Note: Descriptions are shown in the official language in which they were submitted.
~l24~i8~
B.~CKG~QUND OF THE INV~NTION
The pre6ent ~nvention relat~s to a method of producing a
porous ~aterlal having open pores. ~Sore particularly, the
lnvention i~ ooncerned with a method o~ producing a porous
~.aterial h~Ying open pore~ from a raw material whic~ comprise~
a bisphenol-type epoxy re~ln, a fipecific mixture amide
compound as a hardener, iller and water.
~ itherto, as me~ure~ for producing a porous material
having open pore~ for uBe a~ a filtering mediu~, air di~fusion
l~ med~um, casting mold and so forth~ var~ous methods have been
produced ~uch as ~ln~ering of met~l powder, sintering of
powdered thermoplast~c resin, ~intering of inorganic powder,
hydration ~etting of cement or the like, press~ng or stamping
of a mi~ture of thermos~eting resln and filler, hardening of a
re~n 11qu~d containlng por~-formi~g agent followed by the
remo~l of the pore~formlng ~gent by dis~olving, extracti~n or
eYaporation, us~ of a ~lo~ing agent, evaporation of water from
~ater-containing polye~ter resin, an~ ~o forth.
The~e known method~ of producing porou~ material having
open pore~, however, encountered one or more of the following
problems in connectlon wlth the molding proces~. First of
all, it i~ to be pointefl out that the~e known methods
impractically limit or restrict the shape and size of the
pr~duct. In addition, these method~ ot~n require a heat
tr~atment at high temperature, a~ well as a press work at high
pre~urefi. ~he method which makes use of the pore-~orming
agent mu~t em~loy a st~p of heating or vacuum operation for
the rem~val o~ the pore-forming agent hy evaporation,
- 2 -
~6~
Furthermore~ the~e known me'chod~ ar~ generally complicated and
dif f icult to conductO
Another problem i5 that, ~ith these kno~n me~hod~, lt i8
~uite difficult to effect the pore ~ize control wh~ch i~ the
5 most i~portant factor when the porous mater ial i~ use~ as a
filtering medium, ~ir diffu~ >n mediumt ca~ting mold or the
like du~ to the following reason~.
In the production of a pOroslB m8ter ial f ~om metal powder
by ~interirlg, i~ difficu11: ~o obtaln a pore ~ize ~maller
10 than 5 mic:ror~& because of a specif ic relation be~ween the
par~lcle siæe of the metal powa~r and the ~urface energy
durlng the B1nter ing. Con~equently~ it i8 quite dlficul~ to
effect control of the pore ize to obtain pores on the order
of 1 ~ic:ron or ~o. In 'che case of the ~interlng of the p:3wd~r
15 of a cer~ .materia:L or resln, the pas:king den~ity at the
time of moldiny i8 almost impo~sible to control although the
particle size of the mater Lal can be controll~d f inely. In
additlon~ th$s method ~uffer~ from ~ large change in the pore
structure in the cour~e ~f the ~intering, 80 that the pore
20 si~e is distributed over a wlde range to hinder the control o~
th~ pore ~ize.
Referring now to ~he pressing and ~tamping of a solid
powder together w~th a hinder such as an adhesi~e, the control
of the pore ~lze ie impaired particularly when the product has
25 a compl~cated shape, for the re~son~ s~ch a~ non-uniform
packing due to non-uniform application of the molding pressure
attributahle to the complicated shape of the product, non-
uniform mixing of the binder, and sc on.
-- 3 --
~6~
In the case of the hydr~ti~n ~ardening of a ce~lent,
gyp~um, plaster or the like, difficulty is l~olved 1n thecontrol of the nucleation and srowth of the crystal~ o~ the
hydrate, and preci~e control of the mean pore size to ob~ain
pores on the order of 0.5 to 10 microns car.not easily
be effected.
~ ith resard to the method in which the pore for~ing agen~
is evaporate~ or ex~racted from ~he hardened resin con~ainirg
the agent, a techni~ue has been proposed for the production of
a thin film having pores of pore ~izes ranging between 1000
and 100~. This ~e~hod, however, cannot be applied to
the production of a ~roduct havlng ~ large shape. In
the method in which a resin in the form of 0/W- or ~/0-type
emul~ion i5 hardene~ followed ~y the evaporatlon o~ th~
di~per80id, it i~ not easy to control the size of the
disper80id, ~nd many disconnected pores are in~vitably for~ed.
The control of the pore size on the order of ~.5 to 10 mlcrQns
a6 a mean ts also difficult in thi~ method.
In order to obviate these problems of the known methods,
~a~anese PaL2~-L .~o. 924,027 issued on septem~er 2~, 197~ -,o
t~e ~L~plicanL ~-o~oses a met'nod o~ pro~ucing a ~orous mateli21
having open pores and ~ complicated shape, at a high precision
and w~th a good control of the pore si2e. More ~pecifically,
this method compri~e6 the steps of preparing an 0~' type
2S slurry as a mixture of a glycidyl-type epoxy re5in, polymeric
fatty acid polyamide hardener, filler and ~ater, casting the
~lurry in a water-~permeable mold, hardening the water-
containing 81urry, and then dehydratlng the hardened body.
-- 4 --
a~ ~
:~4~
According to this metho~ i8 possible to e~ect the~ c:ontrol
of the pore si~e by varylng and ~dJu~tin~ factor~ such ~ the
part~cle size of the filler~ amount of the reactive diluent,
mixing ratio of the epoxy r~sln, hardener, filler and water,
S and so on. P,mong th~se factors, the amount of the reactive
diluent and the mi~ing ratio of the ~poxy re~in~ hardeneL ~
filler and water a~e limited from the viewpoint of contraction
durlns~ hardening and al~o in view of the ~reng~h of 'che
hardened body. ~or thi~ rea~on, it i~ not pos~ible to c:ontrol
10 the pore ~ize over a wlde range. In order to control the pore
~i2e to obtain pores on the order of O. 5 to lO micron~, it is
neces~ary to largely vary the particle ~ize of the filler.
The use of the filler having large -partlcle slze, however,
reduces the ~trer~gth o~ the hardened body undesirably. The
15 reduct~on of streng~ch can be avoided only through a reduction
ln th~ Elmoun~ of watar added, wh~ch ~n turn is accompaniel9 by
a new proble~ of an increa~ in tne ~l~co~lty of the ~lurry.
The lncreased part~le slze of the ~iller cause~ alæo anotber
problem namely that the effic~ency of the ~ork is lmpaired due
to sedimentation of the filler in the slurry which consist~ of
water and the filler. When ~ flller having a mean slze
~uitable for the work i~ used, t~e mean pore size in the
product porous materlal i8 unde~lrably concentrated to an
ext~eme~y sm~ll level o~ le6~ than 1.5 microns. The poro~
m~terial having such extremely small pore slze can hardly be
used for the a~ore~entioned application~ ~uch ~q filtering
~edium, alr diffu~ion mediu~ ca ting mold and ~o forth and,
hence, has only ~ small pr~ctical utillty. Furthermore, thi~
~4~
propo~ed method ~uffers rom problems such a~ the
impract1cally long tlme requlr~d for the slurry to flow into
the ~old ~nd difflculey ln forming a porous materlal having an
intricate and compllcat~d ~hape, due to the high viscosi~y of
the ~lurry attributabl~ ~o the u~e of a polymerlc ~tty acid
polya~ide solely as the hardener.
~U~ARY ~F T~ V~NTIO~
.... _ _ .
Under this circumstance, the preBent lnvent~on ~lm~ at
1~ provid~ng a method of producing a porou6 material havlng open
pores of a desired mean pore ~ixe (opening), thereby to
obv~ate the problems of the prior art~
Namely, it ~ an object of th~ inventlon to .prov~e a
method o~ produclng a porou~ materi~, wh~ch 1~ improved to
permit the control of the maan pore ~ize over a wide range
without requiring any change in th~ partl~l~ s~ze of the
filler.
~ nother oh~ect of the inYentiOn iB to provide a method of
produ~ing a porous material, whlch is improved to permit the
precise control of the me~n pore ~ize of the open pores within
the range of between 0.5 and 1~ micron6, u~ing a filler of
such a s~all particle size a~ not to cause filler
sed~mentation wh~ch ~ould impair the handling of the flller.
Still another object of the inventlon i~ to provide a
25 methoa of produclng a poro~s material in which the visco~ity
of the ~lurry i~ lowered to permit quick filling of the mvld
and high prec~ BlOn of the product even when the product has a
complicated and intricate shape.
Other o~jects, featur~s and advantage~ of the invention
wlll becQme clear from th~ followins de~cription of the
preferred embodlment~ of the invention.
l~hese ob~ect~ are achieved by using the following
specific ~ixt~re amide compound as the hardener in the
production of the porous materi~l having o~en porPs.
DESCRIPTION OF TB~ INVENTION INCLUDIN~ T~E PREFE~R~D
.. . .. .. . .. .
EMBODIMENTS
1~ In order to ~c&omplish the above-de~cribed objects of the
lnvention, the pre~ent invention propose~ a method of
produclnq a porous materlal compris~ng the ~teps of preparing
a slurry by vigorously stlrrins a mixture c~mpr~ing a
blsphenol-typ~ epoxy resin, a hardener, a filler ~nd water,
c~t~ng the slurry in a wat~r-imper~eable mold, h2rdening the
~lurry wh~le lt con ~lins ~ter r and dehydrating the h~rdened
body, wher¢in the l~prov~ment comprises that the hardener is
ei~her (a) a mlxture of li) an amide compound whlch i6
obt~lned throu~b a re~ction between a monomeric fatty acld and
an ethyleneamine expre~sed by the formula of H2N-(C~2-C~2-
NH)n-~ where "n~ i8 3 to S, and (il) an amide compound of
polymeric atty acld (referred to as ~pol.ymeric fatty acid
polyamlde~ in this speclficat~on) obtained through a reactlon
of a polymeri~ fatty acid and the ethyleneamine, or (~ a
reaction mlxture obtained by mixinq reaction of the monomeric
fatty acid, the polymeric fatty acid ~nd the ethylenea~ine.
The monomer~c at~y ac~d mentioned ahove is a f~tty acid
having a num~er of carbon atoms ranglng between 10 and 2~ per
moleeule. Preferably, tl~e ~onomeric L~tty acid u~ea in the
method of ~he invention }~ con~ti~ute~ ~neinly b~ an o~eic
acid, linolei~ 2cid ~nu/or erucic asicl.
T~le ethylene~mine mentioned a~o~e is the or)e wilich is
S e~:pressed ~y the rollowing orrdula;
H2~-~CH2-Ch2-~)n-~ where n i~ 3 to 5, prefecably 4 to
5~
The amide compound of the monomeric fatty acid and the
polymeric fatty acid polyamide, as weLl as the reaction
IO mixture, as mentioned above, are prepared by re~cting the
fatty acld(s) with the above ethylene amine in a ratio of
about 0. 8 to abQUt 20 0 mol per one carboxyl group of fatty
acid.
The weight ratio o~ the amide compound of monomeric fatty
~cid to the polymerlc fatty aci~ polya~.ide in the mixture
amide co~pound u~ed as the hardener in th~ invention i~
preferably 90:10 tO 5:95, and more preferably 80:20 to
20:80.
The filler used in the method of the invention is of a
m~terial which can be bound by mean of a bisphenol~type epoxy
resin. The material of the fill~r should have a small content
of ~-oluble 6alts, or otherwi~e ~ large contraction will occur
during the hardening. The material should al~o be one which
permit~ control o the particle s~ze. Preferably, the filler
is constituted by hn lnorganic ~ateri~1 haviny a large surface
energy 6uch as powders of silica stone or silica san~.
Ae stated befoce, the known method proposed in Japane~e
Patent Publication No. ~464/1978 makes u~e of a polymeric
", ~
.,
6~
fatty acid polyamide ~olely a8 the hardener. In contrast, in
the pre~ent invention, the mi~ture amide compound aB the
hardener usad in the ~ethod ia either (a) a mixture of an
amide compound produced througb reactlon between a monomeric
fst~y acid and ethyleneamine and a polymeric fatty acid
poly~mide or (b~ reaction ~ixture produced through reaction of
a mo~omeric fat~y aci~ pol~eric fatty acid and
ethyleneamine. In addition, the invention i~ characterized
also in that the hardener contains a ~ignificant amount of
amide compound of monomeric fatty acid.
The ~o-called polymeric fatty acid i8 produced from
tal}ow oleic acid, tall oil fatty acid, ~oybean oil fatty acid
and ~o forth, and i~ composed mainly of di~er acids, although
trimmer acid~ and monomer acids are not exclude~. Th~ content
15 of tbe monomer acid, bowever, is les3 than a~out ~ and the
~ide compound of monomeric fatty acid ~n the polymeri~ fatty
acid polyamide thus produçed i8 ~180 less than about ~. On
the other han~, in the method of the invention, as ~tated
~efore, the amount of the amide compound of monomeric fat~y
acld to be u~ed is higher than that in th~ ordinary polymeric
fatty acld.
The present inventors have found that the mean pore size
in the product porou~ material is llnearly increased while the
vi~cosity of the slurry for the productlon of porous material
having open pores i8 linearly dQcreased as the rate o~ a~ide
compound of the monomeric fatty acid i.n the haraener i~
incre~se~. With ~his knowledge, the inventor~ have
accomplished the pre~ent invention through seeking for the
~L2~6817
optimum conditions such as the kind of the monomeric fatty
acid, kind of the ethyleneamine, and the ratio between -the
fatty acid and ethyleneamine, in relation to the properties
or characteristics in the production of the porous
material and the properties of the hardened porous
material.
The invention will become apparent from the
following detailed description of the invention.
According to the invention, the amide compound
of the monomeric fatty acid in the hardener produces
the following effect.
The known me-thod disclosed in Japanese Patent
Publication No. 2464/1978 employs solely a polymeric
fatty acid polyamide as the hardener. This polymeric
fatty acid polyamide may be one such as obtained as a
product of reaction between VERSADYME V216 (trademark;
produced by Henkel Japan) and tetraethylenepentamine. As
shown in Table l, the porous material produced by this
method showed a concentration of pore size to the
smaller side and cannot have a mean pore size exceeding
1.5 microns, even when the particle size of the filler
and the amount of addition and mixing of the reactive
diluent are varied, insofar as the particle size of the
filler is within a range easy to handle. Also, the
viscosity of the slurry used in the production of the
porous material showed extremely high viscosity.
;~ - 1 0
~246817
. T~ble 1
_
flller pa ~ cla S~ > 50% 5~ ~ 30~
-~\ epoxy _ _.... _ ._ ~ .~ _ .. ,
\~ ~ sin EP828 EPB15 EP8 ~ ~P~ 15
\~ .
f ~ none ~x~t 10~ none about 10~
. .__ ~ _ _ .. .___ . _ , __
~~slu~m3a~ 81u~ ~~ ~lllrry mea~l 5111rry
pO~ ~!5509it~ pc~e v~ ~7 pore Vi~ 3it~t pore vi~
81~ ~CD5 at ~iæ (cps at siæ (cps at size ~cps at
O~) ~oo~) ~/~) 30C) (t~) 3~C) (t~) 30~C)
, .. __ . .... _
1.2 n~7 73,000 1.0 ~6,000 1.1 55,000 103 6Q,000
. _ . . _ .. . . . .
1.~ O.fi 5~,000 lo.9 40,000 100 ,000 1.3 39,000
Note)
i) EP828 and EP815 (trademarks) are bisphenol-type
epoxy resin produced by Yuka Cell Epoxy Company.
ii) ~f~ mean~ he volume ratio of filler to sum of
re~infi .
iii) Water content i6 41% ln terms of volume ratio.
iv) The reactive diluent 15 butylglycldylether.
v) The mean pore size is shown in term of the least
diameter of pores which are filled with mercury, when 50% of the
total pore volume is filled with mercury, as measured by a mercury
press-feeding porosimeter.
vi) The filler is produced by pulverizing a silica
sand for glass produced in Seto district (manufactured by
. ~-
:lZ4681~
Nippo Keisa Kogyo K.K.) into a desired particle size.
vii) The slurry viscosity was measured with the
slurry prepared in accordance with the method of Japanese
Patent Publication No. 2464/1978, using a B-type viscosi-
meter with No. 4 rotor at 6RPM.
In contrast to the above, in the method of the invention
an oleic acid, NNA 35 (trademark; produced by Nippon
Ushi K.K ) was used as the monomeric fatty acid, while the
VERSADYME V216 (produced by ~enkel Japan) was used as the
polymeric fatty acid. At the same time, tetraethylene-
pentamine was used as the ethyleneamine. A porous material
was produced in accordance with the method of the invention,
using the reaction mixture of these three substances as the
hardener. As will be seen from Table 2, the mean pore size
is increased as the content of the amide compound of the
monomeric fatty acid is increased, so that the mean pore
size is controllable within the range of between 1 and 8
microns even when the kinds and the contents of the materials
other than the hardener are unchanged. From Table 2, it will
be seen also that the viscosity of the slurry becomes lower
as the content of the amide compound of monomeric fatty acid
is increased.
- 12 -
~,.
~24~ 17
Tabl~ 2
~ __, , _ ~ _
m~XJe ~ I f W filler dl~ter ccntrac~on ~lurry
fatty acl~ ~ p~cle æ~ze ~.~) (~3 ~3CPogc~t
_ __ ~ _ _ __
0 1~2 41 5,L~ > 3~6 1D3 Q~ll 4!~,~10D
~i .. u o~ 1.~ o~ 11 4~000
~ R 1 ~ ~i O~ 13 32~ OOtl
3 ~ 1~1 # N l . g 0 .16 25~ 0
~i 0 n ~ 1~ ;2~ 0 3,~13 21 ~, ~ 100
iSO ~ ~t ~ ~o;~ 0~20 16,500
~;6 u 1~ u 3~9 0~;~2 15~500
~ ~1 ~ 5~3. 0O30 15~00
~ D~ _ ~ ~55 15~000
. _ .
Note)
1) The mixiny ratio or content of the monomeric fatty
acid amide i~ determln~d as follow~. Tetr~ethyl~nepentamine
20 18 added to the ~ixture of monomeric f~tty acid and poly~leric
fatty acid at a ratio ~f 1 mol for one carboxyl yroup existing
in the m~xture. The mixture with the addition of
tetraethylenepentamine i~ heated up to 230C over 2 hour~ in
N~ atmosphere and then maintained at 230 to 240C for 2 hours
to become the hardener. The mixing ratio of the monol~ric
fatty acid amide i8 the ratio of ~mount of the in~t~al
monomeric f~tty acid before the ~ixiny to the ~um of the
a~ount~ o~ this monomer~c fatty ac~d and the polymeric fatty
-- 13 ~
68~
acid.
i~) "f~ i8 the volume rat~o of the filler to the sum
of resins.
iii) ~W~ iB the volume rat1o of water to the whole of
the prepare~ material.
iv~ The mean pore size i~ the mean diameter vf pores
in the porous material produced by th~ method of the
invention.
v~ The contraction rate is ~xpreased as the
contraction rate ln the hei~htwiae direction of a hardened
body and i~ measured as follow~. A ~lurry is ca3t in an FRP
case haivng a ~ize of 50 (length) x 50 ~wldth) x 500 (height)
mm and is cured for 24 hours in a room of an ~ir temperature
controlled at 45C under ~ drylng prevention (the ca6e ia
sealed). ~fter the harden~ng, the porou~ material is taken
out of the ca3~, and the helghtwlse lineAr contra~tion rate i8
~ea~ured from the contraction mark~ form~d at 450mm intervai
in the FRP c~se and the marks left on the hardened porous
mater1al.
vi) Silica s~nd for glass produced in Seto district
~manufactured by Nippo Keisa Kogyo K.R~) pulverized into size
of 5 m~crons ~30% wa~ used as the filler mater~
vil~ EP815 produced by Yu~a Cell ~poxy Company was used
aa the bisphenol-type epoxy resin.
viil) The 81urry Yi~Cosity i8 the viscosity of the
alurry prepared in accord~nce with the lnvention~ as meaaured
by a B-type v i scometer.
It may appear that the chang~ of the mean pore aize from
-- 14 --
6~:~1L7
the order as shown ln Table 1 to that shown ln Tabl~ 2 1~ only
mlnor and, hence, no ~ubstantlal effect is produce~ by ~uch a
change. A8 a matter of fact however, this 6mall change in
the pore 5ize offers a great advantaqe a~ explained
S hereinbelow.
~ ttention mu~t be drawn to the following formula which i~
known as Poiseuille'~ eguation.
g 5 ~ , h
where, Q representæ the amount of tran3mission through por~
per unit time, ~r~ represents a pore diameter, ~ represent
the vl~cosity of fluid, ~h~ represents the pressure
difference, and ~.0~ represent~ th~ pore leng h. A-~ will ba
under~tood from thi~ iEormula, the veloc~ty o~ 3 fluld flow~ng
through ~he pore iB proportion~l to the fourth power of the
pore ~iameter. Thus, a remarkable practical advantage is
produced even by a s~nall change or adjustment of the above
mean pore ize.
Porou~ material~ were produced ln accordance with the
method of the invention, u~ing pentaethylenehexamine as the
ethyleneamine, wlth various hardener compo~itions without
ch~nging the klnds and amounts of the materials other than the
hardener. Table 3 show the mean pore ~ize6 and contraction
rates a measured wlth these porous materials. From thi~
Table, lt w~ll be understood that the mean pore size i5
lncrea~ed, while the vi~co~ity of the &lurry 1B decre~ed, a~
the content of the amiae compound of monomeric fatty acid is
increased.
681~
. ~
C~ Q Ul ~ O W ~ 3
~o~ r ~ ~1 ~'D D
r-- ~ ~ W ~ V~ Cr ~ ~ ~ ~l D'
O ~ Vl ~ o o ~J ~ ~ ~
___
Y ~ ~ ~b
. _. _ _ _ . ~.
~1~ s s:~ ~ ~ dP :~:
. ~ t~--
~ ai t~D
~ 8 ~ a~ ~
X ~:
~ .
~ d ~ ~
~ ~. ~ ~ ~ w r h ~ ~_
VJ1~ 2 ~ P~ ~ t
. ~ . , ~ ~
~æ
,
- - - ~ ~ a
o ~ 7
;~ O ~ 1~ ~V
~ o 2 ~ ~ ~
. . . . _ _. ; ~ ;r
o o o o
o o~ o ~g
~ dP
. . . _ ._ ~ _--
_
o o o o
_ . _ ., , It , r~ ~,
G~ ~ 0~
~ Uol 'o o o ~ ~ ~
6~
~ote)
i) The ratio between the monomeric fatty acid amide and
the polymeric at~y acld poly~mide is determined a~ follow~.
In the case of the mixture obtained after independent
reactions, the harden~r is prepared by a proces~ comprising
the steps ofs (a~ adding 1 mol of pentaethylenehexamine to 1
mol of the monomeric fatty acid to conduct a ~ynthesis under
the following condition to orm an amide compound of monomeric
fatty acid, and (b) mixing a polymeric fatty acid and
pentaethylene-hexaoine which i~ added at a ratio of 1 mol for
1 ~one~ carboxylic group existing in t~e polymer~c fatty acid
to effect a ~ynthesi~ under the following condition to form a
polymerlc fatty acid polyamide, ancl ~c~ mixing the thus formed
~mide compound of monomeric fatty a~id ~) and polymeric fa~ty
a~id polyamlde ~b) ~t ratios shown ~n Tabl~ 3. The r~tio
between the a~ount of the ~nitial amid~ compound of monomeric
fatty acid ~nd th~ amount of the initlal pol~meric fatty acid
polyamide beforoe they arQ ~.ixed 1~ dete}mined a~ the ratio
between monomerlc fatty acld amide and the polym~ric fatty
acld polyamide in the hardener~ '~t should be noted that the
amide compound of monomeric fatty acid which may exi~t in the
polymeric fatty a~id polyamide i excluded from the above-
mentiGned in~tial amide compound of monomeric fatty acid.
In the ca~e where the reaction mixture ls used as the
hardener, the ~onomeric fatty acid and the polymeric atty
acid ~re mixed at the ratios ~hown ln Table 3. After addin~
pentaethylenehe~amine to thi~ mixtur~ ~t a ratio of 1 mol for
1 ~one~ carboxyllc group ln the mixture, the mixture i~ heated
6~
up to 23~ C over 2 hours and then 1~ maintained at 230 to 2~0C
for 2 hour~ in ~2 gag atmo~phere to cause a reaction thereby
to synthesize ~he hardener. In thi~ case, the ratlo between
the monomeric fatty acid and the polymeri~ f~tty acid beore
the ~xlng i~ determined ~ the ratio between ~onomerlc fa~ty
acid amide and poly~eric fatty acid polyamlde in the hardener.
f~ repre~ents the volume ratio of filler to the
~u~ of re~ins.
iii) ~W~ repre~ents the ~olu~e ~ of water in the
prepared material.
iv) The mean pore s~ze ~hows the mean diameter of
pores in th~ porou~ material produced by the ~.ethod of the
in~ention.
7) ~he contract~on r~ ~B the rate of ccntraction in
the heigh~w~$e direction of a hardened body and i8 measured as
follo~. A slurry is c~st in an FRP case havlng a size of 50
(length) ~ S0 (width) x S00 ~he~ght) nu~ ~nd i~ cured for 24
hours in ~ room of an air temperature controlled at 4SC under
a dr~ing prevention ('che case is sealed). Af~er the
20 hardening, the porou~ material i~ taken out of the c~se, and
the heightwise linear contraction rate ~ 9 measured from the
cor.traction marks formed at 450mm interval in the FRP case and
~he marks left on the hardened porous material.
vi~ An oleic acid (NNA35 manufactured by Nippon Yushi
25 R.E~ used a3 the monomeric fatty ~lcid.
vii) VERSADYME V216 produced by E~enkel Japan is used as
the polymer ic fatty acid .
viii) Pulverized ~llica ~and for gla85 produced 1n Seto
1~ -
~, ....
i ~r=
. ,. ~ .
6~
district (manufactured by Nippo ~eisa Kogyo ~.K.) is used as
the filler.
ix) ~PB15 manufacturæ by Yuka Cell Epo~y Company is
u~ed as the bisphenol-type epoxy resln.
x) The slurry viscoslty is the vi6cosity of the
slurry prepared in accordance with the metho~ of the
invention, as measured ~y a B-type visco~eter.
As ~tated before~ the monomeric fatty ~cid as used in the
method of the invention can include 10 to 22 carbon atoms per
molecule. Fatty acids havlng carbon atom numbers exceeding 22
cannot be u~ed adequately b~cause of too high melting point,
while the fatty acid~ having c~rbon atom numher~ less than 10
cause a problem that the amide compound produced through
reaction with the ethyleneamine shows only a small surfactant
effect sc that the slurry is made un~table to allow a ~arge
contraction during ~he hardening.
Generally, iatty acids produced from animal and vegetable
oils and fat~ are constituted by a nixture of mainly lauric
acid, myri~tic acid, palmitic acid, stearic acid, oleic acid
an~/or linolic acid, as well as other fatty acids having
carbon atom number~ r~nging between 10 and 22. Theae mixed
fatty acids from natural mater ials can be used for tbe
monomeric fatty acid in this invention. Among the mixed fatty
acids, those containiny oleic acid, linoleic acid and/or eruCic
acid as the maior constituent are prefeable from the
vie~points of the properties of the hardener o~tained and the
contraction during the hardening.
-- 19 --
.~ ''
~6~
Table 4 ~how~ the v~ ~cosl~ies ~t ~8C of harden~3r~ which
were prep~red ~y mixlng Yariou~ monomeric atty a::~ds wlth the
polyme~ic fatty Acid at mol~ ratlo of 50s50, ~ddlng thereto
tetrae'chylenepentamine (~) of a ratio of 1 mol for one
5 carboxyl group e~isting in the mixed fatty acids, heating the
mixture up ~o 230~C over 2 hour~ and then maintaining ~he ~ame
at 230 to 240C ~or an ad~itional 2 hour~ to sbtain the
hardener. The table al~o shows th~ ratlo of c~ntraction
during the hardening ln the case where tbe ;?orous ~a~erlal was
10 produced b~ using the absve hardeners.
Tab le
klnd of h~er Filler particl~ C~ltract~on
fat~r ~ld (cps at 25C~ f ~ si2e ha~ening~
. ~ ~ __ ~
olelc acld 3500 1.~ 41 5 f~ > 30~ 0.13
l~ lc a~:ld 3000 ~ .. .. 0.,15
stearic acld ~el ., n ~ 0~17
palJIlltic acld g~l u ~ n 0. 49
rr~ tlc acld gel .. n u 0~31
].aurlc acld 5500 . a _ 0~67
- 20 -
~IL2~68~7
Note)
i) The ~onomeric fat~y acld~ other than oleic acid
~re reagents produced by ~okyo Kasei K.~.
~1) Oleic acid ifi NNA35 manufactured by Nippon Yu~hi
K.R.
iii) V~RSADY~E V216 produced by ~enkel Japan is used a~
the polymeric fatty acit3.
iv) "f~ repre~ents ~he volu~e ratio of filler to the
sum of resin~. `
Y~ ~W" represents the volume % of water in the
prepared material.
vi) Pulverized silica 6an~ for gla~s produced ln Seto
distr~t (manufactured by Nippo Keisa Rogyo X.R.~ i8 used a9
the f~ller.
vii) EP815 ~anufactured by Yuka Cell Epoxy Gompany is
UBed ~5 the bisphenol-type epo~y resin.
viil) The contraction rate is the rate of contraction in
the he~ghtwlse dlrection of a hardened body and i8 ~;ea~ured a~
follows. A slurry is cast ln an FRP case h&ving a size of 50
20 (len~'ch) x 50 (wldth) x 500 (height) m~n and is cured for 24
hours in a room of an ~ir temperature controlled at 45C under
A drying prevention (the case ls sealed). After the
hardening, the porous mater ial ifi taken out of the case, and
the heightwise llnear contraction rate i~ measured from the
~5 contraction ~arks ~ormed at 450~ interval ln the FRP case and
the mark~ left on the hardened porous materlal~
~ 21 -
~ .
~L24~
In the ethy~eneamine ~N-tC~C~-N~ a~ u6ed, the
nunlber ~n~ ~s sele~ted ~o be 3 to S for the followlng reason.
Namely, B slurry ¢o~pr t sing the hardener prepared from th~
ethylenediamine or ~iethylene~riamine having the number "n~ of
1 or 2 e~hib~t~ a hi~h cohesion fo~ce, a8 well as a large
contrac~ion; an~, therefore, the hardener cannot be u~ed
pract~cally i~ the production of the porou~ materlal.
Triethylen~tetramine having ~he number ~n~ o~ 3 al80 ~ends to
exllibit a ~o~ewhat large cohe~ion ana contraction. For th~se
rea60ns, it i8 preferred to use tetraethylerlepentamine and
pentaet~ylenehexamine having the nu~her~ ~n~ o~ 4 and 5,
re~pectively.
As a ~atter of fac~, howe~er, it i6 diff~cult to
co~merclally obtain ~ pure ~thyl~ne~ine having ~ ~lngle
compo~ition. ~he ethyleneam~ne as used ~n the i~vent~on,
therefor~, ~ay be such R ~ixture a~ the ~ommercially available
goods.
In the mel:hod of the invention, ebe ratio between the
amide compound of monomer~c ratty acid and the polymeric fatty
acid polyamide in the hardener is ~elect~d ~referably to range
between 90210 an~ 5:95 by welght. A8 wlll ~e ~een from Table~
2 and 3, a~ the content of the amide compound of the ~,onomeric
f~tty acid iB increa~e~, the r~te of hardening contr~ction is
lncrea~ed to impair the production of porou6 materlal at high
dimensional precision. For this reason, the content of the
~id~ compound of monomeric f~tty ~cid ~hould be ~electe~ not
to exceed 90~ This content i5 preferably up to 80~, when the
product has a l~rge ~ize end complcatea fihape.
- 2~ -
'7
On the oth~r hand, ;~he~s lt is degired to produce ~ porou~
m~terial havlng open pores o ~ pore dla~neter of abou~ 90 5
micron, the conterlt o~ the am~ de compound of the monomer ic
fatty acid may be smaller ~:has~ 59~. ~owever, the production of
S 'che p~rous material having mean pore size not smaller than 1.5
micron encoun~er~ ~ d~fficulty when ~he ~bove-mentioned
content i~ smaller than 5%. For thi~ reason, the preerred
lower limi t of the content of amide compound of monomer ic
~atty acid i~ selec'ced to be 5%.
In the method of the invention, the ~mide comp3und of
monomeric fat'cy ~cid and the polymeric fatty ac~d polyamide
are synthe~lzed w~th the addition of ethyleneamine at a ratio
of about 0. 8 to about 2. 0 mol~ per 1 tone) carboxyl gLQUp.
When the ethyleneallline 1~ increaseB beyond 1.0 mol, the 31urry
15 tend~ to make a cohe~lon c~on raction during hardening~ el8 ~
re3ul'c of the pre~nce of free or ~eparated ethylene~mine. On
the other h~n~, when t~e ethyleneamine i8 decreased below 1. 0
mol, the NH2 radicals at ~:>oth ends of the ethyleneam~ ne react
with COO~. The slurry comprir~ing the hardener obtained showed
20 an increa ed tendency of cohe~ior~ contraction at the time of
hardenins. ~he ethyleneamine content ranging between about
0. 8 an~l about 2. 0 mol~ per 1 ~one) carboxyl group, however,
can produce a ~enerally acceptable result.
A reactive diluent SUCII as butyl ~lycidyl ether, allyl
glycldyl ether, phenyl glycidyl ether, terti2ry carboxylic
acid glycidyl ester, secondary pentyl phenol ~,onoglycidyl
ether or the like may b~ added to the b~sph2nol-type epo~y
re~in. As a r~sult of sdd~tion of suc~ a diluent, the ~lurry
-- 23 ~
~2~6~
visco$1ty i5 decrea~ed and the pore si~e ln the porou~ product
i8 increa~ed. A too la~e ~ount of ~dd~tion o~ such ~
diluent, howev~r, unde~irably causes ~ contraction during the
hardenln~. The li~lit~ o Anlount of addition of the re~ctive
diluent depends on the kind of the diluent. I~ is preferred
to u~e the diluent of not more than 25 parts by ~eight for 100
part~ by weight of the bi6phenol-type epoxy resin.
In the method of the in~ention, lt i~ preferable to add a
hsrdening pro~otion ayent, in order to incre~se the rate of
1~ h~rden1ng and, hence, to enhance the strength of the hardened
body. Vsually, ~ubstances such as phenol, triethanola~ine,
hexamethylenetetramine, benzyldimethylamine, tri dimethyl-
amin~ethylphe~ol or the like ~re u~able as the hardening
promotion a~ent in combLnation wit~ a polyamid~ hardener~ In
15 the m~thod of the invention, a super~or effect i~ obtained
p~rtlcul~rly by the use of a har~ening promotion ~gent of a
tertiary amine of aromatic group such a3 b~nzyldimethylamin~,
trl5dlmethylaminomethylphenol and 80 forth. From the
viewpoint of the strength of the hardened body, ~t is
'preferred to u~e a hardening promotor in about 7 to 15 parts
by weight for 100 parts by ~eight of the hardener.
An ex&~ple of the method of the invention is ~hown below
only for the illustratlng purpose.
Example
796g of ~ polymeric fatty acid ( VERSADYME V216, producea
by IJenkel Japan), 15919 of oleic acid ~NNA 35 produced by
Nippon Yu3hi ~.K.3 and 16139 of tetraethylenepentz~ine
- 24 -
~Z~ 7
(produced by Seitetsu Kagaku K.K.) were put together in a
stainless steel reaction vessel having a volume of 5~. The
mixture was heated from the normal temperature up to 230C in
2 hours while continuing stirring under a supply of N2 gas and
then held at 230 to 240C for 2 hours to synthesize 3790g of
hardener.
Thenr 647.9g of bisphenol-type epoxy resin (EP815
produced by Yuka Epoxy K~K.), 218.2g of the above-mentioned
hardener, 17.7g of a hardening promotion agent TAP (trademark;
made by Kayaku Noulli K.K.), 2803g of silica sand powder of
particle size of 5 microns ~30~ and 1348g of wa~er were put in a
a stainless steel vessel having no lid. These materials were
vigorously stirred or 10 minutes to make a slurry.
This slurry was cast in an FRP case having a size of 50
(length) x 50 (width) x 500 (height) mm and was cured for 24
hours in a room of an air ~emperature controlled at 45C under
a drying prevention ~the case was sealed). Ater the
hardening, the porous material was taken out of the case, and
the heightwise linear contraction rate was measured from the
contraction marks formed at 450mm interval in the FRP case and
the marks left on the hardened porous material. The
contraction rate thus measured was 0.18%. This hardened
porous material was then dried and the pore size distribution
was measured by means of a mercury press-feeding type
porosimeter. This hardened porous material showed a mean pore
size of 4.0 microns.
Test pieces for measurement of bending strength were
molded from this slurry. The bending strength in wet
- 25 -
cond~tion waB ~ne~ured aft~r a drylng prevention harderllng of
~he ca3~ sll~rry at ~5C~c for 24 bour~ The mean bendlng
strengt31 was 70 Rg~cm2. Th~ ~ried test pieCeB ater
mea~urement of the wet bendirlg strength ~howed an apparent
5 porosity of 4196.
2~ -
