10.8
Tables 15 and 16 reveal that the use of a
blowing agent con~ointly with a fungicîde ena~les the
fungicide to volatilize with an efficiency which is lO-odd
times as high as the efficiency achieved by the same quantity
of the fungicide at the same temperature.
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099
Example 6
A mixture of an insecticide and a blowing agent
as listed in Table 17 is placed into an apparatus of this
invention utilizing a heating wire and shown in Fig. 46.
An electric current is applied to the wire to indirectly
heat the mixture to a temperature of up to 300 C with the
resulting heat, whereby the blowing agent is thermally
decomposed to volatilize the insecticide. The effective
fugacity rate of the insecticide is determined.
The same procedure as above is repeated except
that a mixture of an insecticide, an additive and a blowing
agent listed in Table 18 is used.
The results are shown in Tables 17 and 18.
Table 17 effective
Specimen blowing fugacity
No. insecticide (g) agent (g) rate (%)
54 allethrin B 1 AIBN 5 75.6
DDVP 1 TSH 10 66.5
56 " 1 2,4-TSH 10 68.6
57 " 1 OSH 10 74.6
58 allethrin A 1 AZ-A 10 63.4
59 " 1 AZ-B 10 60.2
6Q " 1 CIB 10 67.1
61 " 1 ACHC 10 68.7
62 allethrin B 1 AC 1 60.0
63 " 1 AC 3 69.3
64 " 1 AC 5 ~0.2
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effective
Specimen blowing fugacity
No. insecticide (g) agent (g) rate (%)
allethrin B 1 AC 10 79.0
66 vesmethrin 1 AC 1 62.0
67 ~ 1 AC 3 74.1
68 1 AC 5 76.5
69 " 0.5 AC 2 68.8
" 0.5 AC 4 77.0
71 " 0.5 AC 5 75.5
72 " 0.5 AC 10 73.2
73 " 0.5 DPT 1.5 77.3
74 phthalthrin 1 AC 5 60.2
phenothrin 0.5 " 5 69.2
76 " 1 " 5 71.6
77 permethrin 0.5 " 5 71.6
7~3 " 1 " 5 69.4
79 DDVP 0.5 " 5 79 3
Table 17 showsthat the process of this invention
results in remarkably improved effective fagacity rate.
Table 18
effect.ve
Specimen insectici.d~ additive blowing fu~acity
No. (g) (g) agent (g) rate(%) _
resmethrin 1 S-421 2 AC 3 72.
81 " ]. ~piperonyl 3 " 5 78.7
82 " 1 Lethane 3 " 5 78.4
384
83 " 1 Cynepirine3 " 5 ~0 L~
222
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effective
Specimen insecticide additive blowing fugacity
No. (g) (g) agent (g) rate(%)
84resmethrin 1 ~Cynepirine 3 AC 5 79.0
r 5
" 0.5 citral 0.1 " 2 75.5
86 " 0.5 L~A 0.1 ~' 1 70.0
87 " 0.5 phenethyl- l C~LLMIC 5 82.8
isothiocya- AN
nate
88 " 0.5 dimethyl 1 ' 5 82.2
ester
of himic
acid
The specimen No. 71 is tested for the quantity
of smoke evolved (turbidity), toxity and insecticidal effect
described above. The results of the above tests are sub-
stantially the same as those of the tests using the specimen
No. 20. More specifically stated, the results of the tests
with the use of the specimen No. 71 show:
i) substantially no smoke is emitted from
the specimen;
ii) no toxicity is produced; and
iii) noxious vermin are effectively exterminated.
Comparative Example 5
The same procedure as in Example 6 is repeated
without using any blowing agent. Table l9 shows the results.
llOOQ99
Table 19
Specimen insecticide (g) effective fugacity
No. rate (%)
89 resmethrin 1 0.6
allethrin B 1 2.9
91 phenothrin 1 1.3
92 permethrin 1 0.9
Comparative Example 6
The mixtures listed in Table 20 each composed
of an insecticide and a combustible material as in known
fumigants, were burned for fumigation. Table 20 also shows
the effective fug~city rates achieved.
Table 20
effective
Specimen insecticide (g) combustible (g) fugacity
No material rate (%)
93 resmethrin 0.5 nitr(oce%)lulose 30 6.3
94 allethrin B 0.5 - 3 1.7
phthalthrin 0.5 " 3 7.2
96 phenothrin 0.5 " 30 8.1
97 permethrin 0.5 " 30 8.6
Tables17 to 20 show that the rnethod of this inven-
tion using the present apparatus results in remarkably
improved effective fugacity rate.
~xample 7
A mixture of an insecticide and a blowing agent
as listed in Table 21 ls placed into the inner compartment
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~lOOQ99
108 of an apparatus of this invention as shown in Fig. 49.
A heating element (20g) in the form of a mixture of 4 parts
by weight of sodium sulfide and 6 parts by weight of iron
carbide is broughtinto contact with air by removing the
seal 109 to heat the compartment to about 300 C with the
resulting heat from outside, whereby the blowing agent is
thermally decomposed to volatilize the insecticide. The
effective fugacity rate achieved by the insecticide is
determined. Table 21 shows the results.
Table 21
effective
Specimen insecticide (g) blowing agent (g) fugacity rate
No. (%)
98 allethrin B 1 AIBN 5 69.3
99 DD~P 1 TSH 10 60.5
100 DDVP 1 2,ll-TSH 10 61.8
101 allethrin B 1 AC 3 73-5
102 allethrin A 1 AZ-A 10 63.5
103 " 1 AZ-B 10 61.0
104 allethrin B 1 AC 5 80.5
105 allethrin A 1 ACHC 10 66.0
106 resmethrin 1 AZ-~ 10 60.3
107 " 1 AC 3 70.2
103 " 1 AC 5 75.6
109 l~ 0.5 DPT 1.5 78.6
110 phthalthrin 0.5 AZ-A 10 60.4
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Example 8
A mixture of a fungicide and a blowing agent
as listed in Table 22 is placed into the hollow cylindrical
compartment 108 of an apparatus as shown in Fig. 46. The
compartment is externally heated with the heating wire 101
S to a temperature of up to 300 C to thermally decompose the
blowing agent and to thereby volatilize the ~nglcide. The
effective fugacity rate achieved by the fungicide is
determined. Table 22 also shows the results.
Table 22
effective
Specimen fungicide (g) blowing agent (g) fugacity
No. _ rate (%)
111 IF-2 0.5 AIBN 5 61.4
112 " 0.5 AC 5 71 3
113 " 0-5 AZ-A 10 60.7
114 IF-8 0.5 AZ-B 10 61.3
115 " 0.5 AIBN 5 57.8
116 " 0.5 ACHC 5 62.3
117 IF-7 0.5 AZ-B 5 61.0
118 " 0.5 AC 5 65.0
119 " 0.5 CIB 5 56.9
120 IF-6 0.5 DPT 1.5 72.1
121 IF-3 0.5 AZ-A 3 81.5
122 IF-2 0.5 AIBN 10 71-3
123 IF-l 0.5 " 5 75.3
124 IF-4 0.5 " 5 55.4
125 IF-7 1 ~ AZ-A 57.9
lAZ-B 2
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Comparative Example 7
The procedure of Example 8 ls repeated using a
fungicide listed in Table 23 but without using any
blowing agent. Table 23 also shows the results.
Table 23
Specimen fungicide (g) effective
No. fugacity rate (%)
126 IF-5 1 7-
127 IF-8 1 9.0
128 IF-7 1 2.0
129 IF-2 1 11.0
Tables 22 and 23 reveal.. that the use of a blowing
agent cor,~ointly with a fungicide enables the fungicide
to volatilize with an efficiency which is ten-odd times
to several tens of times as high as the efficiency achieved
by the same quantity of the fungicide when it is heated
alone at the same temperature.
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