Note: Descriptions are shown in the official language in which they were submitted.
;6~3
BACKGROUND OF THE INVENTION:
..
The present invention relates to an adhesive agent con-
twining micro capsules, and more in detail, relates to an adhesive
agent of a chemical reaction type or of an activation-by-solvent
type both containing micro capsules. Still more in detail, the
present invention relates to an adhesive agent containing micro-
capsules, comprising said micro capsules consisting essentially
of a core substance of at least one of the components constructing
said adhesive agent and as a material for the membrane of said
micro capsule, an aminoplast preliminarily treated by a modifier,
and a medium consisting of the other components constructing
said adhesive agent, said micro capsules dispersing in said
medium and said adhesive agent being the type of chemical
reaction or the type of solvent activation, and to a process
for preparing an adhesive agent containing micro capsules, the
pharaoh
process eel the step of dispersing micro capsules con-
sitting essentially of the core substance of at least one of
the components constructing the adhesive agent and a membranes
material consisting essentially of an aminoplast treated by a
modifier in the other components constructing the adhesive
agent.
Adhesive agents are classified according to the method
of ha/denlng hoFeof into the following four groups,
I
:
' . ' - 1 -
:~Z366~8
1) Adhesive agent of solvent-evaporation type:
After applying the agent, all the medium such as a
solvent or water originally contained therein disappears from
the applied agent by evaporation from the jointed end or absorb-
lion to the materials to be adhered, and the thus formed membrane
of the adhesive agent exhibits the maximum strength thereof.
2) Adhesive agent of chemical reaction type:
A hardened adhesive membrane is formed by a chemical
reaction between the resin and the hardener or between the
monomer (or oligomer) and the catalyst by mixing two separate
components of the adhesive agent, one of which contains the
resin or the monomer and the other of which contains the hardener
or the catalyst.
3) Adhesive agent of solvent activation type:
After painting the adhesive agent on the surface of
the body to be adhered and forming a dried membrane of the
agent on the surface, a solvent is sprayed there onto to react
tivate the painted surface of the membrane and then the other
body to be adhered is placed on the thus reactivated surface
of the membrane formed, thereby completing the adhesion.
4) Adhesive agent of hot melt type:
After applying the adhesive agent in the molten state
thereof onto the surface of the bodies -to be adhered, the thus
treated bodies are cooled so as to complete the adhesion.
The adhesive agent of chemical reaction type is composed
of two mutually separated components which are mixed just
before the application thereof and accordingly, such a type
of adhesive agent has the demerits of inconvenience in
- 2 -
lZ36618
application and of the limitation of the operation time after
mixing the two components and of the necessity of discarding
the remnant mixture of the two components.
While in the adhesive agent of solvent activation
type, there are problems of environmental pollution and in
industrial hygiene and safety because of the necessity of using
a large amount of an organic solvent. I
In order to solve the above-mentioned demerits of
some of the conventional adhesive agents, trials of encapsulating
a component thereof have been carried out, and micro capsules
provided with their membrane made of gelatin or polyamide have
been proposed.
However, since the membranes wall of the hitherto
proposed micro capsules are generally semipermeable or perforated
microscopically, the component of the adhesive agent contained
there within is apt to be extracted from the micro capsules,
and because of the poor resistance of the membranes wall to
an organic solvent such as alcohols, kittens and esters, there
has been the same kind of demerit of extraction of the content
in the micro capsule by such a solvent.
Particularly, in order to use micro capsules in an
adhesive agent to which a solvent-resistance is specifically
demanded, it is required that (1) the membranes wall of the
micro capsule is particularly excellent in solvent-resistance
and (2) the micro capsule itself is excellent in pressure-
responsiveness to be easily broken by a minute increment of the
I
pressure loaded thereon, and accordingly, it has been very
difficult to put such an adhesive agent containing the micro-
capsules in practical use. Namely, in order to improve the
solvent resistance of the micro capsules to solvents, there
have been tried a process of immersing the micro capsules in
a basic substance to activate the surface of the micro capsules,
a process of bringing the surface into contact with a vapour
of an alpha-cyanoacrylate and a process of coating the micro-
capsules with a substance resistant to the medium for dispersing
the micro capsules in the adhesive agent to form the double-
layered micro capsules. However, by such a process, the pressure
necessary for braking the micro capsules on application becomes
too large to use the thus treated micro capsules as the component
of the adhesive agent.
An object of the present invention is to provided an
adhesive agent containing the micro capsules excellent in solvent-
resistance and in pressure-responsiveness, the adhesive agent
solving the demerits of the conventional adhesive agents of
chemical reaction type and of solvent activation type and being
convenient and easy to be handled on application without the
necessity of using an excessive amount of components of the
adhesive agent.
SUMMARY OF THE INVENTION:
In the first aspect of the present invention, there is
provided an adhesive agent containing micro capsules, comprising
said micro capsules consisting essentially of a core substance
I:
_ _
:~3661~3
of at least one of the components constructing said adhesive
agent and, as a material for the Myron of said micro capsule,
an aminoplast preliminarily treated by a modifier, and
a medium consisting of the other components constructing
said adhesive agent, said micro capsules dispersing in said medium
and said adhesive agent being the type of chemical reaction or
the type of solvent activation.
In the second aspect, there is provided a process for
preparing an adhesive agent containing micro capsules 7 of the
type of chemical reaction or the type of solvent activation,
comprising
dispersing minute liquid particles of at least one of
the components of said adhesive agent in an aqueous dispersion
of the components for forming an aminoplast, adding an acid
catalyst to said aqueous dispersion, thereby bringing the
prepolymer of said components for forming said aminoplast into
polycondensation, adding a modifier to said aqueous dispersion
during or after the completion of said pol~condensation, thereby
forming said micro capsules encapsulating said at least one of
said components within the membrane consisting essentially of
said aminoplast modified by said modifier,
collecting and drying the thus formed micro capsules,
and
dispersing said micro capsules in the other components
constructing said adhesive agent containing micro capsules.
1~;~66~L~
DETAILED EXPLANATION OF THE INVENTION:
The characteristic of the present invention is in an
adhesive agent containing micro capsules of the type of chemical
reaction or the type of solvent activation, said micro capsules
consisting essentially of (1) a core substance of one or more
than one components of the adhesive agent, which is (are) to be
encapsulated within the micro capsule and (2), as a material of
the membrane of the micro capsule, an aminoplast treated pro-
liminarily by a modifier in a system consisting essentially of the
other components of the adhesive agent.
Namely, the adhesive agent containing the micro capsules,
which is the type of chemical reaction or the type of solvent
activation according to the resent invention takes a form of,
in the case where it is the type of chemical reaction, namely,
for instance, in the case where the component of the adhesive
agent consisting essentially of a resin and a hardener or of
a monomer or an oligomer and a catalyst, an adhesive agent
containing the micro capsules encapsulating, as a component,
the hardener or the catalyst (preferably as small as possible in
amount) dispersed in the resin or the monomer and/or the oligomer.
In addition, in the case where the component is a multi-component
system such as that consisting essentially of the monomer, the
catalyst and the hardener, the micro capsules containing the
catalyst or both the catalyst and the hardener are dispersed in
the monomer in order to prevent the reaction between the catalyst
and the monomer, and between the hardener and the monomer.
: ::
1~3~61~1
In this connection, not less than two components which
do not mutually react may be separately encapsulated, however,
it is preferable to encapsulate not less than two such components
simultaneously, and in addition, the catalyst or the hardener
may be encapsulated in a dissolved state in a solvent.
On the other hand, -the adhesive agent containing micro- I
capsules according to the present invention takes another form of, ¦
in the case where it is the type of solvent activation, an
adhesive agent containing the micro capsules encapsulating a solvent
necessary for dissolving and activating the resin which is to
form the adhering membrane dispersed in a solution which contains
the resin to be painted on the surface of a material to be adhered
(hereinafter referred to as "the resin solution"). Consequently,
according to the present invention, since it is necessary to
encapsulate the smallest amount of the solvent necessary for
activating the resin, the problem of the conventional adhesive
agents of the type of solvent activation, caused by the use of
a large alienate of a solvent, can be solved by this type of adhesive
agent.
The important matter in encapsulating at least one of
the components of the adhesive agent is that the membranes wall
forming the micro capsule is excellent both in solvent-resistance
and in pressure-responsiveness.
As a result of the present inventors' studies for obtain-
in the material for forming a membranes wall of the above-
mentioned specificities, it has been found by them that an amino-
plats preliminarily treated by a modifier is suitable as the
- 7 -
1~3~618
above-mentioned material. The "aminoplast" herein mentioned means
a resin obtained by bringing at least one prepolymer selected from
the group consisting of melamine-formaldehyde prepolymers, urea-
formaldehyde prepolymers, melamine-urea-formaldehyde prepolymers,
melamine-thiourea-formal,dehyde prepolymers and melamine-thiourea-
urea-formaldehyde prepolymers or a mixed prepolymer containing a
melamine-formaldehyde prepolymer and a thiourea-formaldehyde
prepolymer into polycondensation in the presence of both a water-
soluble cat ionic urea resin and an anionic surfactant.
The material for the membrane of the micro capsule
according to the present invention comprises an aminoplast
prepared by polycondensa-tion in the presence of a modifier.
The micro capsule formed of the thus treated aminoplast
is superior in solvent-resistance and free-flowing property to
the micro capsule formed of the aminoplast which has not been
treated, and in the same time, the micro capsule formed of the
thus treated aminoplast exhibits an excellent pressure-responsive-
news.
As the modifier used for the above-mentioned object,
a finlike compound such as phenol, resorcinol, catcall,
hydroquinone, crossly, Tylenol and saligenin and a polyalkylene-
polyamide compound such as hexamethylenetetramine and triethylene
thiamine may be exemplified.
In order to form the micro capsules according to the
present invention, minute liquid particles of the component(s)
:
- 8 -
Jo
of the adhesive agent, which is (are) to be encapsulated are
dispersed in an aqueous liquid in which the aminoplast prepolymer,
the water-soluble cat ionic urea resin and anionic surfactant
have been dissolved, and in the -thus prepared aqueous suspension,
an cold catalyst, for instance, a carboxylic acid of a low mole-
cuter weight such as formic acid, acetic acid and citric acid,
an inorganic acid such as hydrochloric acid, nitric acid and
phosphoric acid or a salt of which the aqueous solution exhibits
an acidity or an easily hydrolyzable salt such as alunimum sulk
fate, titanium oxychloride, magnesium chloride, ammonium chloride,
ammonium nitrate, ammonium sulfate and ammonium acetate is
added, and then, while causing a complex-coacervation by the
water-soluble cat ionic urea resin and the anionic surfactant
both of which have been dispersed in the aqueous dispersion of
the aminoplast, the prepolymer and the water-soluble cat ionic
urea resin are brought into polycondensation to form a hydropho-
big membranes wall of a high molecular weight which completely
covers each of the minute liquid particles of the components
of the adhesive agent, which have been dispersed in the system,
thus resulting in micro-encapsulation.
In the case where the above-mentioned modifier is
added to the system during the polycondensation, the capsular
membranes wall comprising the aminoplast treated with the
modifier as has been explained is formed.
:
1~3SÇ~18
The amount of the modifier is 0.1 to 30% by weight,
preferably 0.5 to 20% by weight to the prepolymer, the modifier
is preferably added as an aqueous solution thereof at a con-
cent ration of 0.02 to 5% by weight.
In this connection, the water-soluble cat ionic urea resin
used for taking place the complex coacervation and for preparing
the above-mentioned aminoplast is the substance obtained by
introducing a cat ionic modifying group into a urea-formaldehyde
resin, namely the product of polycondensation of, for instance,
urea-formaldehyde prepolymer with polyalkylenepolyamine, guanidine,
diaminoethanol, dicyandiamide, diethylaminoethanol and gainlier.
As the anionic surfactant, a substance such as those
having a lipophilic group and an anionic - hydrophilic group
in their molecule, for instance, salts of fatty acid, sulfate
esters of higher alcohols and salts of alkylarylsulfonate may be
mentioned, and for instance, sodium dodecylbenzenesulfonate is
preferably used.
In addition, in the polycondensation for the formation
of the micro capsules in the present invention, it is important
that the two kinds of substances which are mutually different
from each other concerning their sign of electric charge are
coexistent with the prepolymer, the one of the substances being
the water-soluble cat ionic urea resin and the other of the
substances being the anionic surfactant. Owing to such an
important situation, it is possible to obtain a stabilized
aqueous dispersion containing micro capsules uniform in quality.
1~:3~6~8
Since the micro capsules of the present invention can
be processed into a free-flowing powdery state after preparation
by easily separating from the medium for dispersion used in the
preparation thereof and drying thereof, the micro capsules
are excellent in solvent resistance they are favorably suitable
for forming the adhesive agent by uniformly dispersing in the
other components of the adhesive agent.
The following is the concrete explanation of the
adhesive agent containing the micro capsules according to the
present invention (1) in the case where it is the type of
chemical reaction and also (2) in the case where it is the type
of solvent activation.
(1) Adhesive agent of the type of chemical reaction:
For the preparation of the adhesive agent of the type of
chemical reaction, namely the adhesive agent comprising a resin, a
monomer or oligomer for adhesion, an initiator of the reaction and
a hardener, any one of these components may be encapsulated
in the micro capsules and the micro capsules may be dispersed in,
a mixture of the other components. As the component encapsulated
in the micro capsules, the component smaller in amount, namely
the initiator of the reaction or the hardener is generally
selected. The kinds of the components encapsulated in the
micro capsules may be not less than two, and not less than two
kinds of the components may be encapsulated together or the
respective components may be separately encapsulated.
123~
As the resin for adhesion, poly(acrylic acid), polymath-
acrylic acid), epoxy resin, polyester, polyamide, polyurethane
copolymer of urethane and lower alkyd acrylate or lower alkyd
methacrylate, copolymer of dicarboxylic acid, dill and lower alkyd
acrylate or lower alkyd methacrylate, epoxidized poly(lower alkyd
acrylate), epoxidized poly(lower alkyd methacrylate), low-molecular
silicone resin, natural rubber, neoprene rubber, polyvinyl
acetate) and polystyrene may be mentioned. The micro capsules
containing the necessary initiator for the reaction or the
necessary hardener are dispersed in at least one resin selected
from the above-mentioned resin and their monomers or oligomers
for adhesion or in a solution prepared by dissolving thereof in
an organic solvent.
As the initiator of the reaction, dibutyl-tin dilaurate,
stuns caprylate or a solution of an organic peroxide such as
y/
be l peroxide and dibutyl peroxide in an organic solvent may be
mentioned, and as the hardener, N,N-dimethylaniline, N,N-dimethyl-
Teledyne and the like may be mentioned.
In the case of utilizing the adhesive agent containing
micro capsules of the type of chemical reaction, it is painted
on one of the surfaces of a body, which is to be adhered and then
the other body to be adhered to the first body is piled onto the
first body so as to pinch the thus painted surface of the first
body and then a pressure is applied onto the thus piled bodies
from the side of the second body.
Then the micro capsules are easily broken to allow the
free contact of the content of the micro capsules with the other
- 12 -
SLY
components painted on the surface of the first body thereby the
hardening is proceeded to obtain a strong adhesion of the two
bodies. The adhesive agent containing micro capsules of the
type of chemical reaction can b applied -to any surface by one
ox several means such as to spraying, brushing, etc.
(2) Adhesive agent of the type of solvent activation:
For the preparation of the adhesive agent of the type
of solvent activation, the micro capsules containing an organic
solvent activating the resin which constitutes the adhesive
membrane may be dispersed in the resin solution which constitutes
the adhesive membrane.
As the organic solvent possibly encapsulated, almost
all the generally used solvents are suitable for use, and
hexane, Hutton, Bunsen, Tulane, zillion, carbon tetrachloride,
trichloroethylene and tetrachloroethylene may be mentioned.
As the resin activated by the solvent, neoprene rubber,
bottle rubber, styrene-butadiene rubber, natural rubber, polyp
styrenes polyvinyl acetate), methyl cellulose, ethyl cellulose
polyvinyl chloride), copolymer of ethylene and vinyl acetate,
acrylic resin, methacrylic resin, polyamide, copolymer of vinyl
acetate and lower alkyd acrylate may be mentioned.
The adhesive agent of the type of solvent activation
according to the present invention comprising the above-mentioned
micro capsules containing the solvent as the core substance
dispersed in the resin solution which is to constitute the
adhesive membrane and the resin. On the occasion of applying the
~3~i~18
adhesive agent of the type of solvent activation, the adhesive
agent is painted on the surface to be adhered of one of the two
bodies to be adhered, and after drying the thus painted adhesive
agent, the body thus having a painted surface is placed on to
the other of the two bodies to be adhered while applying a pros-
sure onto the first body, thereby the micro capsules being broken
by the pressure to allow the solvent freely activate the
component of the resin in the painted surface resulting in
a good adhesion.
Also the adhesive agent containing microcapsu~es of
the type of solvent activation can be applied by
spraying, brushing etc. onto the surface of a body, which is
to be adhered to other body.
Since the micro capsule used in the present invention
can be easily broken by applying a pressure of lower than
10 kg/cm2, the above mentioned adhesion of two bodies by
lamination and pressing is easily carried out.
Accordingly, the adhesive agent containing micro capsules
according to the present invention has a merit of utilizing in
a broad field of adhering.
The present invention will be more precisely explained
while referring to Examples as follows.
However, the present invention is not restricted
to Examples under-mentioned. From the foregoing description,
one skilled in the art can easily ascertain the essential
characteristics of the present invention, and without departing
1~:36618
from the spirit and scope thereof, can make various changes and
modifications of the invention to adapt it to various usages
and conditions.
EXAMPLE 1:
1-1: Preparation of two prepolymers
After adjusting the pi of 162 g of aqueous 37 solution
of formaldehyde (hereinafter referred to as formal in) by the
addition of aqueous 2 % solution of sodium hydroxide to 9.0, it
was mixed with 63 g of mailmen, and the mixture was brought into
reaction while stirring the mixture at 70~. Just after confirming
the complete dissolution of mailmen in the reaction mixture, 225 g
of water were added to the reaction mixture, and the mixture was
stirred for 3 mix to obtain an aqueous solution of a prepolymer of
melamine-formaldehyde resin hereinafter referred to as M4F pro-
polymer, M4F meaning that the molar ratio of mailmen to formalde-
Hyde is I in the prepolymer).
Separately, after adjusting the pi of 146 g of formal in
by the addition of triethanol amine to 8.5, it was mixed with 60 g
of urea, and the mixture was brought into reaction for 1 hour at
70C to prepare an aqueous solution of a prepolymer of urea-
formaldehyde resin hereinafter referred to as U 1.8 F prepolymer).
1-2: Preparation of a cat ionic urea resin
After adjusting the pi of a mixture prepared by mixing
162 g of formal in and 60 g of urea and stirring the mixture to 8.8
by the addition of triethanolamine, the mixture was brought into
reaction for 30 mix while stirring the mixture at 70C. Into 40 g
.
1~3S6~8
of the reaction mixture, 24 g of water and 3 g of tetraethylene-
pent amine were added, and the pi of the mixture was adjusted to 3.
by the addition of aqueous 15 % hydrochloric acid solution while
stirring the mixture at 70C, and the reaction was carried out
for 1 hour. Since the pi of the reaction mixture was reduced
with the progress of the reaction, aqueous 10% solution of
sodium hydroxide was added to the reaction mixture to adjust
the pi thereof to 3.0, and the reaction was continued at a
reduced temperature of 55C. At the time when the viscosity
of the reaction mixture became 200 cups, the reaction mixture
was neutralized with the addition ox aqueous 10% solution of
sodium hydroxide and 400 g of water were added to the neutralized
mixture to obtain an aqueous solution of the water-soluble
cat ionic urea resin.
1-3: Microcapsulation
A mixture consisting of 100 g of M4F prepolymer (refer
to 1~1), 50 g of U 1.8 F prepolymer (refer to 1-1), 158 g of
the aqueous solution of the water-soluble cat ionic urea resin
(refer to 1-2), 62 g of water and l g of triethanolamine was
adjusted to pi of 5.2 by the addition of aqueous 10% solution of
citric acid, and by admixing the mixture with 3 g of aqueous
10% solution of NEPAL (sodium dodecylbenzenesul~onate, made
by KETTLES Coo Japan) a solution named as A-liquid was
obtained.
Into the thus prepared A-liquid, 200 ml of zillion were
dispersed so tout the mean diameter of -the dispersed particles
- 16 -
1~36611 8
of zillion is 30 to 50 micrometers. The thus obtained aqueous
dispersion was brought into reaction for one hour while gently
stirring the dispersion and maintaining the dispersion at a
temperature of 30C and adding aqueous 10% solution of citric
acid to -the dispersion to adjust the pi of the dispersion at
3.6. After the lapse of further one hour, aqueous 10% solution
of citric acid was added to the reaction mixture to adjust the
pi thereof to 3.0, and then 20 ml of aqueous 10% solution of
resorcinol were added to the mixture. The microcapsulation
was completed after the further continued stirring for 18 hours.
After collecting the thus formed micro capsules, the capsules were
washed with water and dried in an air-drier at 35C to be powdery
micro capsules of the mean diameter of 30 to 50 micrometers.
I Preparation of an adhesive agent being the type
,. .
of solvent activation as the final product:
To a solution prepared by dissolving 100 parts by weigh-t
of masticated neoprene rubber in 500 parts by weight of Tulane,
one part by weight of a phenol resin and one part by weight
of a Cameron resin were dissolved, and after adding 30 parts
by weight of the micro capsules prepared in (1-3) to the thus
prepared mixture, the whole mixture was uniformly mixed to obtain
the adhesive agent containing the micro capsules.
EXAMPLES 2 to 9:
In the same procedures as in Example 1 except for
using each prepolymer for membranes wall-formation and each
modifier show in Tale 1 instep of those used in Example 1,
123~618
eight kinds of the adhesive agents according to the present
invention were obtained.
1;~;3~i6~8
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3~i18
The respective prepolymers specified in Table 1 were
prepared as follows:
Preparation ox the prepolymers
*1: Tug 1.8 F used in Example 4
After adjusting the pi of 146 g of formal in to 8.5 by
the addition or triethanolamine, the former was mixed with
76 g of Thor, and the mixture was brought into reaction for
one hour at 70C to obtain an aqueous solution of the prepolymer
of Tug 1.8 F (one mow of Thor: 1.8 mows of formaldehyde)
*2:_ MTu4F used in Example 7
After adjusting the pi of 324 g of formal in to 9.0 by
the addition of aqueous 2% solution of sodium hydroxide, the
former was mixed with 63 g ox mailmen and 38 g of Thor,
and the mixture was brought into reaction at 70C, and just
after confirming the complete dissolving of mailmen and Thor
into the reaction mixture, 425 g of water were added to the
reaction mixture, and the resultant liquid was cooled to room
temperature as it was.
*3. MTuU5F used in Example 8
After adjusting the pi of 405 g of formal in to 8.5 by
the addition of triethanolamine, the former was mixed with 42 g
of mailmen, 25 g of Thor and 20 g of urea, and the mixture
was brought into reaction at 70C for one hour, and the product
was cooled to room temperature.
3~i18
*4: MUFF used in Example 9
After adjusting the pi of 324 g of formal in to 8.5 by
the addition of triethanolamine, the former was mixed with 63 g
of mailmen and 30 g of urea, and the mixture was brought into
reaction for 30 mix at kiwi After adding 225 g of water to
the reaction mixture, the mixture was cooled to room temperature.
TEST EXAMPLE 1:
Each of the adhesive agents respectively prepared in
Examples 1 to 9 was painted on a plate of posy (vinyl chloride)
of 0.5 Mooney thickness at a rate of 6 g of the adhesive agent/m2
of the plate, and by drying the thus painted plate for 2 hours
at 40C, a painted surface without stickiness was obtained.
; Then, another plate of posy (vinyl chloride) of 0.5 mm
in thickness was piled onto the painted surface of the plate to
have a laminate having two layers of posy (vinyl chloride)
intervened by a layer of the adhesive agent, and the laminate
was passed between the two pitch-rolls of a rolling pressure
adjusted to 10 or 200 kg/cm2 to obtain an adhered body.
After leaving the adhered body as it was in an ordinary
room for 24 hours, the adhesion between the two plates was
tested.
The results are shown in Table 2 wherein the test
results on the adhered body prepared by the adhesive agents
prepared in the following Comparative Examples 1 to 5 are also
shown for comparison.
- 21 -
1~3~i618
Table 2
Adhesion of the two plates adhere
Adhesive agent under a pressure of
prepared in _
10 kg/cm 200 kg/cm
I I
Example 1 good good
Example 2 good good
Example 3 good good
Example 4 good good
Example 5 good good
Example 6 good good
Example 7 good good
Example 8 good good
Example 9 good good
_
Comparative Example 1 poor good
Comparative Example 2 poor poor
Comparative Example 3 poor poor
Comparative Example 4 poor poor
Comparative Example 5 poor poor
I:
123~6~8
Note to Table 2
In Table 2, adhesion good means that the two plates
were so firmly adhered together that any owe ox the two plates
could not be moved in regard to the other of them by hands,
and on the other hand, adhesion poor means that one of the two
plates could be separated easily from the other by hands or the
two plates were not adhered together.
COMPARATIVE EXAMPLE 1:
. __
By the same procedures as in Example 1 except for
dispensing the addition of resorcinol as the modifier, an
adhesive agent containing micro capsules was obtained.
COMPARATIVE EXAMPLES 2 to 4:
While using 100 g of M4F prepolymer prepared by the
same procedures as in Example 1(1-1) and 50 g of U 1.8 F pro-
polymer also prepared by the same procedures as in Example 1(1-1),
however, using one of the third components shown in Table 3
instead of the water-soluble cat ionic urea resin and NEPAL
in Example 1, thereby obtaining a liquid corresponding to A-
liquid in Example 1, 176 g of zillion were dispersed in the liquid
under the same conditions as in Example 1. In the case where the
pi of the thus formed aqueous dispersion became lower than 5.0,
the pi of the liquid corresponding to A-liquid was adjusted to
5.0 by the addition of aqueous solution of sodium hydroxide.
The aqueous dispersions brought into reaction under the
same conditions and according to the same procedures as in
Example 1, however, without adding the aqueous 10 %
::
- 23 -
lZ36618
solution of resorcinol to obtain an aqueous dispersion of micro-
capsules. After collecting the micro capsules and washing thereof
with water, the washed micro capsules were air-dried.
By using the thus prepared micro capsules, an adhesive
agent containing the micro capsules was obtained in the same
procedures as in Example 1.
Table 3: Substance used as the third component
___
instead of water-soluble cat ionic urea
resin and NEPAL
. .
n Comparatlv Sup e eddy I- the ire component
2 loathing used
. . _ Jo . _._
SCRIPPS 520 (copolymer of styrenes and
3 malefic android, made by Monsanto Co.)
as an aqueous 5% solution thereof: 75 g
.. __ _ . _. .-- - ------- ---
a reactive surfactant (disclosed in Japanese
. 4 Patent Application Laying Open No. 46-7313
_ (197~ 20 g .
::
COMPARATIVE EXAMPLE 5:
: After dispersing 176 g of zillion in 275 g of an aqueous
10%~ by weight solution of gelatin at 50C as particles of 30 to
: 50 micrometers in the mean diameter thereof, aqueous 10% solution
I:
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lZ;~i618
of gum Arabic and 450 ml of water were added thereto while
gently stirring thereof, and after adjusting the pi of the thus
formed mixture to 4.4 by the addition of aqueous 10% solution
of acetic acid and leaving the mixture as it was for 10 mint
the mixture was cooled to 5C and 36.5 ml of aqueous 25% solution
of glutaric alluded was added thereto, and the mixture was
stirred for one hour. After heating the mixture again to 50C
and continuing the stirring for 30 mint the mixture was cooled
to room temperature to obtain a slurry of micro capsules. By
using the dried, powdery micro capsules obtained by spray-drying
the slurry of micro capsules, an adhesive agent containing the
micro capsules was prepared in the same procedures as in Example 1.
It was found by examining the respective adhesive
agents prepared in Comparative Examples 2 to 5 that the organic
solvent originally encapsulated in the micro capsules had been
evaporated off completely from the micro capsules without leaving
anything.
EXAMPLE 10:
By the same procedures as in Example 1 except for using
176 g of a 5% solution of triallyl sonority in zillion or 176 g
of a 5% solution of tertiary bottle perbenzoate in deathly
phthalate instead of 176 g of zillion in Example 1, two kinds
of the powdery micro capsules were prepared.
Separately, an adhesive agent was prepared by adding
0.5 part by weight of peroxide and 10 parts by weight of
methyl Matthew yule into a solution prepared by dissolving 0
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I. `
isle
parts by weight of a tripolymer of ethylene, propylene and lo
hexadiene into 360 parts by weight of Tulane and bringing the
mixture into reaction for 5 hours at 80C.
An adhesive agent of the type of chemical reaction was
prepared by blending 100 parts by weight of the thus obtained in-
polymer and 6.5 parts by weight of the powdery micro capsules pro-
pared by using triallyl sonority and 4.0 parts by weight of the
powdery micro capsules prepared by using Perbutyl Z. By painting
the thus prepared adhesive agent on the two respective Lyon
plates and laminating them with their painted surfaces together
and pressing the thus laminated body under a pressure of 10 kg/cm2
at 50C, a favorably laminated and adhered body was obtained.
In addition, the thus prepared adhesive agent containing
the two kinds of the micro capsules retained the original adhesion
even after one month of preservation
EXAMPLE
By the same procedures as in Example 2 except for using
224 g of deathly phthalate containing 56 by weight of
peroxide instead of 176 g of zillion in Example 2, a kind of
micro capsules was prepared.
Separately, a mixed solution was prepared by dissolving
7 parts by weight of poly(methyl methacrylate) in a mixed
solvent consisting of 150 parts by weight of bottle acetate,
120 parts by weight of ethyl acetate and 30 parts by weight of
methyl isobutyl kitten, and further adding 40 parts by weight
of methyl methacrylate and loo part by weight of N,N-dimethyl-
Teledyne to the thus formed solution.
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~Z31j618
By admixing the thus prepared mixed solution with
6.5 parts by weight of the micro capsules prepared as above, an
adhesive agent of the type of chemical reaction, was obtained.
After spraying the adhesive agent onto a soft steel plate
and evaporating the solvent, another soft steel plate was placed
on the thus painted surface of the former soft steel plate, and
by applying a pressure of 10 kg/cm2 onto the thus laminated
soft steel plates, a laminated and adhered body of soft steel
plate was obtained while breaking the micro capsules, and the
body showed a strong adhesion between the components after
10 min.
COMPARATIVE EXAMPLE 6:
,...
In the same procedure of microcapsulation.in Compare-
live Example 5 except for using 224 y of deathly phthalate
containing 5% by weight of be}. peroxide instead of 176 g of
zillion ion Comparative Example 5, a kind of rnicrocapsules was
obtained.
After preparing an adhesive agent by admixing 6.5 parts
by weight of the thus prepared micro capsules with the same mixed
solution as in Example 11, the thus prepared adhesive agent was
I sprayed on a soft steel plate and evaporated the solvent. By plea-
in another soft steel plate on the thus painted and dried surface !
of the former soft steel plate and applying a pressure of 10 kg/cm
onto the thus laminated soft steel plates as in Example 11~ a
laminate body was obtained, however, the adhesion between the
two plates was not satisfactory. No improvement of adhesion was
:
_ I - ` I
'1~3~L8
obtained in another test of soft steel plate lamination even by
applying a pressure of 200 kg/cm2 while using the same adhesive
agent.
EXAMPLE 12:
By the same procedures for preparing the micro capsules
as in Example 6 except for using 180 g of a mixture of 100 parts
by weight of EON 828 (an epoxy-resin, made by duo Pont Co.) and
10 parts by weight of zillion instead of 176 g of zillion in
Example 6, a slurry of micro capsules was prepared.
After collecting the micro capsules from the slurry,
the micro capsules were washed with water and dried to be freely-
flowing powdery micro capsules.
By admixing a solution prepared by dissolving 100 parts
by weight of N-methoxy-(methylated nylon), so-called nylon 8,
into 200 parts by weight of methanol with 20 parts by weight of
the thus prepared free-flowing powdery micro capsules, an ache-
size agent containing micro capsules was prepared.
After painting the thus prepared adhesive agent on a
single Lyon plate, another single Lyon plate was placed thereon
and by applying a pressure of 10 kg/cm2 onto the thus laminated
body at 70C, a strongly adhered body of laminated Lyon plates
was obtained.
Even after leaving the thus laminated body for one
week at a temperature of 70C and a relative humidity of 75 %,
no noticeable deterioration of adhesion was found between the
adhered plot
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~3~L8
In addition, the thus prepared adhesive agent count awn-
in the micro capsules could be preserved in a stable state
without gellifying even after one month.
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