Insecticidal resin coating film

An insecticidal resin coating film comprising a combination of an acrylonitrile and/or methacrylonitrile copolymer resin and an insecticidal component selected from the group consisting of specified compounds exhibits an insecticidal effect, since the compound is kept on the surface of the coating film in a state capable of exhibiting its insecticidal effect for a long period of time.

BACKGROUND OF THE INVENTION 
1. Field of the Invention: 
The present invention relates to an insecticidal resin coating film which 
is formed mainly on a substrate so as to continuously and effectively kill 
and exterminate insects such as cockroaches, flies and termites which 
crawl thereon. 
2. Prior Art: 
Compositions comprising an insecticidal component and a high molecular 
resin used heretofore can be classified into those in the form of an 
emulsion to be sprayed on the soil to kill insects therein (Japanese 
Patent Laid-Open No. 58-93738) and those in the form of a sheet or coating 
film to be used for killing insects in institutions and houses. 
The products comprising latter composition include, for example, a paper or 
fibrous material coated or impregnated with an insecticidal component or 
insect repellent (Japanese Patent Publication No. 3761/1986), a mixture of 
latex and an insectproofing agent (Japanese Patent Laid-Open No. 
60-238376) and a high molecular resin containing an insecticidal component 
(GB No. 2142239 A). However, they are yet insufficient in the application 
range, insecticidal effect, effect-lasting time and safety. Under these 
conditions, an improvement of them has been demanded. 
SUMMARY OF THE INVENTION 
An object of the present invention is to provide an insecticidal resin 
coating film having a strong, long lasting insecticidal effect, high 
safety and wide application range. 
The inventors have found that the above-mentioned problems can be solved by 
a coating film comprising a specified resin component containing a 
specified insecticidal component which film is capable of keeping the 
effective insecticidal component on the surface of the coating film over a 
long period of time. The present invention has been completed on the basis 
of this finding. 
The present invention provides an insecticidal resin coating film 
characterized by comprising 100 parts dry base by weight of a copolymer of 
acrylonitrile and/or methacrylonitrile and another monomer and 0.1 to 10 
parts dry base by weight of an insecticidal component of any of the 
following general formulae (I) to (XII): 
##STR1## 
wherein R.sub.1, R.sub.2 and R.sub.3 each represent a hydrogen or halogen 
atom or a lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy or 
methylenedioxy group, R.sub.4 represents a lower alkyl group, R.sub.5 
represents a hydrogen atom or a methyl or ethyl group, or R.sub.4 and 
R.sub.5 may form a cycloalkyl group having 3 to 6 carbon atoms together 
with carbon atom bonded with them, the cycloalkyl group being 
unsubstituted or substituted with a halogen atom or a methyl group, 
R.sub.6 represents a hydrogen or halogen atom, R.sub.7 represents a 
hydrogen or halogen atom or a lower alkyl or lower alkoxy group and X 
represents an oxygen or sulfur atom or a methylene group; 
##STR2## 
wherein R.sub.8, R.sub.9 and R.sub.10 each represent a hydrogen or halogen 
atom or a lower alkyl group, R.sub.11 represents a hydrogen atom or a 
cyano or ethynyl group and R.sub.6 and R.sub.7 are as defined above; 
##STR3## 
wherein R.sub.12, R.sub.13, R.sub.14 and R.sub.15 each represent a 
hydrogen or halogen atom or a lower alkyl or lower alkenyl group, and 
R.sub.6 and R.sub.7 are as defined above; 
ester-type pyrethroid compounds of the general formula: 
##STR4## 
wherein R.sub.6, R.sub.7, R.sub.11, R.sub.12, R.sub.13 and R.sub.14 are as 
defined above and R.sub.16 represents a hydrogen or halogen atom or a 
lower alkyl, lower alkenyl or halogen-substituted lower alkenyl group; 
ester-type pyrethroid compounds of the general formula: 
##STR5## 
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.6, R.sub.7 and R.sub.11 are as 
defined above, R.sub.17 represents a lower alkyl group, R.sub.30 
represents a hydrogen atom or R.sub.17 and R.sub.30 form an unsubstituted 
or substituted cycloalkyl group together with the carbon atom bonded with 
them, and Y represents an oxygen atom, --NH-- group or methylene group; 
ester-type pyrethroid compounds of the general formula: 
##STR6## 
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.7, R.sub.11 and R.sub.17 are as 
defined above, R.sub.18 represents a hydrogen or halogen atom or a lower 
alkyl or lower alkoxy group and W represents an oxygen atom or a methylene 
group; 
##STR7## 
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6, R.sub.7 and R.sub.11 
are as defined above; 
pentafluorobenzyl 
2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate: 
##STR8## 
3'-phenylbenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate: 
##STR9## 
2'-methyl-3'-phenylbenzyl 
3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate: 
##STR10## 
6-phenoxypyridyl-.alpha.-cyanomethyl 
2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate: 
##STR11## 
6-phenoxypyridyl-.alpha.-cyanomethyl 
2,2-dimethyl-3-(4-tertbutylphenyl)cyclopropanecarboxylate: 
##STR12## 
DETAILED DESCRIPTION OF THE INVENTION 
A resin prepared by copolymerizing (meth)acrylonitrile with another monomer 
is used as the resin component in the present invention, since the 
inventors have found that when such a resin is used together with a 
specified insecticidal component, a coating film capable of exhibiting the 
remarkable effect of the insecticidal component can be formed. When a 
given insecticidal component in a given amount is incorporated in various 
resins and coating films are formed from the resins, coating films 
prepared from some resins exhibit no insecticidal effect and those 
prepared from some other resins exhibit only an extremely weak 
insecticidal effect. On the contrary, when the resin of the present 
invention is used, a coating film exhibiting a surprisingly remarkable 
insecticidal effect can be prepared. When the special combination of the 
resin and the insecticidal compound is employed, the compound migrates 
onto the coating film surface to effectively exhibit its effect over a 
long period of time. 
Examples of the monomers other than (meth)acrylonitrile usable as the 
comonomer in the present invention include acrylic esters such as methyl, 
ethyl, isopropyl, n-butyl, isobutyl, n-amyl, isoamyl, n-hexyl, 
2-ethylhexyl, n-octyl, decyl and dodecyl acrylates; methacrylic esters 
such as methyl, ethyl, propyl, n-butyl, isobutyl, n-amyl, isoamyl, 
n-hexyl, n-octyl, 2-ethylhexyl, decyl and dodcecyl methacrylates; styrene 
monomers such as styrene, vinyltoluene, m2-methylstyrene, t-butylstyrene 
and chlorostyrene; hydroxyl group-containing monomers such as hydroxyethyl 
acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and 
hydroxyethyl methacrylate; N-substituted (meth)acrylic monomers such as 
N-methylol(meth)acrylamide and N-butoxy(meth)acrylamide; and epoxy 
group-containing monomers such as glycidyl acrylate and glycidyl 
methacrylate. These monomers can be used either singly ro as a combination 
of them. Among them, the methacrylic esters and styrene are preferred. 
The amount of the (meth)acrylonitrile is 5 to 65 wt.%, preferably 15 to 50 
wt.%, based on the copolymer resin and the amount of other monomer(s) is 
95 to 35 wt.%. When the amount of (meth)acrylonitrile is less than 5 wt.%, 
the insecticidal effect is not always sufficient and when it exceeds 65 
wt.%, the coating film cannot be formed easily. 
The copolymer resin of the present invention can be prepared by 
polymerizing a given amount of the above mentioned (meth)acrylonitrile and 
other monomer(s) by a known polymerization method such as emulsion 
polymerization, solution polymerization, suspension polymerization or mass 
polymerization method. 
The molecular weight of the polymer thus prepared is usually 20,000 to 
200,000, preferably 50,000 to 150,000. 
Examples of the insecticidal components of the present invention include 
compounds described below. 
Examples of the insecticidal components of the present invention 
represented by the general formula (I): 
##STR13## 
include the following compounds (Ia) to (Id) and, among them, compounds 
(Ia) to (Ic) exhibit particularly excellent effects: 
(Ia): compounds of the general formula (I) wherein X represents an oxygen 
atom, R.sub.5 represents a methyl group, R.sub.6 represents a hydrogen 
atom and R.sub.7 represents a hydrogen or halogen atom, 
(Ib): compounds of the general formula (I) wherein X represents an oxygen 
or sulfur atom, R.sub.6 represents a halogen atom and R.sub.7 represents a 
hydrogen or halogen atom or a lower alkoxy group, 
(Ic): compounds of the general formula (I) wherein X represents a methylene 
group, and 
(Id): compounds of the general formula (I) wherein R.sub.5 represents a 
hydrogen atom and R.sub.6 and R.sub.7 each represent a hydrogen or halogen 
atom. 
Examples of the above-mentioned compounds include the following ones: 
Compounds (Ia) 
3-phenoxybenzyl 2-(4-methylphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-bromophenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(3-chloro-4-methylphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(3,4-dibromophenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-chlorophenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(4-tert-butylphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-chlorophenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(3-bromo-4-chlorophenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(3,4-dichlorophenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-bromophenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-ethylphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-fluorophenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(3-chloro-4-fluorophenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(4-ethylphenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(3,4-dichlorophenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(4-chloro-3-methylphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-tert-butylphenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(3,4-dimethylphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(3-chloro-4-methylphenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(3-bromo-4-chlorophenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(3,4-dibromophenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(4-chloro-3-methylphenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(4-chlorophenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(3,4-dimethylphenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(4-methylphenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(3-chloro-4-fluorophenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(3,4-difluorophenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(3,4-difluorophenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(3-bromo-4-fluorophenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(3-bromo-4-fluorophenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(3-fluoro-4-bromophenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-methoxyphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-methoxyphenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(4-propoxyphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-propoxyphenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(4-pentyloxyphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(3-chloro-4-ethoxyphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(3-bromo-4-ethoxyphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-difluoromethoxyphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-difluoromethoxyphenyl)-2-ethylpropyl ether, 
3-phenoxybenzyl 2-(4-trifluoromethoxyphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-chlorodifluoromethoxyhenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(4-bromodifluoromethoxyphenyl)-2-methylpropyl ether, 
3-phenoxybenzyl 2-(3,4-methylenedioxyphenyl)-2-methylpropyl ether, and 
3-phenoxybenzyl 2-(4-trifluoromethylphenyl)-2-methylpropyl ether. 
Compounds (Ib) 
3-(4-fluorophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether, 
3-phenoxy-4-fluorobenzyl 2-(phenyl-2-methylpropyl ether, 
3-phenoxy-4-chlorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether, 
3-phenoxy-4-fluorobenzyl 2-(4-methoxyphenyl)-2-methylpropyl ether, 
3-phenoxy-4-fluorobenzyl 2-(3,4-dimethylphenyl)-2-methylpropyl ether, 
3(4-fluorophenoxy)-4-fluorobenzyl 2-(4-methoxyphenyl)-2-methylpropyl ether, 
3-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-2-ethylbutyl ether, 
3-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)butyl ether, 
3-phenoxy-6-chlorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether, 
3-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-3-methylbutyl ether, 
3-(4-fluorophenoxy)-4-fluorobenzyl 2-(3,4-dichlorophenyl)-2-methylbutyl 
ether, 
3-phenoxy-4 -fluorobenzyl 2-(4 -ethoxyphenyl)-2-methylpropyl ether, 
3-(3-chlorophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether, 
3-(3-chlorophenoxy)-4-fluorobenzyl 2-(3,4-dimethyl)-2,3-dimethylbutyl 
ether, 
3-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether, 
3-(2-fluorophenoxy)-4-fluorobenzyl 
2-(3-chloro-4-chlorophenoxy)-2-methylpropyl ether, 
3-(2-fluorophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether, 
3-(4-fluorophenoxy)-4-chlorobenzyl 2-(3,4-dimethoxyphenyl)-2-butylpropyl 
ether, 
3-phenoxy-4-fluorobenzyl 2-(4-methoxy-3,5-dimethylphenyl)-2-methylpropyl 
ether, 
3-phenoxy-4-fluorobenzyl 2-(4-tert-butylphenyl)-2-methylpropyl ether, 
3-(4-methoxyphenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl 
ether, 
3-phenoxy-4-fluorobenzyl 2-(3,4-dichlorophenyl)-2-methylpropyl ether, 
3-(4-bromophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether, 
3-(4-fluorophenoxy)-4-fluorobenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether, 
3-(4-ethoxyphenyl)-4-fluorobenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether, 
3-phenoxy-4-fluorobenzyl 2-(4-difluoromethoxyphenyl)-2-methylpropyl ether, 
3-(4-fluorophenoxy)-4-fluorobenzyl 
2-(4-difluoromethoxyphenyl)-2-methylpropyl ether, 
3-phenoxy-4-fluorobenzyl 2-(4-trifluoromethoxyphenyl)-2-methylpropyl ether, 
3-(4-fluorophenoxy)-4-fluorobenzyl 
2-(4-trifluoromethoxyphenyl)-2-methylpropyl ether, 
3-phenoxy-4-fluorobenzyl 2-(4-chlorodifluoromethoxyphenyl)-2-methylpropyl 
ether, 
3-(4-fluorophenoxy)-4-fluorobenzyl 
2-(4-chlorodifluoromethoxyphenyl)-2-methylpropyl ether, 
3-phenoxy-4-fluorobenzyl 2-(4-bromodifluoromethoxyphenyl)-2-methylpropyl 
ether, 
3-(4-fluorophenoxy)-4-fluorobenzyl 
2-(4-bromodifluoromethoxyphenyl)-2-methylpropyl ether, 
3-phenoxy-4-fluorobenzyl 2-(3,4-methylenedioxyphenyl)-2-methylpropyl ether, 
3-(4-fluorophenoxy)-4-fluorobenzyl 
2-(3,4-methylenedioxyphenyl)-2-methylpropyl ether, 
3-phenoxy-4-fluorobenzyl 2-(4-trifluoromethylphenyl)-2-methylpropyl ether, 
3-(4-fluorophenoxy)-4-fluorobenzyl 
2-(4-trifluoromethylphenyl)-2-methylpropyl ether, 
3-phenoxy-4-fluorobenzyl 2-(4-propoxyphenyl)-2-methylpropyl ether, 
3-(4-fluorophenoxy)-4-fluorobenzyl 2-(4-propoxyphenyl)-2-methylpropyl 
ether, and 
thioethers corresponding to these ethers. 
Compounds (Ic) 
1-(3-phenoxyphenyl)-4-(4-methoxyphenyl)-4-methylpentane, 
1-{3-(4-fluorophenoxy)phenyl}-4-(4-fluorophenyl)-4-methylhexane, 
1-(3-phenoxyphenyl)-4-(4-methoxyphenyl)-4-methylhexane, 
1-{3-(4-fluorophenoxy)phenyl}-4-(4-fluorophenyl)-4-methylpentane, 
1-{3-(4-fluorophenoxy)phenyl}-4-(4-methylphenyl)-4-methylpentane, 
1-{3-(4-bromophenoxy)phenyl}-4-(4-chlorophenyl)-4-methylpentane, 
1-{3-(4-bromophenoxy)phenyl}-4-(4-chlorophenyl)-4-methylhexane, 
1-(3-phenoxyphenyl)-4-phenyl-4-methylpentane, 
1-(3-phenoxyphenyl)-4-phenyl-4-methylhexane, 
1-(3-phenoxyphenyl)-4-(4-chlorophenyl)-4-methylhexane, 
1-{3-(4-fluorophenoxy)phenyl}-4-(4-chlorophenyl)-4-methylpentane, 
1-{3-(4-fluorophenoxy)phenyl}-4-(4-ethoxyphenyl)-4-methylpentane, 
1-{3-(4-fluorophenoxy)phenyl}-4-(4-chlorophenyl)-4-methylhexane, 
1-{3-(4-fluorophenoxy)phenyl}-4-(3,4-dimethylphenyl)-4-methylpentane, 
1-(3-phenoxyphenyl)-4-(3,4-dimethylphenyl)-4-methylpentane, 
1-(3-phenoxyphenyl)-4-(3,4-methylenedioxyphenyl)-4-methylpentane, 
1-{3-(4-methoxyphenoxy)phenyl}-4-(4-ethoxyphenyl)-4-methylpentane, 
1-{3-(3-chlorophenoxy)phenyl}-4-(4-chlorophenyl)-4-methylpentane, 
1-{3-(3-chlorophenoxy)phenyl}-4-(4-chlorophenyl)-4-methylhexane, 
1-{3-fluorophenoxy)phenyl}-4-(4-chlorophenyl)-4-methylpentane, 
1-{3-(3-fluorophenoxy)phenyl}-4-(4-chlorophenyl)-4-methylhexane, 
1-{3-(4-fluorophenoxy)phenyl}-4-(4-difluoromethoxyphenyl)-4-methylpentane, 
1-{3-(4-fluorophenoxy)phenyl}-4-(4-difluoromethoxyphenyl)-4-methylhexane, 
1-{3-(4-methoxyphenoxy)phenyl}-4-phenyl-4-methylpentane, 
1-{3-(4-methoxyphenoxy)phenyl}-4-phenyl-4-methylhexane, 
1-(3-phenoxyphenyl)-4-(4-ethoxyphenyl)-4-methylpentane, 
1-{3-(4-fluorophenoxy)phenyl}-4-(4-ethoxyphenyl)-4-methylpentane, 
1-(3-phenoxy-4-fluorophenyl)-4-(4-ethoxyphenyl)-4-methylpentane, 
1-{3-(4-fluorophenoxy)-4-fluorophenyl}-4-(4-ethoxyphenyl)-4-methylpentane, 
1-{3-(4-ethoxyphenoxy)-4-fluorophenyl}-4-(4-ethoxyphenyl)-4-methylpentane, 
1-(3-phenoxy-4-fluorophenyl)-4-(4-chlorophenyl)-4-methylpentane, 
1-{3-(4-fluorophenoxy)-4-fluorophenyl}-4-(4-chlorophenyl)-4-methylpentane, 
1-{3-phenoxy-4-fluorophenyl}-4-(4-ethoxyphenyl)-4-methylhexane, 
1-(3-phenoxyphenyl)-4-(4-difluoromethoxyphenyl)-4-methylpentane, 
1-(3-phenoxy-4-fluorophenyl)-4-(4-difluoromethoxyphenyl)-4-methylpentane, 
1-{3-(4-fluorophenoxy)-4-fluorophenyl}-4-(4-difluoromethoxyphenyl)-4-methyl 
pentane, 
1-(3-phenoxyphenyl)-4-(4-trifluoromethoxyphenyl)-4-methylpentane, 
1-(3-phenoxy-4-fluorophenyl)-4-(4-trifluoromethoxyphenyl)-4-methylpentane, 
1-{3-(4-fluorophenoxy)phenyl}-4-(4-trifluoromethoxyphenyl)-4-methylpentane, 
1-{3-(4-fluorophenoxy)-4-fluorophenyl}-4-(4-trifluoromethoxyphenyl)-4-methy 
lpentane, 
1-(3-phenoxyphenyl)-4-(4-chlorodifluoromethoxyphenyl)-4-methylpentane, 
1-{3-(4-fluorophenxoy)phenyl}-4-(4-chlorodifluoromethoxyphenyl)-4-methylpen 
tane, 
1-(3-phenoxy-4-fluorophenyl)-4-(4-chlorodifluoromethoxyphenyl)-4-methylpent 
ane, 
1-{3-(4-fluorophenoxy)-4-fluorophenyl}-4-(4-chlorodifluoromethoxyphenyl)-4- 
methylpentane, 
1-(3-phenoxyphenyl)-4-(4-bromodifluoromethoxyphenyl)-4-methylpentane, 
1-{3-(4-fluorophenoxy)phenyl}-4-(4-bromodifluoromethoxyphenyl)-4-methylpent 
ane, 
1-(3-phenoxy-4-fluorophenyl)-4-(4-bromodifluoromethoxyphenyl)-4-methylpenta 
ne, 
1-{3-(4-fluorophenoxy)-4-fluorophenyl}-4-(4-bromodifluoromethoxyphenyl)-4-m 
ethylpentane, 
1-(3-phenoxyphenyl)-3-{1-(4-ethoxyphenyl)dichloropropyl}propane, 
1-(3-phenoxy-4-fluorophenyl)-3-{1-(4-ethoxyphenyl)-4-cyclopropyl}propane, 
1-{3-(4-fluorophenoxy)-4-fluorophenyl}-3-{1-(4-ethoxyphenyl) 
cyclopropyl}propane, 
1-(3-phenoxyphenyl)-3-{4-(4-chlorophenyl)-2,2-dichlorocyclopropyl}propane, 
1-(3-phenoxy-4-fluorophenyl)-3-{1-(4-chlorophenyl)-2,2-dichlorocyclopropyl} 
propane, 
1-{3-(4-fluorophenoxy)-4-fluorophenyl}-3-{1-(4-chlorophenyl)-2,2-dichlorocy 
clopropyl}propane, 
1-(3-phenoxyphenyl)-3-{1-(4-ethoxyphenyl)-2,2-difluorocyclopropyl}propane, 
1-(3-phenoxy-4-fluorophenyl)-3-{1-(4-ethoxyphenyl)-2,2-difluorocyclopropyl} 
propane, 
1-{3-(4-fluorophenoxy)phenyl}-3-{1-(4-ethoxyphenyl)-2,2-difluorocyclopropyl 
}propane, 
1-{3-(4-fluorophenoxy)-4-fluorophenyl}-3-{1-(4-ethoxyphenyl)-2,2-difluorocy 
clopropyl}propane, 
1-(3-phenoxyphenyl)-3-{1-(4-ethoxyphenyl)cyclobutyl}propane, 
1-(3-phenoxy-4-fluorophenyl)-3-{1-(4-ethoxyphenyl)cyclobutyl}propane, 
1-(3-phenoxyphenyl)-3-{1-(4-ethoxyphenyl)-3,3-dichlorocyclobutyl}propane, 
1-(3-phenoxy-4-fluorophenyl)-3-{1-(4-ethoxyphenyl)-3,3-dichlorocyclobutyl}p 
ropane, 
1-(3-phenoxyphenyl)-3-{1-(4-ethoxyphenyl)-2,2-dimethylcyclopropyl}propane, 
and 
1-(3-phenoxy-4-fluorophenyl)-3-{1-(4-ethoxyphenyl)-2,2-dimethylcyclopropyl} 
propane. 
Compounds (Id) 
3-phenoxybenzyl 2-(4-chlorophenyl)-2-isopropylethyl ether, 
3-phenoxybenzyl 2-(4-methylphenyl)-2-isopropylethyl ether, 
3-phenoxybenzyl 2-(4-methoxyphenyl)-2-isopropylethyl ether, 
3-phenoxybenzyl 2-(4-chlorophenyl)-2-isopropyl ether sulfide, 
3-phenoxybenzyl 2-(3-methylphenyl)-2-isopropylethyl ether, 
3-phenoxybenzyl 2-(3,4-dimethoxyphenyl)-2-isopropylethyl ether, 
3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-isopropylethyl ether, 
3-(4-fluorophenoxy)-4-fluorobenzyl 2-(4-methoxyphenyl)-2-isopropyl ether, 
3-(4-fluorophenoxybenzyl) 2-(4-difluoromethoxyphenyl)-2-isopropylethyl 
ether, 
3-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-2-isopropylethyl ether, and 
3-phenoxy-4-fluorobenzyl-2-(4-ethoxyphenyl)-2-isopropylethyl ether. 
Among the insecticidal compounds of the present invention represented by 
the following general formula (II): 
##STR14## 
wherein R.sub.8, R.sub.9 and R.sub.10 each represent a hydrogen or halogen 
atom or a lower alkyl group, R.sub.11 represents a hydrogen atom or a 
cyano or ethynyl group, and R.sub.6 and R.sub.7 are as defined above, 
those having particularly excellent effects include the following 
compounds: 
3-phenoxybenzyl neopentyl ether, 
3-phenoxybenzyl 1,1,1-trichloroethyl ether, 
.alpha.-cyano-3-phenoxybenzyl neopentyl ether, 
3-(4-fluorophenxoy)benzyl neopentyl ether, 
3-(4-methoxyphenoxy)benzyl neopentyl ether, 
3-phenoxybenzyl 2-methylpropyl ether, 
.alpha.-ethynyl-3-phenoxybenzyl neopentyl ether, 
3-phenoxy-4-fluorobenzyl neopentyl ether, 
3-(4-fluorophenoxy)-4-fluorobenzyl neopentyl ether, and 
.alpha.-cyano-3-phenoxy-4-fluorobenzyl neopentyl ether. 
Among the insecticidal compounds of the present invention represented by 
the following general formula (III): 
##STR15## 
wherein R.sub.12, R.sub.13, R.sub.14 and R.sub.15 each represent a 
hydrogen or halogen atom or a lower alkyl or lower alkenyl group, and 
R.sub.6 and R.sub.7 are as defined above, those having particularly 
excellent effects include the following compounds: 
3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropylmethyl ether, 
3-phenoxybenzyl 2,2-dimethyl-3-isobutenylcyclopropylmethyl ether, 
3-phenoxybenzyl 2,2-dimethylcyclopropylmethyl ether, 
3-phenoxybenzyl cyclopropylmethyl ether, 
3-(4-chlorophenoxy)benzyl 2,2-dichlorocyclopropylmethyl ether, and 
3-phenoxy-4-fluorobenzyl cyclopropylmethyl ether. 
Examples of the insecticidal ester-type pyrethroid compounds of the present 
invention represented by the following general formula (IV): 
##STR16## 
wherein R.sub.6, R.sub.7, R.sub.11, R.sub.12, R.sub.13 and R.sub.14 are as 
defined above and R.sub.16 represents a hydrogen or halogen atom or a 
lower alkyl, lower alkenyl or halogen-substituted lower alkenyl group, 
include the following compounds: 
3'-phenoxybenzyl 2,2-dimethyl-3-isobutenylcyclopropanecarboxylate, 
3'-phenoxybenzyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate, 
3'-phenoxy-.alpha.-cyanobenzyl 
2,2-dimethyl-3-isobutenylcyclopropanecarboxylate, 
3'-phenoxy-.alpha.-cyanobenzyl 
2,2-dimethyl-3,3-dimethylcyclopropanecarboxylate, 
3'-phenoxy-4'-fluorobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate, 
3'-phenoxy-.alpha.-cyanobenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate, 
3'-phenoxy-4'-fluorobenzyl-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropaneca 
rboxylate, 
3'-phenoxy-.alpha.-4'-fluorobenzyl 
2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate, 
3'-phenoxybenzyl 
2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate, 
3'-phenoxy-.alpha.-cyano-4'-fluorobenzyl 
2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate, 
3'-phenoxy-.alpha.-cyanobenzyl 
3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate, 
3'-phenoxy-4'-fluorobenzyl 
2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)cyclopropanecarboxylate, 
3'-phenoxybenzyl 2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropanecarboxylate, 
3'-phenoxy-.alpha.-cyanobenzyl 
2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropanecarboxylate, 
3'-phenoxy-4'-fluorobenzyl 
2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropanecarboxylate, 
3'-phenoxy-.alpha.-cyano-4'-fluorobenzyl 
2,2-dimethyl-3-(2,2-dibromovinyl)cyclopropanecarboxylate, 
3'-phenoxy-.alpha.-cyanobenzyl 
2,2-dimethyl-3-(1,2,2,2-tetrabromoethyl)cyclopropanecarboxylate, 
3'-phenoxy-.alpha.-cyanobenzyl 
2,2-dimethyl-3-(2,2-dibromo-1,2-dichloroethyl)cyclopropanecarboxylate, and 
3'-phenoxy-.alpha.-cyanobenzyl 
2,2-dimethyl-3-(4-tert-butylphenyl)cyclopropanecarboxylate. 
Examples of the insecticidal ester-type pyrethroid compounds of the present 
invention represented by the following general formula (V): 
##STR17## 
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.6, R.sub.7 and R.sub.11 are as 
defined above, R.sub.17 represents a lower alkyl group, R.sub.30 
represents a hydrogen atom or R.sub.17 and R.sub.30 form an unsubstituted 
or substituted cycloalkyl group together with the carbon atom bonded with 
them, and Y represents an oxygen atom, --NH-- group or methylene group 
include the following compounds: 
3'-phenoxybenzyl .alpha.-isopropyl(3,4-dimethoxyphenyl)acetate, 
3'-phenoxy-.alpha.'-cyanobenzyl .alpha.-isopropyl(p-ethoxyphenyl)acetate, 
3'-benzylbenzyl .alpha.-isopropyl-(3-methoxy-4-methyl)phenylacetate, 
3'-phenoxybenzyl .alpha.-isopropyl-p-methoxyphenylacetate, 
3'-phenoxybenzyl .alpha.-ethyl(2,4,6-trimethyl)phenylacetate, 
3'-phenoxybenzyl .alpha.-ethyl-p-methoxyphenylacetate, 
3'-phenoxybenzyl .alpha.-isopropenyl-p-methoxyphenylacetate, 
3'-benzylbenzyl .alpha.-isopropyl-p-methoxyphenylacetate, 
3'-phenoxybenzyl .alpha.-isopropyl-p-methylthiophenylacetate, 
3'-phenoxybenzyl .alpha.-isopropenyl-m-methoxyphenylacetate, 
3'-phenoxybenzyl .alpha.-isopropenyl-3,4-dimethoxyphenylacetate, 
3'-phenoxybenzyl .alpha.-isopropyl-4-chlorophenylacetate, 
3'-phenoxy-.alpha.'-cyanobenzyl .alpha.-isopropyl-4-chlorophenylacetate, 
3'-phenoxy-4'-fluorobenzyl .alpha.-isopropyl-4-chlorophenylacetate, 
3'-phenoxy-.alpha.'-cyano-4'-fluorobenzyl 
.alpha.-isopropyl-4-chlorophenylacetate, 
3'-phenoxybenzyl .alpha.-isopropyl-4-difluoromethoxyphenylacetate, 
3'-phenoxy-.alpha.'-cyanobenzyl 
.alpha.-isopropyl-4-difluoromethoxyphenylacetate, 
3'-phenoxy-4'-fluorobenzyl 
.alpha.-isopropyl-4-difluoromethoxyphenylacetate, 
3'-phenoxy-.alpha.'-cyano-4'-fluorobenzyl 
.alpha.-isopropyl-4-difluoromethoxyphenylacetate, 
3'-phenoxy-.alpha.'-cyanobenzyl 
2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate, and 
3'-phenoxy-.alpha.'-ethynylbenzyl 
1-(4-ethoxyphenyl)-2,2,3,3-tetrafluorocyclobutanecarboxylate. 
Examples of the insecticidal ester-type pyrethroid compounds of the present 
invention represented by the following general formula (VI): 
##STR18## 
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.7, R.sub.11 and R.sub.17 are as 
defined above, R.sub.18 represents a hydrogen or halogen atom or a lower 
alkyl or lower alkoxy group and W represents an oxygen atom or a methylene 
group including the following compounds: 
5'-benzyl-3'-furylmethyl .alpha.-isopropyl(p-methoxyphenyl)acetate, 
5'-benzyl-3'-furylmethyl .alpha.-ethyl-(m-methoxyphenyl)acetate, 
5'-benzyl-3'-furylmethyl .alpha.-isopropyl(p-allylphenyl)acetate, 
5'-phenoxy-2'-furylmethyl 
.alpha.-isopropyl(2-methyl-4-methoxy)phenylacetate, 
5'-benzyl-3'-furylmethyl .alpha.-ethyl-m-methylphenylacetate, 
5'-benzyl-3'-thienyl .alpha.-isopropyl-2-methyl-3-isopropenylphenylacetate, 
5'-benzyl-3'-furylmethyl .alpha.-isopropyl-4,5-dimethylphenylacetate, 
5'-benzyl-3'-furylmethyl .alpha.-isopropyl-3,4-dimethoxyphenylacetate, and 
5'-benzyl-3'-furylmethyl .alpha.-isopropyl-m-methoxyphenylacetate. 
Examples of the insecticidal compounds of the present invention represented 
by the following general formula (VII): 
##STR19## 
wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.6, R.sub.7 and R.sub.11 
are as defined above, including the following compounds: 
3'-phenoxybenzyl .alpha.-isopropylanilinoacetate, 
3'-phenoxybenzyl .alpha.-isopropyl-(4-chloroanilino)acetate, 
3'-phenoxybenzyl .alpha.-isopropyl-(4-methylanilino)acetate, 
3'-phenoxy-.alpha.'-cyanobenzyl 
.alpha.-isopropyl-(2-chloro-4-trifluoromethylanilino)acetate, 
3'-phenoxybenzyl .alpha.-isopropyl-(4-trifluoromethylanilino)acetate, and 
3'-phenoxy-.alpha.'-cyanobenzyl 
.alpha.-isopropyl-4-trifluoromethylanilino)acetate. 
Among the insecticidal compounds of the above general formula (I), those of 
the following general formula (XIV) have particularly excellent effects. 
Examples of them include those shown in the following Table 1: 
##STR20## 
TABLE 1 
______________________________________ 
Compound No. 
X B R.sub.6 
Refractive index (20.degree. C.) 
______________________________________ 
1 O Br H 1.5545 
2 O Br F 1.5440 
3 CH.sub.2 
Br H 1.5482 
4 CH.sub.2 
Br F 1.5480 
5 O Cl H 1.5441 
6 O Cl F 
7 CH.sub.2 
Cl H 
8 CH.sub.2 
Cl F 
9 O F H 1.5312 
10 O F F 1.5208 
11 CH.sub.2 
F H 1.5340 
12 CH.sub.2 
F F 1.5248 
______________________________________ 
Among the compounds of the general formula (XIV), those wherein X 
represents an oxygen atom [i.e. compounds of the following general 
formulae (XIVa), (XIVb) and (XIVc)] can be easily prepared from compounds 
(XV) by the following processes: 
##STR21## 
wherein Y is as defined above. 
A phenol derivative of the general formula (XV) is reacted with 
dibromodifluoromethane or difluorobromochloromethane in the presence of a 
base such as sodium hydride or potassium t-butoxide in a polar solvent 
such as dimethylformamide (DMF) or 1,3-dimethyl-2-imidazolidinone (DMI) to 
prepare a compound (XIVa) or (XIVb) (reference: Tetrahedron Letters, 1981, 
323). The compound (XIVa) thus prepared is reacted with hydrogen fluoride 
to prepare a compound (XIVc) (reference: Japanese Patent Laid-Open No. 
128374/1983). 
Compounds (XIVa), (XIVb) and (XIVc) can be easily prepared from compounds 
(XVIa), (XVIb) and (XVIc), respectively with compound XVIII by the 
following processes: 
##STR22## 
wherein R.sub.6 is as defined above and Z represents a halogen atom. 
Namely, the intended compounds can be prepared from the 
2-aryl-2-methylpropyl alcohols of the above formula (XVIa), (XVIb) or 
(XVIc) and benzyl halides of the general formula (XVIII) by an ordinary 
etherification reaction. The 2-aryl-2-methylpropyl alcohols of the 
formulae (XVIa), (XVIb) and (XVIc) have not been described in literatures. 
The 2-aryl-2-methylpropyl alcohols of the general formula (XVI) [i.e. 
general formulae (XVIa), (XVIb) and (XVIc)] can be prepared by the 
following processes: 
##STR23## 
wherein R.sub.28 and R.sub.29 each represent a hydrogen or halogen atom or 
an alkyl, alkoxy or phenoxy group. 
In this process, a benzyl ether derivative of the general formula (XIX) is 
reacted with trimethylsilyl iodide in an inert solvent such as hexane or 
chloroform and then the product thus obtained is reacted with water to 
obtain the intended product easily. 
The compounds of the general formula (XIV) wherein A represents a methylene 
group [compounds of the general formulae (XIVd), (XIVe) and (XIVf)] can be 
prepared easily from compounds of the following formula (XX) as follows: 
##STR24## 
wherein Y is as defined above. 
The compounds (XIVd), (XIVe) and (XIVf) can be prepared from the compounds 
(XV) under the same conditions as in the preparation of the compounds 
(XIVa), (XIVb) and (XIVc). 
The amount of the insecticide is 0.1 to 10 parts by weight, preferably 0.5 
to 10 parts by weight, per part of the resin component. When the amount is 
less than 0.1 part by weight, the insecticidal effect is insufficient and, 
on the contrary, even when it exceeds 10 parts by weight, the insecticidal 
effect is no more improved and such an excess amount is economically 
disadvantageous. The insecticidal resin coating film of the present 
invention may contain additives in addition to the insecticidal component. 
The additives include, for example, waxes, fusing agents and plasticizers. 
Usually excellent effects are obtained when a wax such as carnauba wax, 
rice bran wax, bees wax, spermaceti, candelilla wax, haze wax, montan wax, 
ceresine wax, paraffin wax, microcrystalline wax, polyethylene wax or 
Fischer-Tropsch wax is used. 
The insecticidal resin coating film of the present invention can be 
prepared by, for example, the following processes: 
(1) a process wherein an insecticidal component per se or its solution is 
mixed with an emulsion of a copolymer resin of (meth)acrylonitrile and 
another monomer, the mixture is applied to a substrate by a known method 
such as bar coating, roll coating, air knife coating, spray coating, 
dipping, brush coating or screen printing method and the coating film thus 
formed is dried, 
(2) a process wherein (meth)acrylonitrile is emulsion-polymerized with 
another monomer in the presence of an insecticidal component, the polymer 
emulsion thus prepared is applied to a substrate by a known method and the 
coating film thus formed is dried, 
(3) a process wherein an insecticidal component per se or its solution is 
mixed with a solution of a copolymer resin of (meth)acrylonitrile and 
another monomer, the mixture is applied to a substrate by a known method 
and the coating film thus formed is dried, 
(4) a process wherein (meth)acrylonitrile is solution-polymerized with 
another monomer in the presence of an insecticidal component, the polymer 
solution thus obtained is applied to a substrate by a known method and the 
coating film thus formed is dried, and 
(5) a process wherein a copolymer resin of (meth)acrylonitrile and another 
monomer is kneaded with an insecticidal component by means of a blender 
such as roll blender and the mixture thus obtained is pressed onto a 
substrate under heating. 
Further, modifications of these processes can also be employed. As a matter 
of course, the processes are not limited to those mentioned above. Though 
the drying conditions are not particularly limited in the above processes 
(1) to (4), the drying is usually conducted at ambient temperature to 
150.degree. C. for 1 min to 24 h. 
Among the above-mentioned processes, the process (1) is most preferred from 
the viewpoint of the insecticidal effect. 
In case the insecticidal component is used in the form of its solution, the 
solvents usable therefor include ketones, esters, halogenated 
hydrocarbons, aromatic hydrocarbons and alicyclic hydrocarbons. These 
solvents are used either singly or in the form of a mixture of them. The 
substrates to which the resin is to be applied are not particularly 
limited. They are preferably papers, synthetic papers, plastic sheets, 
steel plates, etc. Although the thickness of the coating film is not 
particularly limited, it is usually 20 to 100.mu..