Note: Descriptions are shown in the official language in which they were submitted.
CA 02415784 2004-12-21
DESCRIPTION
MESOPOROUS SILICA, PROCESS FOR SYNTHESIZING THE SAME AND
UTILIZATION THEREOF
Technical Field
This invention relates to mesoporous silica, a process
for synthesizing the mesoporous silica, ink absorbents
containing the mesoporous silica which are to be used in ink-jet
recording sheets, etc. and the recording sheets.
Background Art
Mesoporous silica, which is porous silica having uniform
pores in the mesopore region of 1.5 to 10 nm, clearly shows
crystallinity in the powder X-ray diffraction. It is a new
material expected as widely applicable to selective catalytic
reactions, adsorption/separation, etc.
Usual porous silica materials such as silica gel have
hydrophilic surface. In contrast thereto, mesoporous silica
has hydrophobic surface.
With respect to processes of the synthesis of mesoporous
silica, there have been known, fog example, the following three
processes with the use of a combination of a silica source with
a template. In the first process reported in US Patent 3, 556, 725,
JP-W-5-503499, JP-A-8-39607, etc., the synthesis is carried out
within the alkaline region by using amorphous silica powders,
aqueous alkali silicate solutions, active silica, etc. as the
silica source and quaternary ammonium salts having long-chain
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alkyl group or phosphonium salts as the template. In the second
process reported in JP-A-4-238810, etc., the synthesis is
carried out by the ion exchange method with the use of layered
silicates like kanemite as the silica source and long-chain alkyl
ammonium cations as the template. In the third process reported
in US Patent 5,672,556, etc., alkoxides such as
tetraethoxysilane are used as the silica source and alkylamines,
etc . are used as the template _ (The term "JP-A" as used herein
means an "unexamined published Japanese patent application", and
the term "JP-W" as used herein means an "published Japanese
patent application in the national stage of International
application".)
In the first process, the synthesis is performed within
the alkaline region using a strongly cationic surfactant such
as a quaternary ammonium salt as the template, so that mesoporous
silica is obtained by removing the template_ To remove the
template, either oxidative destruction in the atmosphere or
proton exchange with an acid and a solvent should be performed.
In the second process,_it is further required to synthesize
kanemite, etc. used as the starting material. Although the
third process with the use of an amine is advantageous from the
viewpoint of removing the template, it is inadequate for mass
production on an industrial scale, since expensive alkoxides
(tetraethoxysilane, etc.) should be used therein.
To synthesize mesoporous silica, therefore, it is un-
avoidable either to perform the reaction in the alkaline region
with the use of strongly cationic surfactants (quaternary
ammonium salts, etc.) as the template or to use expensive
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starting materials such as alkoxides_ The mesoporous silica
synthesized under these conditions has hydrophobic surface,
which makes it disadvantageous in absorbing aqueous waters, etc.
with the spread of Internet and digital cameras,
opportunities to output rich full-colored images on paper, etc.
have been increasing. Ink-jet printers have been rapidly
spreading as instruments for outputting these images owing to
the merits thereof such as being able to easily give full-colored
images, being available at a low cost, and making little noise.
In the ink-jet system, ink droplets are jetted from a nozzle
at a high speed and adhered to a recording material to give a
record. Since droplets of ink containing much solvents are
continuously jetted, there frequently arise some problems such
that the ink droplets are fused with each other on a recording
sheet to thereby form enlarged dots or mixtures of dots with
different colors. It is therefore required that an ink-jet
recording sheet can quickly absorb inks so that the inks are
neither mixed with each other even in overlapping dots nor blur.
It is also required that the recording sheet can keep the image
to be recorded in a favorable state (i _ e. , having excellent water
resistance, light resistance, etc.).
From these points of view, it has been proposed ink-jet
recording sheets produced by applying various organic matters
or inorganic matters optionally together with binders onto base
materials or incorporating 'these matters into base materials.
For example, there have been known recording sheets provided
with an ink receptor layer made of a water-soluble resin
(polyvinyl alcohol, etc.) on paper, a plastic film, etc. and
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recording sheets provided with an ink receptor layer containing
a filler such as silica gel (see, for example, JP-A-55-146786,
JP-A-56-99692, JP-A-59-174381, JP-A-2-276670). However,
there has been obtained no recording sheet so far which is free
from dot blurs, shows a high ink-absorptivity and, at the same
time, has satisfactory water resistance and light resistance.
The present invention provides mesoporous silica having
highly hydrophilic surface compared with the conventional ones
and a process for synthesizing the mesoporous silica under mild
conditions with the use of inexpensive materials.
The invention also provides ink absorbents, ink absorbent
slurries and recording sheets which are free from dot blurs,
have a high ink-absorptivity and are excellent in water
resistance and light resistance.
lei sc~l n~nrP of the Inyenti on
The gists of the invention are as follows_
1. Mesoporous silica characterized by having an average
pore diameter in the mesopore region of from 1.5 to 10 nm, a
nitrogen adsorption specific surface area determined by the BET
method of from 500 to 1400 mZ/g and a monolayer adsorption of
water at 25°C of 1.7/nm'' or more.
2. A process for synthesizing mesoporous silica
characterized by successively performing the step of mixing and
reacting active silica with a neutral template to synthesize
an active silica/neutral template complex, and the step of
removing the neutral template from the complex.
3. The process for synthesizing mesoporous silica as
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described in the above 2, wherein the neutral template is an
amine represented by the following structural formula (1):
RNHZ (1)
wherein R represents an alkyl group having 8 to 20 carbon atoms.
4. The process for synthesizing mesoporous silica as
described in the above 2, wherein the neutral template is a
nonionic surfactant represented by the following structural
formula (2):
R ( OCHpCH2 ) nOH ( 2 )
wherein R represents an alkyl group having 12 to 20 carbon atoms;
and n is from 2 to 30.
5. The process for synthesizing mesoporous silica as
described in the above 2, wherein the neutral template is an
amine oxide represented by the following structural formula (3)
R(CH;)~NO (3)
wherein R represents an alkyl group having 8 to 20 carbon atoms _
6. The process for synthesizing mesoporous silica as
described in the above 2, 3, 4 or S, characterized in that the
neutral template is removed by bringing into contact with a
solvent.
7_ The process for synthesizing mesoporous silica as
described in the above 6, characterized in that the solvent to
be used in removing the neutral template is an alcohol.
8_ An ink absorbent characterized by containing
mesoporous silica.
9. An ink absorbent slurry comprising the ink absorbent
as described in the above 8 and a solvent.
10. A recording sheet characterized by containing the ink
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absorbent as described in the above 8.
11. The ink absorbent as described in the above 8 wherein
the mesoporous silica is the mesoporous silica as described in
the above 1.
12. An ink absorbent composed of the ink absorbent as
described in the above 11 and a solvent.
13. A recording sheet characterized by containing the ink
absorbent as described in the above 12_
RriPf Description of the Drawings
Fig. 1 is a chart showing the pore distribution of the
mesoporous silica synthesized in Example I.
Fig. 2 is a chart showing the pore distribution of the
mesoporous silica synthesized in Example S.
Fig. 3 is a chart showing the pore distribution of the
mesoporous silica synthesized in Example 7.
Fig. 4 is a powder X-ray diffraction pattern of the
mesoporous silica synthesized in Example 1.
Fig. 5 is a powder X-ray diffraction pattern of the
mesoporous silica synthesized in Example 5.
Fig. 6 is a powder X-ray diffraction pattern of the
mesoporous silica synthesized in Example 7.
RP~t Mn~IP fnr Carrying Out the Tnvention
Now, the invention will be described in greater detail.
The mesoporous silica according to the invention is
characterized by having an average pore diameter in the mesopore
region of from 1.5 to 10 nm, a nitrogen adsorption specific
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surface area determined by the BET method of from 500 to 1400
m'/g and a monolayer adsorption of water at 25°C of 1.7/iim' or
more_ The monolayer adsorption of water at 25°C of 1_7/nm' or
more contributes to the achievement of the excellent ability
to absorb aqueous solutions, etc_
The process for synthesizing mesoporous silica according
to the invention is characterized by mixing and reacting active
silica with a neutral template and then removing the neutral
template from the complex thus obtained. The invention is also
characterized in that the neutral template can be easily removed,
recovered and reused by bringing into contact with an organic
solvent such as an alcohol.
The active silica to be used in the invention can be
prepared by being extracted from water-glass with an organic
solvent or subjecting water-glass to ion exchange. When the
active silica is prepared by bringing water-glass into contact
with an H-type canon exchanger, for example, it is industrially
preferable to use No_ 3 water-glass which contains only a small
amount of Na and is less expensive_ In this case, the wa
ter-glass is mixed with water and then brought into contact with
a can on exchange resin to give active silica_ From the
viewpoint of efficiency, it is favorable that the mixing ratio
of the water-glass to water ranges from 0.2 to 0 _ 6. As the cation
exchange resin, it is preferable to use strongly acidic exchange
resins based on sulfonated polystyrene divinylbenzene (for
TM
example, Amberlite IR-120B manufactured by Rohm & Hass Co_ ~ etc. ,
though the invention is not restricted thereto.
The neutral template to be used in the invention is not
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particularly restricted. For example, long-chain alkylamines,
nonionic surfactants, long-chain alkylamine oxides and the like
are may be used therefor. It is preferable to use primary amines
having long-chain alkyl, nonionic surfactants of the
polyethylene glycol type, dimethylalkylamine oxides, etc.
As the amines to be.used in the invention, those having
a structural formula RNHZ (wherein R represents an alkyl group
having 8 to 20 carbon atoms) are preferable_ Particular
examples thereof include dodecylamine, tetradecylamine,
hexadecylamine, octadecylamine, etc.
As the nonionic surfactants to be used in the invention,
those having a structural formula R (OCH.,CH4 ) "OH (wherein R
represents an alkyl group having 12 to 20 carbon atoms; and n
is form 2 to 30) are preferable. Particular examples thereof
include polyoxyethylene lauryl ether, polyoxyethylene cetyl
ether, polyoxyethylene stearyl ether, etc_
As the amine oxides to be used in the invention, those
having a structural formula R(CH3)ZNO (wherein R represents an
alkyl group having 8 to 20 carbon atoms) are preferable_
Particular examples thereof include N,N-dimethylundecylamine
N,N-dimethyldodecylamine N-oxide, N,N-
N-oxide,
dimethyltetradecylamine N-oxide, etc.
The composition expressed in the molar ratio of
Si02/neutral template to be used in these reaction ranges from
1 to 30, preferably from 1 to 10. When two or more templates
are employed, use is made of a value expressed in the average
molecular weight_
To alter the pore diameter, it is possible to further add
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an organic auxiliary such as aromatic hydrocarbons having 6 to
20 carbon atoms, alicyclic hydrocarbons having 5 to 20 carbon
atoms, aliphatic hydrocarbons having 3 to 16 carbon atoms, and
amines and halides thereof, for example, trimethylbenzene,
triethylbenzene, etc. The molar ratio of the organic auxil-
iary/SiO~ ranges from 0.05 to 20, preferably from 0. 1 to 10, while
the molar ratio of the organic auxiliary/template ranges from
0.02 to 100, preferably from 0.05 to 35.
Owing to the high reactivity of active silica, the reaction
can easily proceed even at ordinary temperature. However, the
reaction may be performed under heating up to 100°C, if necessary.
It.is unnecessary to employ conditions exceeding 100°C as in
hydrothermal reactions. The reaction time is from 0.5 to 100
hours, preferably from 3 to 50 hours. The pH range at the
reaction preferably falls within a range of from 4 to 10, still
preferably from 5 to 9.
The reaction between active silica and the template can
be carried out by, for example, mixing/stirring an aqueous
j solution of active silica, obtained by bringing water-glass into
contact with an ion exchange resin, with the template dissolved
or dispersed in a solvent or the template as such, though the
invention is not restricted thereto. When active silica is
obtained by extracting water-glass with an organic solvent, a
solution of the active silica in the organic solvent is reacted
with the template_ When the template is to be dissolved or
dispersed, use may be made of water, an organic solvent or a
mixture of water with an organic solvent . As the organic solvent,
alcohols are preferably employed. Preferable examples of the
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alcohols include lower alcohols such as ethanol and methanol.
The molar ratio of the solvent/template in the reaction
preferably ranges from 1 to 1,000, still preferably from 5 to
500.
The complex thus obtained is separated by filtration, etc. ,
washed with water and dried. Next, the template contained
therein is removed by bringing into contact with a solvent such
as an alcohol or calcination. Thus, mesoporous silica can be
obtained. Calcination is performed at such a temperature as
ensuring burning-off of the template, i.e., about 500°C or above.
The calcination time is appropriately determined depending on
the relationship with temperature. In general, it ranges from
about 30 minutes to 6 hours . The solvent to be used in removing
the template may be an arbitrary one, so long as the template
is soluble therein. Although use can be made of alcohols,
supercritical fluids, etc. therefor, it is preferable to use
alcohols which can be easily handled and have high dissolving
power. Preferable examples of the alcohols include lower
alcohols such as methanol and ethanol. The template may be
removed by, for example, mixing the solvent with the complex
and stirring, or passing a solvent through a column packed with
the complex. 'The removal temperature preferably ranges from 20
to 80°C_, though it may vary depending on the solvent and template
employed. In the process of removing the template by mix-
ing/stirring, it is preferable that the mixing ratio by weight
of solvent to the complex (i.e., the weight of the solvent/the
weight of the complex) is 5 or more_ When the weight ratio is
excessively high, the efficiency of removing the template is
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elevated but the device becomes too large. When the weight
ratio is lower than 5, on the other hand, a compact device can
be employed but the removal efficiency is lowered. In such a
case, it is therefore necessary to elevate the mixing/stirring
frequency or to prolong the mixing/stirring time. The template
thus removed can be reused after eliminating the solvent
therefrom.
The ink absorbent according to the invention is
characterized by containing mesoporous silica. The mesoporous
silica to be contained in the ink absorbent of the invention
is one having a porous structure with a nitrogen adsorption
specific surface area determined by the BET method of preferably
from 500 to 1400 m'/g (still preferably form 700 to 1900 mZ/g)
and a pore volume of preferably from 1 to 4 cclg. When the
specific surface area is less than 500 m~/g or the pore volume
is less than 1 cc/g, it is feared that only an insufficient
ink-absorptivity can be obtained. By using mesoporous silica
which satisfies the above-mentioned requirement andfurther has
a monolayer adsorption of water at 25°C of I.7/nm' or more, the
water resistance of the ink absorbent can be further elevated
owing to the hydrophilic surface.
It is preferable that the average particle diameter of
the mesoporous silica to be used in the ink absorbent of the
invention ranges from 0.02 to 20 Vim. It is not favorable that
the average particle diameter is larger than 20 ~~m, since the
smoothness of a recording sheet is sometimes worsened in this
case.
The mesoporous silica to be used in the ink absorbent of
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the invention may be synthesized by an arbitrary process without
restriction, so long as the physical properties as defined above
are imparted thereby. for example, use may be made therefor of
a process of synthesizing in the alkaline region with the use
of an amorphous silica powder, an aqueous alkali silicate
solution, active silica, etc. as the silica source and a
quaternary ammonium salt having long-chain alkyl or a
phosphonium salt as the template, as described in JP-W-5-503499,
JP-A-8-34607, etc. Alternatively, it is possible to use a
process of synthesizing by the ion exchange method with the use
of a layered silicate such as kanemite as the silica source and
a long-chain alkylammonium cation as the template, as described
in JP-A-4-238810, etc. It is also possible to use a process with
the use of an alkoxide such as tetraethoxysilane as the silica
source and an alkylamine,,etc. as the template, as described
in US Patent 5,672,556. Moreover, use may be made of the
synthesis processes as claimed in claims 2 to 7 of the present
invention.
Although the content of the mesoporous silica in the ink
absorbent varies depending on the utilization mode thereof
without restriction, it is preferable that the content is l0a
by weight or more, still preferably 30% by weight or more.
Although other components of the ink absorbent are not
particularly restricted, it may contain a binder, a pigment,
and the like depending on the purpose and mode of the utilization
As the binder, use can be made of organic matters publicly known
in the art, for example, starch, modifications thereof, wa-
ter-soluble resins such as polyvinyl alcohol (hereinafter
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referred to simply as PVA) and modifications thereof, latexes
and emulsions_ The binder is used usually in an amount of from
to 300 parts by weight per 100 parts by weight of the mesoporous
silica in the ink absorbent. Examples of the pigment as de-
scribed above include silica gel, calcium carbonate, kaolin,
zeolite, alumina, etc.
The ink absorbent may be in the form of either a powder,
a mass or a paste. Namely, it is not particularly restricted
in form, so long as it is usable as an ink-absorbent element
to be applied onto the surface of a base material (a synthetic
resin film, a paper, etc.) or incorporated thereinto.
In addition to the binder and pigment as described above,
the ink absorbent may further contain other publicly known
additives such as an ultraviolet absorber, a fading inhibitor,
a dispersant, a thickener, a defoaming agent, etc_ depending
on the purpose of utilization.
In the recording sheet according to the invention, a base
material (a synthetic resin film, a paper, etc_) is sur-
face-coated with the above-described ink absorbent, which
serves as an ink-absorbing element, or the ink absorbent is
incorporated into the base material.
Examples of the base material usable herein include
synthetic resin films and papers. As the synthetic resin films,
use can be made of, for example, polyesters, polyolefins,
polyamides, polyester amides, polyvinyl chloride and the like.
Moreover, it is possible to use copolymers of these polymers,
blends thereof, crosslinked products thereof, films opacified
by incorporating pigments, foamed films, glossy films, etc_
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Among the base materials as cited above, it is particularly
preferable to use polyester, still preferably polyethylene
terephthalate, from the viewpoints of mechanical properties,
handling properties, etc. As the papers, use can be made of
woodfree paper, moderate-grade paper, art paper, cast-coat
paper, coated paper, synthetic paper, resin-coated paper, etc.
In addition to the synthetic resin films and papers, it is also
possible to use fabrics (cotton, rayon, acrylic fabric, etc_ ) ,
glass plates, metals, etc. as the base material depending on
the purpose. The thickness of the base material ranges from 10
to 200 Eun in many cases, though the invention is not restricted
thereto.
To coat the surface of the base material, the ink absorbent
may be applied by using various publicly known methods (die
coating, roll coating, rod coating, blade coating, air knife
coating, etc.) and then dried. Alternatively, use may be made
of the dip coating method wherein the base material is soaked
in the ink absorbent, the spray method wherein the ink absorbent
is sprayed onto the base material, or the transfer method wherein
a surface of a molded article is coated with the ink absorbent
followed by transfer onto the base material.
In the step of coating, it is a practice to use a slurry
prepared by mixing the ink absorbent with a solvent. In this
case, it is also possible that a dispersion of the mesoporous
silica (i.e., one of the components of the ink absorbent) and
a liquid having other components (i_e., binder, etc. ) dispersed
therein are prepared separately and then mixed together to give
a slurry for coating.
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As the solvent, use may be made of various ones depending
on the coating method and binder employed without restriction.
Use may be made therefor of water and various publicly known
organic solvents such as alcohols (ethanol, isopropyl alcohol,
etc. ) , acetone, methyl ethyl ketone, etc. The amount of the ink
absorbent varies depending on the coating method and the
utilization mode without restriction. Itispreferablethatthe
ink absorbent content in the slurry is 5o by weight or more,
still preferably 10% by weight or more.
If needed, the base material may be preliminarily
subjected to a publicly known surface-treatment (corona dis-
charge, primer treatment, etc_) in air or another atmosphere
so as to improve the coating properties or adhesiveness of the
ink absorbent. Furthermore, it is possible to employ multi-
layer coating, to coat both faces of the base material, or to
laminate layers) having different properties (a protective
layer, a gloss layer, an adhesive layer, etc.) thereon.
It is appropriate that the coating thickness ranges from
1 to 100 Vim, preferably from 5 to 50 ~un_ The content of the
mesoporous silica in the coating layer preferably ranges from
0_5 to 30 g/mi. When the content of the mesoporous silica is
. less than 0. 5 g/m2, it is feared that the ink-absorptivity becomes
insufficient.
As a means for incorporating the ink absorbent in case
of, for example, paper, the above-described ink absorbent or
a slurry containing the ink absorbent is added to a paper slurry
and then the resultant mixture is processed with a paper machine.
Alternatively, it is also possible that the ink absorbent is
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mixed with a synthetic resin, etc. and the thus obtained mixture
is molded into a film or a sheet by the casting method, the
extrusion method, the calendering method, etc_ Although the
synthetic resin to be used herein is not particularly restricted,
it is preferable to use therefor those having a high water
permeability such as vinyl alcohol resins, acrylic resins,
urethane resins, amino acid resins, etc. The content of the
mesoporous silica based on the whole sheet preferably ranges
from 0.5 to 30o by weight.
Now, the invention will be described in greater detail
with reference to the following Examples.
In these Examples, powder X-ray diffraction patterns were
formed by using RINT2500 manufactured by Rigaku.
Pore distribution and specific surface area were measured
with nitrogen by using Autosorb 1 manufactured by Quantachrome.
Pore distribution was calculated by the BJH method. The average
pore diameter was calculated from the peak value in the
differentiated pore distribution curve determined by the BJH
method_ Specific surface area was calculated by the BET method.
Water monolayer adsorption was calculated by dividing
monolayer adsorption, which had been determined by the BET method
with the use of an adsorption isotherm of water by using BELSORP
18 manufactured by Bel Japan, INC. , with the BET specific surface
area determined by the nitrogen adsorption.
Average particle diameter was measured with a laser
diffraction grain size distribution meter SALD-1100 manufac-
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tured by Shimadzu Corporation.
Mesoporous silica content in ink absorbent layer was
determined from the ratio of the weight of coated ink absorbent
layer after drying to the weight of the mesoporous silica and
binder fed into the slurry.
~~ample 1
172.5 g of No.3 water-glass (SiOz = 29° by weight, Na-O
- 9.5o by weight) was diluted with 327_5 g of water and the
resultant solution was passed through a column preliminarily
packed with an H'-type cation exchange resin (Amberlite IR-120B)
to give 350 g of an aqueous solution of active silica. This
aqueous active silica solution contained 8.3o by weight of SiOt.
10.9 g of hexadecylamine was dissolved in 76.8 g of ethanol and
then 100g of the above-described aqueous active silica solution
was added thereto under stirring_ The obtained mixture had a
pH value of 9. Then the mixture was reacted by allowing to stand
at room temperature for 22 hours. The complex thus obtained was
filtered, washed with water and then dried at 70°C for 18 hours
to give a powder of a silica/template complex. A 3 g portion
of this powder was dispersed in 30 ml of ethanol, stirred at
60°C for 30 minutes and filtered. After repeating this procedure
thrice, the dispersion was dried at 100°C for 23 hours to give
mesoporous silica. A peak (d = 4.6 nm) was observed in the X-ray
diffraction pattern of this sample_ This sample showed a
specific surface area of 780 m~/g, an average pore diameter of
4.0 nm and a water monolayer adsorption of 1.70/nmz.
A 5 g portion of the silica/template complex obtained in
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Example 1 was calcinated at 550°C in the atmosphere for 6 hours
to give mesoporous silica . A peak (d = 4 . 3 nm) was observed in
the X-ray diffraction pattern of this sample. This sample
showed a specific surface area of 970 m'/g, an average pore
diameter of 3. 9 nm and a water monolayer adsorption of 1 _ 49/nmZ.
A silica/template complex powder was prepared as in
Example 1 but using 8 _ 34 g of dodecylamine as a substitute for
hexadecylamine employed as the template. The white powder thus
obtained was calcinated as in Example 2 to give mesoporous silica.
A peak (d = 3. 6 nm) was observed in the X-ray diffraction pattern
of this sample. This sample showed a specific surface area of
1020 m'/g, an average pore diameter of 2. 8 nm and a water monolayer
adsorption of 1.57/nmZ.
Example 4
3.0 g of polyoxyethylene lauryl ether (Emulgen 108,
manufactured by Kao Corporation) was added to 13.9 g of water
and dissolved therein_ Next, 50 g of the active silica prepared
in Example 1 was added thereto. The obtained mixture showed a
pH value of 5. Then the mixture was reacted by allowing to stand
at room temperature for 22 hours. The complex thus obtained was
filtered, washed with water and then dried .at 70°C for 18 hours
to give a powder of a silica/template complex. The white powder
thus obtained was treated with ethanol as in Example 1 to give
mesoporous silica. A peak (d = 4 .0 nm) was observed in the X-ray
diffraction pattern of this sample. This sample showed a
specific surface area of 900 mZ/g, an average pore diameter of
2.0 nm and a water monolayer adsorption of 2.10/nm:.
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Example 5
A 5 g portion of the silica/template complex obtained in
Example 4 was calcinated at 550°C in the atmosphere for 6 hours
to give mesoporous silica. A peak (d = 4 _0 nm) was observed in
the X-ray diffraction pattern of this sample. This sample
showed a specific surface area of 1000 m'/g and an average pore
diameter of 2.1 nm.
13.7 g of N,N-dimethyltetradecylamine N-oxide was added
as a template to 15.7 g of water and dissolved therein. Next,
50 g of the active silica prepared in Example 1 was added thereto:
The obtained mixture showed a pH value of 5. Then the mixture
was reacted by allowing to stand at room temperature for 22 hours.
The complex thus obtained was filtered, washed with water and
then dried at 70°C for 18 hours to give a powder of a sil-
ica/template complex_ The white powder thus obtained was
treated with ethanol as in Example 1 to give mesoporous silica.
A peak (d = 3. 9 nm) was observed in the X-ray diffraction pattern
of this sample. This sample showed a specific surface area of
1000 m~/g, an average pore diameter of 2 . 5 nm and a water monolayer
adsorption of 2.47/nms.
Example 7
A 5 g portion of the silica/template complex obtained in
Example 6 was calcinated at 550°C in the atmosphere for 6 hours
to give mesoporous silica . A peak (d = 3. 9 nm) was observed in
the X-ray diffraction pattern of this sample. This sample
showed a specific surface area of 1200 mr/g and an average pore
diameter of 2_6 nm.
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Exam~,le 8
8.1 g of hexadecylamine was added as a template to 70 ml
of ethanol and dissolved therein. Next, 27.32 g of tetraeth-
oxysilane was added thereto under stirring. The obtained
mixture showed a pH value of 9. Then the mixture was reacted
by allowing to stand at room temperature for 18 hours_ The
obtained complex was filtered, washed with water and air-dried
for 48 hours to give a silica/template complex powder. An 8 g
portion of the thus obtained white powder was dispersed in 800
ml of ethanol and stirred at 60°C for 30 minutes . Next, it was
filtered and washed by adding from top 800 ml of ethanol. After
repeating this procedure twice, the mixture was dried at 70°C
for 23 hours to give mesoporous silica. A peak (d = 4.5 nm) was
observed in the X-ray diffraction pattern of this sample. This
sample showed a specific surface area of 860 mt/g, an average
pore diameter of 3_4 nm and a water monolayer adsorption of
1.92/nm~'.
Example 9
I 138 g of No.3 water-glass (Si02 = 29% by weight, NazO =
9.5o by weight) was diluted with 262 g of water and the resultant
solution was passed through a column preliminarily packed with
an H'-type cation exchange resin (Amberlite IR-120B) to give 400
g of an aqueous solution of active silica _ This aqueous active
silica solution contained 8.1o by weight of SiO~_ 10.9 g of
hexadecylamine was dissolved in 76.8 g of ethanol and then 100
g of the above-described aqueous active silica solution was added
thereto under stirring. The obtained mixture had a pH value of
9. Then the mixture was reacted by allowing to stand at room
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CA 02415784 2004-12-21
temperature for 22 hours. The complex thus obtained was fil-
tered, washed with water and then dried at 100°C for 10 hours
to give 18.2 g of a white powder. This dry powder was calcinated
at 550°C in the atmosphere for 6 hours to give a white calcinated
product. A peak (d - 3.98 nm) was observed in the X-ray
diffraction pattern of this sample. This sample showed a
specific surface area of 870 m'/g, an average pore diameter of
4.3 nm, and a water monolayer adsorption of 1.4/nm~.
A mixture prepared as in Example 9 was reacted by allowing
to stand at room temperature for 22 hours. The complex thus
obtained was filtered, washed with water and dried at 100°C for
hours to give a white powder. A 2 g portion of this dry powder
was dispersed in 200 ml of ethanol, mixed by stirring at 60°C
for 1 hour and then filtered. After repeating this procedure
thrice, the mixture was dried at 100°C for 3 hours to give 0 _ 8
g of a white powder. This sample showed a specific surface area
of 900 m~/g, an average pore diameter of 4_3 nm, and a water
monolayer adsorption of 1.7/nm~. After evaporating off the
ethanol from the extract, 1.1 g of the hexadecylamine contained
as the template in the dry powder was recovered.
Example 11
The mesoporous silica synthesized in Example 1 was ground
with a jet mill manufactured by Seisin Enterprise Co. , Ltd. to
give a sample having an average particle diameter of 2.7 pm
(hereinafter referred to as the sample A) . This sample A showed
a specific surface area of 700 m~/g, a pore volume of 1.6 cc/g
and an average pore diameter in the mesopore region of 4.0 nm.
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CA 02415784 2004-12-21
The sample A was mixed with water to give a dispersion
having a mesoporous silica concentration of 13.8°s by weight.
This dispersion was mixed with a 10 o by weight aqueous solution
of ration PVA and a loo by weight aqueous solution of sila-
nol-modified PVA to give a slurry having a weight ratio of
mesoporous silica:cation PVA:silanol-modified PVA of 6.2:2 and
a solid content of 12 o by weight . This slurry was applied onto
a polyethylene terephthalate sheet (thickness: 100 Eun) with a
bar coater and dried to give a recording sheet provided with
an ink absorbent layer of about 30 ~m in thickness. This
recording sheet contained about 12 g/m' of the mesoporous silica.
Fxam ~ 1
A recording sheet was prepared as in Example 11 but using
the sample synthesized in Example 2 as a substitute for the sample
A employed in Example 11.
Example 13
A recording sheet was prepared as in Example 11 but using
the sample synthesized in Example 8 as a substitute for the sample
A employed in Example 11.
Comparative Example I
A recording sheet was prepared as in Example 11 but using
silica gel (CarplexT~'' 304N, manufactured by Shionogi & Co_ , Ltd. ,
average particle diameter: 9 Pm) as a substitute for the sample
A employed in Example 11.
Comparative Example 2
As a recording sheet, use was made of a marketed ink
jet paper (MJOHP1N manufactured by SEIKO EPSON CORPORATION)_
The printing characteristics of the samples of Examples
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CA 02415784 2004-12-21
11, 12 and 13 and Comparative Examples 1 and 2 were evaluated
in the following manner.
In evaluating the following items (1) to (3) , use was made
of each recording sheet formed above having been solid-printed
in yellow, magenta, cyan, black, green, red and blue by using
a marketed ink-jet printer (PM-750C manufactured by SEIKO EPSON
CORPORATION) . In evaluating the item (4), use was made of each
recording sheet formed above having been solid-printed in yellow
by using a marketed ink-jet printer (DJ-694C manufactured by
Hewlett-Packard, Ltd.).
Optical density was measured by using DM400 manufactured
by SCREEN.
(1) Printing performance:
Ink cissing and blurring at borders were evaluated with
the naked eye:
O: no blurring; D: somewhat blurring;
x: serious blurring.
(2) Ink dryness:
Immediately after printing, a white paper sheet was
pressed against the printed part and the extent of ink transfer
was judged:
O: no transfer after 60 sec.; 0: no transfer after
90 sec.; and x: transfer after 90 sec.
(3) Water resistance
A printed recording sheet was immersed in water for 2
minutes and dried. Then the extent of ink blurring and run-
off was evaluated with the naked eye:
O: little ink run-off; O: moderate ink run-off; and
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CA 02415784 2004-12-21
x: serious ink run-off.
(4) Light resistance
A printed recording sheet was irradiated with light
corresponding to~a spectrophotometeric distribution of AM 1.5
at an irradiation intensity of 100 mW/cm' from a solar simulator
(WXS-50S-1_5 manufactured by WACOM). After irradiating for 60
hours, the optical density was measured and the change ratio
was determined.
Table 1 summarizes the evaluation results.
Table 1
Printing per- Ink dryness Water resis-Light resis-
formance tance tance
Ex. 11 O O O -130
Ex. 12 O O D -14%
Ex. 13 O O D -14~
C_Ex. 1 O O x -320
C_Ex. 2 O O O -52
Industrial Ap~licabil;tv
The present invention provides mesoporous silica having
highly hydrophilic surface compared with the conventional ones
and a novel process for synthesizing the mesoporous silica. The
mesoporous silica of the invention is superior in the capability
of absorbing aqueous solutions, etc. to the conventional ones.
Also, the mesoporous silica can be synthesized under mild
conditions (for example, room temperature, neutral conditions,
etc.) with the use of inexpensive materials. Also, the
invention is advantageous in that, for example, the template
contained in the complex obtained by the reaction can be easily
removed by a solvent without calcination at a high temperature.
A recording sheet containing mesoporous silica can
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CA 02415784 2004-12-21
provide printed matters which are free from ink blurs, have a
high ink-absorptivity and are excellent in water resistance and
light resistance. In particular, one containing mesoporous
silica having a monolayer adsorption of water at 25°C of 1. 7/nm~'or
more shows an improved water resistance compared with the
conventional ones.
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