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Description  |
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a synthetic resin product containing various
substance(s) selected from among perfumes, insectifuges, rust preventive,
mildewproofing agent and bactericide in the form of an inclusion compound
in cyclodextrin and a process for the production of the same.
2. Description of the Prior Art
There have been developed various processes for the production of smelling
and/or insectifugal synthetic resin products. Some processes comprise
applying perfume(s) and/or insectifuge(s)/insecticide onto the surface of
a synthetic resin product. Others comprise injecting perfume(s) and/or
insectifuge(s)/insecticide into a space in a synthetic resin product or
laminating synthetic resin sheets and injecting perfumes(s) and/or
insectifuge(s)/insecticide between these sheets. It is also possible to
mix perfume(s) and/or insectifuge(s)/insecticide with a synthetic resin
compound followed by molding the obtained mixture. Perfume(s) and/or
insectifuge(s)/insecticide applied on the surface of a synthetic resin
product would vaporize so soon that they might not exhibit a persistent
effect. On the contrary, those injected into a synthetic resin product
would hardly vaporise and might not exhibit an expected effect. Further
direct addition of perfume(s) and/or insectifuge(s)/insecticide to a
synthetic resin compound is not as effective as it seems. This is because
perfumes and/or insectifuges/insecticides are generally so volatile,
liable to denature and unstable to heat that it is difficult in practice
to mold a mixture of perfume(s) and/or insectifuge(s)/insecticides and a
synthetic resin compound into a desired shape. It was further attempted to
adsorb desired perfume(s) and/or insectifuge(s)/insecticide(s) by porous
inorganic substances such as calcium silicate, zeolite or powdery alumina
or porous polymer powders obtained by quenching and artificially grinding
synthetic resins with the use of liquid nitrogen during the preparation
thereof and to incorporate the obtained composition in a plastic followed
by molding. However the desired perfume(s) and/or
insectifuge(s)/insecticide(s) are adsorbed merely in pores in each process
so that it is necessary to adsorb an excessive amount of them, including
those which vaporize at the molding temperature, to give a sufficient
amount of the same in molded products, which brings about an additional
cost. Thus these processes are not preferable. Further perfume(s) and/or
insectifuge(s)/insecticide(s) are not chemically bonded to cyclodextrin
but merely absorbed in pores. Therefore some might be completely removed
when heated for molding or might bleed in a short period. Thus these
processes are not practical.
Under these circumstances, we have previously invented a process for
producing a smelling synthetic resin product which comprises forming an
inclusion compound consisting of a perfume included in cyclodextrin,
drying and powdering the obtained inclusion compound and mixing the
obtained powder with a synthetic resin compound (cf. Japanese Pat. No.
1090861).
We have further invented a process for producing an insectifugal and
insecticidal film which comprises forming an inclusion compound consisting
of an insectifugal and insecticidal agent included in cyclodextrin, drying
and powdering the obtained inclusion compound and mixing the obtained
powder with a synthetic resin compound followed by molding into a film
(cf. Japanese Patent Application No. 188212/1984).
Machines as well as their parts have been packaged by applying rust
preventives such as liquid paraffin thereon to warp them with oil membrane
to thereby prevent rusting. The rust preventives such as liquid paraffin
are removed at use. Therefore it is required to apply a rust preventive
and to remove the same each time a machine is packaged. Conventional
oilpapers exhibit some rust preventive effect. However this effect is so
insufficient that it is necessary to directly apply a rust preventive on a
machine to be packaged. It has been also attempted to package a machine
with a paper impregnated with a rust preventive. However this method is
available only in a limited range since fine paper pieces entering
apertures of a precision machine would cause trouble.
It is a large problem to prevent rust or mildew in silicone and epoxy
resins which have been recently employed in semiconductor materials. Since
these resins are used in precision electrical instruments, it is
impossible to spray or apply rust preventive(s) or mildewproofing agent(s)
thereon. Thus these materials are packaged with paper sheets exhibiting a
rust preventive and/or mildew-proofing effect.
Also it is sometimes required to prevent rusting in coatings, tackifiers
and adhesives. Furthermore those products having a smell or an
insectifugal and/or rust preventive effect may be available in a wider
range. We have previously invented a product wherein an inclusion compound
consisting of a perfume included in cyclodextrin is formed, the inclusion
compound thus obtained is mixed with a latex and the mixture is applied on
the surface of a tacky substrate (cf. Japanese Patent Laid-Open No.
185372/1982).
A smelling synthetic resin product produced by forming an inclusion
compound consisting of a perfume included in cyclodextrin, powdering and
drying the obtained inclusion compound and mixing the obtained powder with
a synthetic resin compound is much more excellent than those produced by
conventional methods. Subsequent studies have proved that not only
perfumes but also various substances such as insectifuges, mildew-proofing
agents and rust preventives may be formed into an inclusion compound so
long as it can be included in cyclodextrin to thereby produce synthetic
resin products having the effect of each substance.
However these inclusion compounds consisting of perfumes, insectifuges,
mildew-proofing agents or rust preventives included in cyclodextrin can
not be used in practice in synthetic resin products of a high molding
temperature, i.e. 180.degree. C. or above. Cyclodextrin per se is stable
at high temperatures and shows no chemical change so that it is
theoretically possible to use it in a synthetic resin of a high molding
temperature. However pure cyclodextrin is so expensive that decomposed
starches containing cyclodextrin are employed in practice. These
decomposed starches contain reducing sugars which would be denatured and
charred when molded at a high temperature.
Although there is no problem in the production of a synthetic resin product
having various effects by forming an inclusion compound consisting of
perfume(s), insectifuge(s) or rust preventive(s) included in cyclodextrin,
drying and powdering the obtained inclusion compound and mixing the
obtained powder with a synthetic resin compound on a laboratory scale with
the use of pure cyclodextrin, there remains a problem to be solved in the
production thereof on an industrial scale.
In addition, the volatility of each substance is somewhat depressed by
including the same in cyclodextrin to thereby form an inclusion compound,
which allows its effect to persist for a much longer period than with
conventional products. However the persistence is somewhat insufficient
yet.
SUMMARY OF THE INVENTION
Under these circumstances, the present invention provides a synthetic resin
product containing a compound included in cyclodextrin and a process for
the production of the same. The synthetic resin product according to the
present invention contains an inclusion compound consisting of one or more
substances selected from among perfumes, insectifuges, rust preventives,
mildew-proofing agents and bactericides included in cyclodextrin and a
glycitol wherein said perfume(s), insectifuge(s), rust preventive(s)
and/or mildew-proofing agent(s) are inactivated by formulating into the
inclusion compound in cyclodextrin and coated with said glycitol to
thereby enhance the persistence of the effects thereof. The synthetic
resin product exhibiting the abovementioned effects may be produced by
mixing one or more substances selected from among perfumes, insectifuges,
rust preventives, mildew-proofing agents and bactericides with a reduced
cyclodextrin millet jelly optionally containing cyclodextrin or a reduced
millet jelly containing cyclodextrin to thereby form an inclusion compound
consisting of said perfume(s), insectifuge(s), rust preventive(s),
mildew-proofing agent(s) and/or bactericide(s) included in cyclodextrin;
drying and powdering the obtained material containing the inclusion
compound; melting 1 to 60% by weight of the obtained powder together with
a synthetic resin compound; pelletizing the molten mixture; and molding
the obtained pellets optionally with an appropriate amount of the
synthetic resin compound. Alternately one or more substances selected from
among perfumes, insectifuges, rust preventives, mildew-proofing agents and
bactericides are mixed with a reduced cyclodextrin millet jelly optionally
containing cyclodextrin or a reduced millet jelly containing cyclodextrin
to thereby form an inclusion compound consisting of perfume(s),
insectifuge(s), rust preventive(s), mildew-proofing agent(s) and/or
bactericide(s) included in cyclodextrin. Then the obtained material
containing the inclusion compound is dried and powdered and 1 to 60% by
weight of the resulting powder is mixed with a synthetic resin coating, a
synthetic resin adhesive or a synthetic resin tackifier as it is, ie.,
without heating or under heating. Accordingly reducing sugars contained as
impurities in the cyclodextrin decomposed starch are converted into
chemically stable glycitols which are used to form an inclusion compound
consisting of perfume(s), insectifuge(s), rust preventive(s) and/or
mildew-proofing agent(s). Then the obtained inclusion compound is dried
and powdered and the resulting powder is converted into a chemically
stable form by mixing with various synthetic resin materials, synthetic
resin coating, synthetic resin adhesive or synthetic resin tackifier thus
enabling the use of various synthetic resin materials and prolonging the
duration period of the effect of each substance by taking advantage of the
glycitol coating.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph which shows the amounts (%) of residual fenitrothion
(Sumithion) in samples 1 and 2 determined with the initial amount thereof
as 100, wherein and .circle. refer to samples and 1 and 2,
respectively.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The reduced millet jelly used in the present invention is obtained by
hydrolyzing starch with an acid or an enzyme to give a maltoligosaccharide
mixture comprising glucose, maltose, maltotriose and similar compounds and
hydrogenating the mixture in the presence of a nickel catalyst under
elevated pressure. Thus reductive terminals of the reducing sugars are
hydrogenated to give the corresponding glycitols. That is, glucose,
maltose and maltotriose are converted into sorbitol, maltitol and
maltotriitol, respectively, and lose their reductivity. Thus the D.E.
(dextrose equivalent; the ratio of reducing sugars to the total solid
matters) of the mixture turns to 0. Therefore the mixture becomes more
stable to heat and shows little coloration caused by a reaction with amino
radicals contained in amino acids or the like, i.e. aminocarbonyl
reaction.
The reduced cyclodextrin millet jelly used in the present invention
includes the abovementioned reduced millet jelly containing cyclodextrin.
Since cyclodextrin exhibits no reductivity, the D.E. of the same is 0. In
practice, the reduced cyclodextrin millet jelly can be obtained by
catalytically reducing a millet jelly containing cyclodextrin, e.g.
Celldex CH-20 or CH-30 mfd. by Nippon Shokuhin Kako K. K., in the manner
as described above. The cyclodextrin contained therein shows no change by
the above procedure but reducing sugars other than the cyclodextrin are
reduced and converted into the corresponding glycitols.
Either natural or synthetic perfumes may be used in the present invention.
Examples of natural perfumes are animal or vegetable perfumes such as
lavender oil, citronella oil, rose oil, lemon oil and jasmin oil. Examples
of synthetic perfumes are ethyl acetoacetate (C.sub.6 H.sub.10 O.sub.3),
acetophenone (C.sub.8 H.sub.8 O), anisic aldehyde (C.sub.8 H.sub.8
O.sub.2), benzyl benzoate (C.sub.14 H.sub.12 O.sub.2), amyl cinnamic
aldehyde (C.sub.14 H.sub.18 O), methyl benzoate (C.sub.8 H.sub.8 O.sub.2),
ethyl isovalerate (C.sub.7 H.sub.14 O.sub.2), ethyl vanillin (C.sub.9
H.sub.10 O.sub.3), ethylene brassylate (C.sub.15 H.sub.26 O.sub.4), ethyl
formate (C.sub.3 H.sub.6 O.sub.2), citronellyl formate (C.sub.11 H.sub.20
O.sub.8), coumarin (C.sub.9 H.sub.6 O.sub.2), cuminaldehyde (C.sub.10
H.sub.12 O), cinnamyl alcohol (C.sub.9 H.sub.10 O), geraniol (C.sub.10
H.sub.18 O), acetyl eugenol (C.sub.12 H.sub.14 O.sub.3), citronellyl
acetate (C.sub.12 H.sub.22 O.sub.2), terpinyl acetate (C.sub.12 H.sub.20
O.sub.2), benzyl acetate (C.sub.9 H.sub.10 O.sub.2), isoamyl salicylate
(C.sub.12 H.sub.16 O.sub.3), benzyl salicylate (C.sub.14 H.sub.13
O.sub.3), cyclamen aldehyde (C.sub.13 H.sub.18 O), citral (C.sub.10
H.sub.16 O), citronellol (C.sub.10 H.sub.20 O), tetrahydrolinalool
(C.sub.10 H.sub.22 O), terpineol (C.sub.10 H.sub.18 O), vanillin (C.sub.8
H.sub.8 O.sub.3), ethyl phenylacetate (C.sub.10 H.sub.12 O.sub.2),
heliotropin (C.sub.6 H.sub.6 O.sub.3), musk ambrette (C.sub.12 H.sub.16
O.sub.5 N.sub.2), p-methylacetophenone (C.sub.9 H.sub.10 O), methylionone
(C.sub.14 H.sub.22 O), ethyl methyl phenylglycidate (C.sub.12 H.sub.14
O.sub.3), 1-menthol (C.sub.10 H.sub.20 O), butyric acid (C.sub.4 H.sub.8
O.sub.2), linalool (C.sub.10 H.sub.18 O), linonene & dipentene (C.sub.10
H.sub.16), rosephenone (C.sub.10 H.sub.9 Cl.sub.3 O.sub.2) and rosinol
(C.sub.10 H.sub.20 O).
The mildewproofing agents used in the present invention are those having an
antibacterial and bactericidal effect. Examples of a substance which
mainly serves as an antibacterial agent or a bactericide are chlorhexydine
gluconate (C.sub.22 H.sub.30 Cl.sub.2 N.sub.10.2C.sub.6 H.sub.12 O.sub.7 :
897.77), N-(fluorodichloromethylthio)phthalimide and
.alpha.-bromocinnamaldehyde (C.sub.9 H.sub.2 OBr).
Examples of compounds mainly available as a mildew-proofing agent are as
follows:
thiabendazole;
##STR1##
2-hydroxydiphenyl;
##STR2##
N-dimethyl-N'-phenyl-(N'-fluorodichloromethylthio)sulfamide;
##STR3##
3-methyl-4-chlorophenol (p-chloro-m-cresol);
##STR4##
tolyltriazole (1H-4/5-methylbenzotriazole);
##STR5##
benzotriazole (1,2,3-benzotriazole);
##STR6##
The insectifuges used in the present invention include not only repellents
such as citronella oil but also those having an insectifugal and
insecticidal effect. More particularly it is preferable to use organic
phosphorus or pyrethroid insecticides.
An example of the organic phosphorus insecticide used in the present
invention is fenitrothion (O,O-dimethyl )
O-(3-methyl-4-nitrophenyl)thiophosphorate;
##STR7##
Examples of the pyrethroid insecticides are as follows.
allethrin [dl-3-allyl-2-methyl-4-oxo-2-cyclopentenyl
dl-cis/trans-chrysanthemate];
##STR8##
phthalthrin [(1,3,4,5,6,7-hexahydro-1,3,dioxo-2-isoindolyl)methyl
dl-cis/trans-chrysanthemate];
##STR9##
resmethrin [(benzyl-3-furyl)methyl dl-cis/trans-chrysanthemate];
##STR10##
furamethrin [(5-(2-propinyl)-2-furyl)methyl dl-cis/trans-chrysanthemate];
##STR11##
phenothrin [3-phenoxybenzyl d-cis/trans-chrysanthemate];
##STR12##
permethrin [3-phenoxybenzyl
dl-cis/trans-3-(2,2-dichlorovinyl)-2,2-dimethyl-1-cyclopropanecarboxylate]
;
##STR13##
and 2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether
##STR14##
Organic phosphorus and pyrethroid insecticides are used as an insectifugal
and insecticidal agents since they exhibit an excellent effect, a low
toxicity and a high stability and are available in a wide range. Further
they can be readily formulated into an inclusion compound in cyclodextrin.
Furthermore they are so stable at high temperatures that they can be mixed
with a synthetic resin compound for molding.
Any rust preventive such as liquid paraffin or spindle oil may be used in
the present invention so long as they can be included in cyclodextrin.
Volatile rust preventives or volatile rust preventive oils such as
dicyclohexylammonium nitrite [(C.sub.6 H.sub.10).sub.2 NH.sub.3 HNO.sub.2
], di-isopropylamine nitrite [(CH.sub.3).sub.2 CH).sub.2 NH.HNO.sub.2)
(dipan)] and ferro-bright oil may be employed.
Any synthetic resin coating, synthetic resin tackifier and synthetic resin
adhesive may be used in the present invention so long as they comprise
synthetic resin(s). Examples thereof are synthetic rubbers, synthetic
rubber adhesives and synthetic rubber tackifiers.
Examples of the synthetic resin coatings are alkyd resin coatings, amino
alkyd resin coatings, vinyl resin coatings, acrylic resin coatings, epoxy
resin coatings, polyurethane coatings and unsaturated polyester coatings.
Examples of synthetic resin adhesives are thermoplastic resin adhesives
such as vinyl resin adhesives, acrylic resin adhesives,
.alpha.-cyanoacrylate and tetraethylene glycol dimethacrylate and
thermosetting resin adhesives such as phenol resin adhesives, resorcinol
resin adhesives, xylene resin adhesives, furan resin adhesives, urea resin
adhesives, melamine resin adhesives; epoxy resin adhesives and
polyurethane adhesives.
Examples of the synthetic resin product containing a compound included in
cyclodextrin according to the present invention and a process for the
production of the same will now be described.
EXAMPLE 1
20 parts by weight of .alpha.-cyclodextrin and 65 parts by weight of a
reduced millet jelly were added to 15 parts by weight of geraniol and the
mixture was stirred at 70.degree. C. for one hour to give a material which
contained a molecular inclusion compound of geraniol in cyclodextrin. The
obtained material was dried and ground in a vacuum drier at 60.degree. C.
to give a powder of 150 mesh or finer. 10 parts by weight of this powder
was melted together with 90 parts by weight of polyethylene pellets and
the molten mixture was pelletized by cold cut method. These pellets were
injection molded to give cups, pen cases and toys having a smell of rose.
EXAMPLE 2
90 parts by weight of a reduced cyclodextrin millet jelly containing 20% by
weight of cyclodextrin was added to 10 parts by weight of jasmin oil and
the mixture was stirred at 70.degree. C. for one hour to give a material
containing a molecular inclusion compound of jasmine in cyclodextrin. The
obtained material was dried and ground in a vacuum drier at 60.degree. C.
to give a powder of 150 mesh or finer. 20 parts by weight of this powder
was melted together with 80 parts by weight of polyethylene pellets. The
molten mixture was pelletized by cold cut method. From the obtained
pellets, a packaging film having smell of jasmine was produced by blown
film extrusion.
EXAMPLE 3
20 parts by weight of .beta.-cyclodextrin and 65 parts by weight of a
reduced cyclodextrin millet jelly containing 20% of cyclodextrin were
added to 15 parts by weight of coffee oil and the mixture was stirred at
65.degree. C. for one hour to give a material containing a molecular
inclusion compound of coffee oil in cyclodextrin. The obtained material
was dried and ground in a spray drier at 80.degree. C. to give a powder of
150 mesh or finer. 10 parts by weight of this powder was melted together
with 90 parts by weight of a plasticized polyvinyl chloride molding
compound. The molten mixture was pelletized by hot cut method. Then 20
parts by weight of the obtained pellets were mixed with 80 parts by weight
of the plasticized polyvinyl chloride molding compound and the mixture was
molded to make straws by extrusion.
EXAMPLE 4
10 parts by weight of .beta.-cyclodextrin and 70 parts by weight of a
reduced cyclodextrin millet jelly containing 20% of cyclodextrin were
added to 20 parts by weight of dimethyl phthalate and the mixture was
stirred at 70.degree. C. for one hour to give a material containing a
molecular inclusion compound of dimethyl phthalate in cyclodextrin. The
obtained material was dried and ground in a spray drier at 80.degree. C.
to give a powder of 150 mesh or finer. 30 parts by weight of this powder
was melted together with 70 parts by weight of polyethylene pellets. The
molten mixture was pelletized by hot cut method. From the obtained
pellets, a vermin-proof polyethylene film was produced by calendering.
EXAMPLE 5
20 parts by weight of .beta.-cyclodextrin and 65 parts by weight of a
reduced millet jelly were added to 15 parts by weight of fenitrothion and
the mixture was stirred at 70.degree. C. for one hour to give a material
containing a molecular inclusion compound of fenitrothion in cyclodextrin.
The obtained material was dried and ground in a vacuum drier at 60.degree.
C. to give a powder of 150 mesh or finer. 50 parts by weight of this
powder was melted together with 50 parts by weight of a plasticized
polyvinyl chloride molding compound. The molten mixture was pelletized by
cold cut method. Then 10 parts by weight of the obtained pellets were
mixed with 90 parts by weight of the plasticized polyvinyl chloride
molding compound. From the resulting material, a pipe for use in the
cultivation of plants was produced by extrusion molding.
EXAMPLE 6
20 parts by weight of .beta.-cyclodextrin and 70 parts by weight of a
reduced millet jelly containing 20% of cyclodextrin were added to 10 parts
by weight of phthalthrin and the mixture was stirred at 65.degree. C. for
one hour to give a material containing a molecular inclusion compound of
phthalthrin in cyclodextrin. The obtained material was dried and ground in
a spray drier at 90.degree. C. to give a powder of 150 mesh or finer. 30
parts by weight of this powder was melted together with 70 parts by weight
of a plasticized polyvinyl chloride molding compound. The molten mixture
was pelletized by hot cut method. Then 20 parts by weight of the obtained
pellets were mixed with 80 parts by weight of the plasticized polyvinyl
chloride molding compound. From the resulting material, a belt was molded
by extrusion for use in growing tree.
EXAMPLE 7
85 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% of .alpha.-, .beta.- and
.gamma.-cyclodextrins was added to 15 parts by weight of resmethrin and
the mixture was stirred at 70.degree. C. for one hour to give a material
containing a molecular inclusion compound of resmethrin in cyclodextrin.
The obtained material was dried and ground in a vacuum drier at 60.degree.
C. to give a powder of 150 mesh or finer. 20 parts by weight of this
powder was melted together with 80 parts by weight of polyethylene
pellets. The molten mixture was pelletized by cold cut method. From the
obtained pellets, a flower pot was produced by injection.
EXAMPLE 8
80 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% of .alpha.-, .beta.- and
.gamma.-cyclodextrins and 5 parts by weight of .beta.-cyclodextrin were
added to 15 parts by weight of furamethrin and the mixture was stirred at
70.degree. C. for one hour to give a material containing a molecular
inclusion compound of furamethrin in cyclodextrin. The obtained material
was dried and ground in a spray drier at 90.degree. C. to give a powder of
150 mesh or finer. 10 parts by weight of this powder was melted together
with 90 parts by weight of a polyvinyl acetate compound. The molten
mixture was pelletized by underwater cut method. Then 20 parts by weight
of the obtained pellets were mixed with 80 parts by weight of a polyvinyl
acetate compound. From the resulting material, a bag for use in protecting
fruits was produced by blown film extrusion.
EXAMPLE 9
80 parts by weight of a reduced cyclodextrin millet jelly containing 20% of
cyclodextrin was added to 20 parts by weight of phenothrin and the mixture
was stirred at 70.degree. C. for one hour to give a molecular inclusion
compound of phenothrine in cyclodextrin. The obtained inclusion compound
was dried and ground in a drum drier at 130.degree. C. to give a powder of
150 mesh or finer. 10 parts by weight of this powder was melted together
with 90 parts by weight of an ethylene-vinyl acetate compound. The molten
mixture was pelletized by sheet cutting from which a film was produced by
extrusion.
EXAMPLE 10
85 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% of .alpha.-, .beta.- and
.gamma.-cyclodextrins was added to 15 parts by weight of permethrin and
the mixture was stirred at 65.degree. C. for one hour to give a material
containing a molecular inclusion compound of permethrin in cyclodextrin.
The obtained material was dried and ground in a vacuum drier at 60.degree.
C. to give a powder of 150 mesh or finer. 20 parts by weight of this
powder was melted together with 80 parts by weight of polyethylene
pellets. The molten mixture was pelletized by cold cut method from which a
square board was molded by injection, for cockroach avoiding.
EXAMPLE 11
10 parts by weight of .beta.-cyclodextrin and 80 parts by weight of a
reduced millet jelly were added to 10 parts by weight of allethrin and the
mixture was stirred at 70.degree. C. for one hour to give a material
containing a molecular inclusion compound of allethrin in cyclodextrin.
The obtained material was dried and ground in a spray drier at 90.degree.
C. to give a powder of 150 mesh or finer. 30 parts by weight of this
powder was melted together with 70 parts by weight of a plasticized
polyvinyl chloride molding compound. The molten mixture was pelletized by
hot cut method. Then 20 parts by weight of the obtained pellets were mixed
with 80 parts by weight of the plasticized polyvinyl chloride molding
compound. From the resulting material, a lamp shade was produced by blow
molding for mosquitoes killing/avoiding.
EXAMPLE 12
10 parts by weight of .beta.-cyclodextrin and 75 parts by weight of a
reduced millet jelly were added to 15 parts by weight of fenitrothion and
the mixture was stirred at 70.degree. C. for one hour to give a material
containing a molecular inclusion compound of fenitrothion in cyclodextrin.
The obtained material was dried and ground in a vacuum drier at 60.degree.
C. to give a powder of 150 mesh or finer. 50 parts by weight of this
powder was melted together with 50 parts by weight of a plasticized
polyvinyl chloride molding compound. The molten mixture was pelletized by
cold cut method. Then 10 parts by weight of the obtained pellets were
mixed with 90 parts by weight of the plasticized polyvinyl chloride
molding compound and the resulting material was molded into a film by
calender process.
EXAMPLE 13
At first, 5 parts by weight of camphur oil was added to 10 parts by weight
of fenitrothion, and into this mixture, 10 parts by weight of
.beta.-cyclodextrin and 75 parts by weight of a reduced cyclodextrin
millet jelly containing 20% of cyclodextrin were added, and the mixture
was stirred at 70.degree. C. for one hour to give a material containing a
molecular inclusion compound of fenitrothion in cyclodextrin. The obtained
material was dried and ground in a spray drier at 80.degree. C. to give a
powder of 150 mesh or finer. 30 parts by weight of this powder was melted
together with 70 parts by weight of a plasticized polyvinyl chloride
molding compound. The molten mixture was pelletized by hot cut method.
Then 10 parts by weight of the obtained pellets were mixed with 90 parts
by weight of the plasticized polyvinyl chloride molding compound and the
resulting material was molded into a film by extrusion.
EXAMPLE 14
85 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% of .alpha.-, .beta.- and
.gamma.-cyclodextrins was added to 15 parts by weight of allethrin and the
mixture was stirred at 70.degree. C. for one hour to give a material
containing a molecular inclusion compound of allethrin in cyclodextrin.
The obtained material was dried and ground in a vacuum drier at 60.degree.
C. to give a powder of 150 mesh or finer. 20 parts by weight of the
obtained powder was melted together with 80 parts by weight of
polyethylene pellets. The molten mixture was pelletized by cold cut
method. The resulting pellets were molded into a film by calender process.
EXAMPLE 15
90 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% by weight of .alpha.-, .beta.-
and .gamma.-cyclodextrins was added to 10 parts by weight of phthalthrin
and the mixture was stirred at 70.degree. C. for one hour to give a
material containing a molecular inclusion compound of phthalthrin in
cyclodextrin. The obtained material was dried and ground in a spray drier
at 80.degree. C. to give a powder of 150 mesh or finer. 10 parts by weight
of this powder was melted together with 90 parts by weight of a polyvinyl
acetate compound. The molten mixture was pelletized by underwater cut
method. Then 30 parts by weight of the obtained pellets were mixed with 70
parts by weight of a polyvinyl acetate compound. The resulting mixture was
molded into a film by extrusion.
EXAMPLE 16
5 parts by weight of .alpha.-cyclodextrin and 75 parts by weight of a
reduced millet jelly were added to 20 parts by weight of resmethrin and
the mixture was stirred at 70.degree. C. for one hour to give a material
containing a molecular inclusion compound of resmethrine in cyclodextrin.
The obtained mixture was dried and ground in a drum drier at 140.degree.
C. to give a powder of 150 mesh or finer. 10 parts by weight of this
powder was melted together with 90 parts by weight of an ethylene-vinyl
acetate compound. The molten mixture was pelletized by sheet cut method.
The resulting material was molded into a film by extrusion.
EXAMPLE 17
5 parts by weight of .beta.-cyclodextrin and 75 parts by weight of a
reduced millet jelly were added to 20 parts by weight of liquid paraffin
and the mixture was stirred at 70.degree. C. for one hour to give a
material containing a molecular inclusion compound of liquid paraffin in
cyclodextrin. The obtained material was dried and ground in a spray dried
at 90.degree. C. to give a powder of 150 mesh or finer. 20 parts by weight
of this powder was melted together with 80 parts by weight of polyethylene
pellets. The molten mixture was pelletized by cold cut method. The
resulting pellets were molded into a rust preventive film.
EXAMPLE 18
90 parts by weight of a reduced cyclodextrin millet jelly containing 20% of
cyclodextrin was added to 10 parts by weight of spindle oil and the
mixture was stirred at 70.degree. C. for one hour to give a material
containing a molecular inclusion compound of spindle oil in cyclodextrin.
The obtained material was dried and ground in a spray drier at 90.degree.
C. to give a powder of 150 mesh or finer. 20 parts by weight of this
powder was melted together with 80 parts by weight of polyethylene
pellets. The molten mixture was pelletized by cold cut method. The
resulting pellets were molded into a rust preventive film for packaging.
EXAMPLE 19
85 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% of .alpha.-, .beta.- and
.gamma.-cyclodextrins was added to 15 parts by weight of thiavendazole and
the mixture was stirred at 70.degree. C. for one hour to give a material
containing a molecular inclusion compound of thiavendazole in
cyclodextrin. The obtained material was dried and ground in a vacuum drier
at 60.degree. C. to give a powder of 150 mesh or finer. 20 parts by weight
of this powder was melted together with 80 parts by weight of polyethylene
pellets. The molten mixture was pelletized by cold cut method. The
resulting pellets were molded into a film having a mold/mildew-proofing or
anti-fungi effect by calender process.
EXAMPLE 20
90 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% by weight of .alpha.-, .beta.-
and .gamma.-cyclodextrins was added to 10 parts by weight of
3-methyl-4-chlorophenol and the mixture was stirred at 70.degree. C. for
one hour to give a material containing a molecular inclusion compound of
3-methyl-4-chlorophenol in cyclodextrin. The obtained material was dried
and ground in a spray drier at 90.degree. C. to give a powder of 150 mesh
or finer. 10 parts of weight of this powder was melted together with 90
parts by weight of a polyvinyl acetate compound. The molten mixture was
pelletized by underwater cut method. Then 40 parts by weight of the
obtained pellets were mixed with 60 parts by weight of the polyvinyl
acetate compound and the resulting material was molded into a film having
a mold/mildew-proofing or anti-fungi effect by extrusion.
EXAMPLE 21
85 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% of .alpha.-, .beta.- and
.gamma.-cyclodextrins was added to 15 parts by weight of tolyltriazole and
the mixture was stirred at 70.degree. C. for one hour to give a material
containing a molecular inclusion compound of tolyltriazole in
cyclodextrin. The obtained material was dried and ground in a vacuum drier
at 60.degree. C. to give a powder of 150 mesh or finer. 20 parts by weight
of this powder was melted together with 80 parts by weight of polyethylene
pellets. The molten mixture was pelletized by cold cut method. The
resulting pellets were molded into a flower pot having a
mold/mildew-proofing or anti-fungi effect by injection.
EXAMPLE 22
10 parts by weight of .beta.-cyclodextrin and 80 parts by weight of a
reduced millet jelly were added to 10 parts by weight of liquid paraffin
and 10 parts by weight of benzotriazole and the mixture was stirred to
70.degree. C. for one hour to give a molecular inclusion compound of
liquid paraffin and benzotriazole included in cyclodextrin. The obtained
material was dried and ground in a vacuum drier at 60.degree. C. to give a
powder of 150 mesh or finer. 20 parts by weight of this powder was melted
together with 80 parts by weight of silicone resin. By the use of
injection molding machine (mfd. by Sanjo-Seiki Co. Ltd.), the molten
mixture was molded into a semiconductor substrate exhibiting a
rust-preventive and mold/mildew-proofing or anti-fungi effect.
EXAMPLE 23
10 parts by weight of .beta.-cyclodextrin and 60 parts by weight of a
reduced millet jelly were added to 15 parts by weight of liquid paraffin
and 15 parts by weight of 2-hydroxydiphenyl and the mixture was stirred at
70.degree. C. for one hour to give a material containing a molecular
inclusion compound of liquid paraffin and 2-hydroxydiphenyl in
cyclodextrin. The obtained material was dried and ground in a spray drier
at 80.degree. C. to give a powder of 150 mesh or finer. 20 parts by weight
of this powder was melted together with 80 parts by weight of epoxy resin.
The molten mixture was pelletized. The resulting pellets were molded into
a semiconductor substrate having a rust-preventive and
mold/mildew-proofing or anti-fungi effect.
EXAMPLE 24
90 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% by weight of .alpha.-, .beta.-
and .gamma.-cyclodextrins was added to 10 parts by weight of
3-methyl-4-chlorophenol and the mixture was stirred at 70.degree. C. for
one hour to give a material containing a molecular inclusion compound
consisting of 3-methyl-4-chlorophenol in cyclodextrin. The obtained
material was dried and ground in a spray drier at 80.degree. C. to give a
powder of 150 mesh or finer. 10 parts by weight of this powder was mixed
with 90 parts by weight of an alkyd resin coating to give a
mold/mildew-proofing or anti-fungi coating.
EXAMPLE 25
85 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% of .alpha.-, .beta.- and
.gamma.-cyclodextrins was added to 15 parts by weight of tolyltriazole and
the mixture was stirred at 70.degree. C. for one hour to give a material
containing a molecular inclusion compound of tolyltriazole in
cyclodextrin. The obtained material was dried and ground in a vacuum drier
at 60.degree. C. to give a powder of 150 mesh or finer. 10 parts by weight
of this powder was mixed with 90 parts by weight of a vinyl resin coating
to give a mold/mildew-proofing or anti-fungi coating.
EXAMPLE 26
90 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% by weight of .alpha.-, .beta.-
and .gamma.-cyclodextrins was added to 10 parts by weight of phthalthrin
and the mixture was stirred at 70.degree. C. for one hour to give a
material containing a molecular inclusion compound consisting of
phthalthrin in cyclodextrin. The obtained material was dried and ground in
a spray drier at 90.degree. C. to give a powder of 150 mesh or finer. 10
parts by weight of this powder was mixed with 90 parts by weight of an
acrylic resin adhesive to give a vermin-proofing adhesive.
EXAMPLE 27
85 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% by weight of a .alpha.-,
.beta.- and .gamma.-cyclodextrins was added to 15 parts by weight of
allethrin and the mixture was stirred at 65.degree. C. for one hour to
give a material containing molecular inclusion compound of allethrin in
cyclodextrin. The obtained material was dried and ground in a vacuum drier
at 60.degree. C. to give a powder of 150 mesh or finer. 10 parts by weight
of this powder was mixed with 90 parts by weight of a phenol resin
adhesive to give a vermin-proofing adhesive.
EXAMPLE 28
85 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% of .alpha.-, .beta.- and
.gamma.-cyclodextrins was added to 15 parts by weight of tolyltriazole and
the mixture was stirred at 70.degree. C. for one hour to give a material
containing a molecular inclusion compound of tolyltriazole in
cyclodextrin. The obtained material was dried and ground in a vacuum drier
at 60.degree. C. to give a powder of 150 mesh or finer. 10 parts by weight
of this powder was mixed with 90 parts by weight of a urea resin adhesive
to give a mold/mildew-proofing or anti-fungi adhesive.
EXAMPLE 29
85 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% of .alpha.-, .beta.- and
.gamma.-cyclodextrins was added to 15 parts by weight of
2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether and the mixture
was stirred at 70.degree. C. for one hour to give a material containing a
molecular inclusion compound of 2-(4-ethoxyphenyl in cyclodextrin. The
obtained material was dried and ground in a vacuum drier at 60.degree. C.
to give a powder of 150 mesh or finer. 20 parts by weight of this powder
was melted together with 80 parts by weight of polyethylene pellets. The
molten mixture was pelletized by cold cut method. The resulting pellets
were molded into a bactericidal film by calender process.
EXAMPLE 30
90 parts by weight of a reduced cyclodextrin millet jelly obtained by
reducing a decomposed starch containing 20% by weight of .alpha.-, .beta.-
and .gamma.-cyclodextrins was added to 10 parts by weight of
.alpha.-bromocinnamaldehyde and the mixture was stirred at 70.degree. C.
for one hour to give a material containing a molecular inclusion compound
consisting of .alpha.-bromocinnamaldehyde in cyclodextrin. The obtained
material was dried and ground in a spray drier at 90.degree. C. to give a
powder of 150 mesh or finer. 10 parts by weight of this powder was mixed
with 90 parts by weight of an acrylic resin adhesive to give a
bacteria-proofing or anti-fungi adhesive.
EXAMPLE 31
20 parts by weight of a mold/mildew-proofing and bacteria-proofing agent
N-(flurodichloromethylthio)phthalimide (Preventol A3; mfd. by Bayer Co.,
Ltd.) dissolved in acetone, 20 parts by weight of .alpha.-cyclodextrin and
60 parts by weight of mannitol (or xylitol) were mixed and the mixture was
stirred at 65.degree. C. in a conventional manner to give a molecular
inclusion compound. The obtained inclusion compound was powdered in a
spray drier. 10% of this powder was added to an acrylic emulsion coating
to give an emulsion coating having an excellent mold/mildew-proofing and
anti-fungi effect.
EXAMPLE 32
An unmodified liquid epoxy resin (Epikote; mfd. by Shell Chemicals Co.,
Ltd.) was included in cyclodextrin to form a molecular inclusion compound
which was then powdered at a low temperature drying. A polyolefinic
polymer powder (Dumiran; mfd. by Takeda Chemical Industries Co., Ltd.) was
mixed with the above cyclodextrin powder in a ratio of 3:1 and the mixture
was pelletized by the use of a special pelletizer and stored at room
temperature. This product was used in hot-melt coating with a coating
machine at an arbitrary time at a temperature of 90.degree. to 120.degree.
C. Thus an excellent adhesion accompanied by crosslinkage was facilitated.
Conventional nonincluded adhesives must be stored at lower temperature but
the product as described above can be stored at room temperature without
showing any crosslinkage, which is highly advantageous.
COMPARATIVE EXAMPLE 1
A vermin-proofing and insecticidal film containing fenitrothion produced in
a conventional manner (hereinafter referred to as sample 1) and another
vermin-proofing and insecticidal film containing fenitrothion and produced
by the process of the present invention (hereinafter referred to as sample
2) were prepared. Each film was allowed to stand at 25.degree. C. and the
change in the amount of fenitrothion contained therein was monitored by
high performance liquid chromatography. Samples 1 and 2 were as follows.
Sample 1: Fenitrothion (Sumithion; mfd. by Sumitomo Chemical Co., Ltd.) was
included in a millet jelly containing cyclodextrin (Celldex CH-20; mfd. by
Nippon Shokuhin Kako K. K. and containing 20% by cyclodextrin). The
obtained molecular inclusion compound was mixed with polyethylene pellets
and the mixture was molded into a film by inflation process.
Sample 2: This sample is a product of the present invention. The same
procedure as described relating to the above sample 1 was followed to
prepare film, except that the millet jelly containing cyclodextrin was
substituted by hydrogenated millet jelly containing cyclodextrin
(tentatively named 20H).
The following table shows the amounts (%) of residual fenitrothion
(Sumithion) in samples 1 and 2 determined with the initial amount of the
same as 100%. FIG. 1 s | | |
