U.S. patent application number 09/874055 was filed with the patent office on 2002-07-25 for coated fiber material and coating solution used therefor.
This patent application is currently assigned to KAZARI-ICHI CO., LTD.. Invention is credited to Iwamiya, Yoko, Yagi, Osamu.
Application Number | 20020096284 09/874055 |
Document ID | / |
Family ID | 18733312 |
Filed Date | 2002-07-25 |
United States Patent
Application |
20020096284 |
Kind Code |
A1 |
Iwamiya, Yoko ; et
al. |
July 25, 2002 |
Coated fiber material and coating solution used therefor
Abstract
An object of the present invention is to provide a method for
the manufacture of a coated material having an appropriate
strength, a good light transmitting property and a good water
repelling property by applying to fiber material ready at hand such
as Japanese paper, western paper, cloth, etc. in view of a property
of a fiber material such as softness and also to provide a coating
solution used for the coated material. The above object can be
achieved by a method for the manufacture of a coated material in
which a coating solution of a silane type is applied to a fiber
material and hardened/solidified by the action of a catalyst to
give a coated paper to which an appropriate strength and good light
transmitting property and water repelling property are given and
also by a coating solution used therefor.
Inventors: |
Iwamiya, Yoko; (Yokohama,
JP) ; Yagi, Osamu; (Yokohama, JP) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT PC
FOURTH FLOOR
1755 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
US
|
Assignee: |
KAZARI-ICHI CO., LTD.
Yokohama
JP
|
Family ID: |
18733312 |
Appl. No.: |
09/874055 |
Filed: |
June 6, 2001 |
Current U.S.
Class: |
162/164.4 |
Current CPC
Class: |
D21H 17/59 20130101;
C09D 4/00 20130101; D21H 25/06 20130101; D21H 17/06 20130101; D21H
19/32 20130101; C09D 4/00 20130101; C08G 77/04 20130101 |
Class at
Publication: |
162/164.4 |
International
Class: |
D21H 017/13 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 10, 2000 |
JP |
2000-242269 |
Claims
What is claimed is:
1. A coated material, characterized in that, a surface is formed
where a coating solution of a silane type mainly comprising a
compound represented by the formula 1 is applied to a fiber
material and hardened/solidified by the action of a catalyst. 6(in
the formula 1, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 may be same or
different and each is hydrogen or an alkyl group having 1-4
carbon(s)).
2. The coated material according to claim 1, wherein the surface is
formed where, prior to the application of the coating solution, the
said fiber material is dipped in alcohol and dried and ultraviolet
ray is further irradiated thereto.
3. The coated material according to claim 1, wherein the surface is
formed where a hydrolyzable organic metal compound is used as a
catalyst for hardening/solidifying the said coating solution of a
silane type.
4. The coated material according to claim 3, wherein the surface is
formed where one or more organometallic compound(s) selected from a
group consisting of titanium, zirconium, aluminum and tin is/are
used as the said hydrolyzable organometallic compound.
5. The coated material according to claim 1, wherein the surface is
formed where, in addition to the above-mentioned main component, a
coating solution containing a compound represented by the formula 2
having three hydrolyzable substituents and one unhydrolyzable
substituent is used as the said coating solution of a silane type.
7(in the formula 2, R.sub.5, R.sub.6 and R.sub.7 may be same or
different and each is a monomer comprising hydrogen, an alkyl group
or an alkenyl group; a bond of R.sub.5O, R.sub.6O and R.sub.7O to
Si is an oligomer comprising a siloxane bond; and R.sub.8 is an
alkenyl group or a phenyl group which may contain an epoxy group or
a glycidyl group in a molecule)
6. The coated material according to claim 1, wherein the surface is
formed where, in addition to the above-mentioned main component, a
coating solution containing a compound represented by the formula 3
having two hydrolyzable substituents and two unhydrolyzable
substituents is used as the said coating solution of a silane type.
8(in the formula 3, R.sub.9 and R.sub.11 may be same or different
and each is a monomer comprising hydrogen, an alkyl group or an
alkenyl group; a bond of R.sub.9O and R.sub.11O to Si is an
oligomer comprising a siloxane bond; and R.sub.10 and R.sub.12 each
is an alkyl group, an alkenyl group or a phenyl group which may
contain an epoxy group or a glycidyl group in a molecule)
7. The coated material according to claim 1, wherein the surface is
formed where, in addition to the above-mentioned main component, a
coating solution containing the compound represented by the formula
2 and the compound represented by the formula 3 is used as the said
coating solution of a silane type. 9 10(in the formula 2 R.sub.5,
R.sub.6 and R.sub.7 may be same or different and each is a monomer
comprising hydrogen, an alkyl group or an alkenyl group; a bond of
R.sub.5O, R.sub.6O and R.sub.7O to Si is an oligomer comprising a
siloxane bond; and R.sub.8 is an alkyl group, an alkenyl group or a
phenyl group which may contain an epoxy group or a glycidyl group
in a molecule; and in the formula 3, R.sub.9 and R.sub.11 may be
same or different and each is a monomer comprising hydrogen, an
alkyl group or an alkenyl group; a bond of R.sub.9O and R.sub.11O
to Si is an oligomer comprising a siloxane bond; and R.sub.10 and
R.sub.12 each is an alkyl group, an alkenyl group or a phenyl group
which may contain an epoxy group or a glycidyl group in a
molecule)
8. A coating solution of a silane type for giving an appropriate
strength and good light transmitting and water repelling properties
to a fiber material where the said coating solution contains the
main component compound represented by the above formula 1 and a
catalyst for hardening/solidifying thereof. 11(in the formula 1,
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 may be same or different and
each is hydrogen or an alkyl group having 1-4 carbon(s)).
9. The coating solution according to claim 8, wherein the catalyst
for hardening/solidifying the said coating solution of a silane
type is a hydrolyzable organometallic compound.
10. The coating solution according to claim 9, wherein the
hydrolyzable organometallic compound is one or more organometallic
compound(s) selected from a group consisting of titanium,
zirconium, aluminum and tin.
11. The coating solution according to claim 8, wherein the coating
solution of a silane type contains a compound represented by the
formula 2 having three hydrolyzable substituents and one
unhydrolyzable substituent in addition to the above main component.
12(in the formula 2, R.sub.5, R.sub.6 and R.sub.7 may be same or
different and each is a monomer comprising hydrogen, an alkyl group
or an alkenyl group; a bond of R.sub.5O, R.sub.6O and R.sub.7O to
Si is an oligomer comprising a siloxane bond; and R.sub.8 is an
alkenyl group or a phenyl group which may contain an epoxy group or
a glycidyl group in a molecule)
12. The coating solution according to claim 8, wherein the coating
solution of a silane type contains a compound represented by the
formula 3 having two hydrolyzable substituents and two
unhydrolyzable substituents in addition to the above main
component. 13(in the formula 3, R.sub.9 and R.sub.11 may be same or
different and each is a monomer comprising hydrogen, an alkyl group
or an alkenyl group; a bond of R.sub.9O and R.sub.11O to Si is an
oligomer comprising a siloxane bond; and R.sub.10 and R.sub.12 each
is an alkyl group, an alkenyl group or a phenyl group which may
contain an epoxy group or a glycidyl group in a molecule)
13. The coating solution according to claim 8, wherein the coating
solution of a silane type contains the compound represented by the
formula 2 and the compound represented by the formula 3 In addition
to the above main component. 14(in the formula 2 R.sub.5, R.sub.6
and R.sub.7 may be same or different and each is a monomer
comprising hydrogen, an alkyl group or an alkenyl group; a bond of
R.sub.5O, R.sub.6O and R.sub.7O to Si is an oligomer comprising a
siloxane bond; and R.sub.8 is an alkyl group, an alkenyl group or a
phenyl group which may contain an epoxy group or a glycidyl group
in a molecule; and in the formula 3, R.sub.9 and R.sub.11 may be
same or different and each is a monomer comprising hydrogen, an
alkyl group or an alkenyl group; a bond of R.sub.9O and R.sub.11O
to Si is an oligomer comprising a siloxane bond; and R.sub.10 and
R.sub.12 each is an alkyl group, an alkenyl group or a phenyl group
which may contain an epoxy group or a glycidyl group in a molecule)
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a coated material which
gives an appropriate strength, a good light transmission, good
water repelling property and softness and a flame retarding
property to a paper material such as Japanese paper and western
paper or a cloth material such as nonwoven fabric and cloth
(hereinafter, all of them will be inclusively referred to as "fiber
material") and also to a coating solution used therefor.
[0003] 2. Description of the Related Art
[0004] Essentially, any paper material has no light transmitting
property except paraffin paper, cellophane paper, etc. and, in
addition, such a material is weak to water because of the fact that
it is paper. Thus, paper having a light transmitting property which
has been known already has a poor water repelling property. If the
material is not limited to paper, materials having a light
transmitting property and a water repelling property are available
and they are prepared, for example, by spreading a plastic material
or a vinyl material into a sheet form.
[0005] In addition, a paper material is much used for houses and
dwellings. For example, with regard to a shoji (a paper sliding
door) used as a partition for Japanese rooms, there have been used
a Japanese shoji paper, rayon shoji paper manufactured by
compounding pulp with rayon, polypropylene, etc. in a predetermined
ratio, a shoji paper manufactured by subjecting the rayon shoji
paper to a laminating treatment with a plastic film, and a shoji
paper manufactured by subjecting the surface of Japanese paper to a
laminating treatment with an acrylate material or a vinyl chloride
material.
[0006] However, paper having an excellent light transmitting
property such as paraffin paper and cellophane paper has, first of
all, a high hygroscopicity to water having no excellent
strength.
[0007] On the other hand, although a plastic sheet, a vinyl sheet,
etc. having a high light transmitting property and an excellent
water repelling property are able to give higher light transmitting
property and better water repelling property as compared with
paper, their manufacture is to be carried out by means of a factory
production and it is not possible to easily manufacture a substance
having a good light transmitting property and an excellent water
repelling property from the materials which are ready at hand.
[0008] In addition, in houses and in public facilities such as
hotels and inns in recent years, a tough rayon shoji paper is used
and there is a disadvantage in the rayon shoji paper that static
electricity is apt to be generated and dust is apt to adhered
thereto. Since the rayon shoji paper is relatively resistant to
water, it can be cleaned by wiping with wet cloth although there is
a problem that, since it absorbs water when washed, the adhered
part is detached.
[0009] In order to solve the problems as mentioned above, a surface
coating by means of the so-called sol-gel method has been carried
out. Usually, a sol-gel liquid used here is that where
tetraalkoxysilane is a main chain and an organic substituent is
introduced thereinto with an object of giving a water repelling
property. In that case, the tetraalkoxysilane which is a main chain
has a strong inorganic property and, therefore, it is necessary to
use the so-called silane coupling agent represented by a phenyl
alkoxysilane for the introduction of an organic substituent.
However, the so-called silane coupling agent is expensive and,
moreover, its effect is not achieved until a certain amount is
used. Unfortunately, since there is a significant difference in the
hydrolyzing speeds between a silane coupling agent and a
tetraalkoxysilane as the main chain (where the tetraalkoxysilane is
quicker), there is a problem that, when a silane coupling agent is
used in a large amount, the reaction is apt to occur unevenly and
the strength of the resulting coated layer significantly
lowers.
[0010] For solving such a problem, the so-called organic-inorganic
hybrid material where an organic substituent is directly introduced
into a silicon atom has been synthesized and used. Although the
above object can be well achieved by the organic-inorganic hybrid
material, its synthesis is difficult whereby there is a
disadvantage that it is an expensive material.
[0011] In order to solve the above problem, the present applicant
also proposed a coated paper, etc. where a certain compounded
solution (coating solution) containing boron ion and halogen ion as
catalysts necessary for hardening the sol-gel liquid is applied to
paper, nonwoven fabric, etc. so that a good water repelling
property, etc. are given to such a material (Japanese Patent No.
3020934). However, in the case of the said coated paper, etc.,
neutralization of the paper takes place and that is not always
suitable for a long-term preservation of paper since halogen ion is
contained in the coating solution.
[0012] In addition, in the case of the coated paper, etc. mentioned
in the Japanese Patent No. 3020934, the coated layer is only
composed of a network where all of four bonds of silicon atom are
in a hard siloxane bond. There is another problem that, although
the surface of the coated paper is as hard as ceramics, it is
fragile as well whereby, when a fiber material such as paper having
softness is coated by that, the softness of the fiber material is
lost.
SUMMARY OF THE INVENTION
[0013] In view of such properties of the fiber material, etc., an
object of the present invention is to provide a coated material
having an appropriate strength, a good light transmitting property
and a good water repelling property by applying to a fiber material
ready at hand such as Japanese paper, western paper, cloth, etc.
and also to provide a coating solution used for the coated
material.
[0014] The invention of claim 1 of the present application
conducted for achieving the above object is a coated material,
characterized in that, a surface is formed where a coating solution
of a silane type mainly comprising a compound represented by the
formula 1 is applied to a fiber material and hardened/solidified by
the action of a catalyst. 1
[0015] (in the formula 1, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 may
be same or different and each is hydrogen or an alkyl group having
1-4 carbon(s)).
[0016] The invention of claim 2 of the present application relates
to the invention of the above claim 1 and is the coated material
according to claim 1, wherein the surface is formed where, prior to
the application of the coating solution, the said fiber material is
dipped in alcohol and dried and ultraviolet ray is further
irradiated thereto. The invention of claim 3 of the present
application relates to the invention of the above claim 1 and is
the coated material according to claim 1, wherein the surface is
formed where a hydrolyzable organic metal compound is used as a
catalyst for hardening/solidifying the said coating solution of a
silane type. The invention of claim 4 of the present application
relates to the invention of the above claim 3 and is the coated
material according to claim 3, wherein the surface is formed where
one or more organometallic compound(s) selected from a group
consisting of titanium, zirconium, aluminum and tin is/are used as
the said hydrolyzable organometallic compound.
[0017] The invention of claim 5 of the present application relates
to the invention of the above claim 1 and is the coated material
according to claim 1, wherein the surface is formed where, in
addition to the above-mentioned main component, a coating solution
containing a compound represented by the formula 2 having three
hydrolyzable substituents and one unhydrolyzable substituent is
used as the said coating solution of a silane type. 2
[0018] (in the formula 2, R.sub.5, R.sub.6 and R.sub.7 may be same
or different and each is a monomer comprising hydrogen, an alkyl
group or an alkenyl group; a bond of R.sub.5O, R.sub.6O and
R.sub.7O to Si is an oligomer comprising a siloxane bond; and
R.sub.8 is an alkenyl group or a phenyl group which may contain en
epoxy group or a glycidyl group in a molecule)
[0019] The invention of claim 6 of the present application relates
to the invention of the above claim 1 and is the coated material
according to claim 1, wherein the surface is formed where, in
addition to the above-mentioned main component, a coating solution
containing a compound represented by the formula 3 having two
hydrolyzable substituents and two unhydrolyzable substituents is
used as the said coating solution of a silane type. 3
[0020] (in the formula 3, R.sub.9 and R.sub.11 may be same or
different and each is a monomer comprising hydrogen, an alkyl group
or an alkenyl group; a bond of R.sub.9O and R.sub.11O to Si is an
oligomer comprising a siloxane bond; and R.sub.10 and R.sub.12 each
is an alkyl group, an alkenyl group or a phenyl group which may
contain en epoxy group or a glycidyl group in a molecule)
[0021] The invention of claim 7 of the present application is the
coated material according to claim 1, wherein the surface is formed
where, in addition to the above-mentioned main component, a coating
solution containing the compound represented by the formula 2 and
the compound represented by the formula 3 is used as the said
coating solution of a silane type. 4
[0022] (in the formula 2 R.sub.5, R.sub.6 and R.sub.7 may be same
or different and each is a monomer comprising hydrogen, an alkyl
group or an alkenyl group; a bond of R.sub.5O, R.sub.6O and
R.sub.7O to Si is an oligomer comprising a siloxane bond; and
R.sub.8 is an alkyl group, an alkenyl group or a phenyl group which
may contain en epoxy group or a glycidyl group in a molecule; and
in the formula 3, R.sub.9 and R.sub.11 may be same or different and
each is a monomer comprising hydrogen, an alkyl group or an alkenyl
group; a bond of R.sub.9O and R.sub.11O to Si is an oligomer
comprising a siloxane bond; and R.sub.10 and R.sub.12 each is an
alkyl group, an alkenyl group or a phenyl group which may contain
en epoxy group or a glycidyl group in a molecule)
[0023] The invention of claim 8 of the present application is a
coating solution of a silane type for giving an appropriate
strength and good light transmitting and water repelling properties
to a fiber material where the said coating solution contains the
main component compound represented by the above formula 1 and a
catalyst for hardening/solidifying thereof. The invention of claim
9 of the present application relates to the invention of the above
claim 8, wherein the catalyst for hardening/solidifying the said
coating solution of a silane type is a hydrolyzable organometallic
compound. The invention of claim 10 of the present application
relates to the invention of claim 9, wherein the hydrolyzable
organometallic compound is one or more organometallic compound(s)
selected from a group consisting of titanium, zirconium, aluminum
and tin.
[0024] The invention of claim 11 of the present application relates
to the invention of the claim 8, wherein the coating solution of a
silane type contains a compound represented by the formula 2 having
three hydrolyzable substituents and one unhydrolyzable substituent
in addition to the above main component. The invention of claim 12
of the present application relates to the invention of the claim 8,
wherein the coating solution of a silane type contains a compound
represented by the formula 3 having two hydrolyzable substituents
and two unhydrolyzable substituents in addition to the above main
component.
[0025] The invention of claim 13 of the present application relates
to the invention of the claim 8, wherein the coating solution of a
silane type contains the compound represented by the
above-mentioned formula 2 and the compound represented by the
above-mentioned formula 3 in addition to the above main component.
The present invention will now be illustrated in detail as
hereunder.
BRIEF DESCRIPTION OF THE DRAWING
[0026] FIG. 1 is to illustrate the testing apparatus used for the
evaluation of the water repelling property.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0027] In the present invention, a fiber material is coated with a
compound where, as shown in the formula 1, a repeating unit in
which one of four substituents of silicon atom is substituted with
an unhydrolyzable substituent is contained whereby the problems in
the prior art is solved. As compared with the conventionally used
compounds, the compound of the formula 1 has less one strong
siloxane bond between the adjacent silicon atom and such an
unreacted bond according thereto remains in the so-called unsettled
state whereby the softness of the coated layer can be retained and,
as a result, the softness of the coated material can be
retained.
[0028] In addition, since R.sub.4 in the formula 1 is not
hydrolyzed even when the compound of the formula 1 is hydrolyzed
and polycondensed later, an organic property is given to the
manufactured coated layer and, as a result, an organic property or,
in other words, a water repelling property is given to the coated
material.
[0029] As such, as compared with tetraalkoxysilane which is less
expensive but has a strong inorganic property, the material
(monomer) for preparing the compound of the formula 1 can be
purchased at a low cost in the similar degree to the above.
Accordingly, when the compound of the formula 1 is used, it is now
possible to manufacture a coated material having a layer having a
sufficient organic property and also a sufficient strength even if
the expensive silane coupling agent is not used together. As such,
the invention of the present application is characteristic in using
the compound represented by the formula 1 for achieving the
above-mentioned object.
[0030] In the invention of the present application, a fiber
material represented by a paper material such as Japanese paper and
western paper and a cloth material such as nonwoven fabric and
cloth is applied with a coating solution mainly comprising a
compound represented by the formula 1 and the solution is hardened
and solidified by the action of a catalyst. R.sub.1, R.sub.2 and
R.sub.3 in the formula 1 may be same or different and each is
hydrogen or an alkyl group having 1-4 carbon(s) while n is
preferably 2-10.
[0031] Such a compound may be manufactured by a condensation of a
monomer (such as methyltrimethoxysilane). The reason why the
repetition (n) of the main chain is 2-10 is that, if a monomer
(n=1) is used, the polymerization thereof is time-consuming and it
is difficult to manufacture a coated layer having a sufficient
strength within a short time. On the other hand, when n is 11 or
more, numbers of a alkoxy group, etc. for polymerization on the
fiber material after applying on the fiber material are
insufficient whereby it is difficult to manufacture a coated
membrane having a sufficient strength. Accordingly, the preferred
substance in the invention of the present application is a
condensate where n is 2-10 or, particularly, n is 2-8.
[0032] Generally speaking, in the synthesis of a condensate of the
formula 1 from a monomer, it is substantially impossible from a
technical viewpoint to correctly control its degree of
polymerization. Accordingly, the use of a substance where n is 2-10
or, preferably, n is 2-8 in the invention of the present
application means that a coating solution which mainly comprises
the substance where n is 2-10 or, preferably, 2-8 in view of
distribution of degree of polymerization is used and, therefore,
there is no problem even if a substance where n is 11 or more, for
example, is contained therein.
[0033] Specific examples of the compound represented by the formula
1 are condensates such as methyltrimethoxysilane,
ethyltrimethoxysilane, propyltrimethoxysilane,
butyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane,
propyltriethoxysilane, butyltriethoxysilane, methyltripropoxysilane
and ethyltripropoxysilane. Incidentally, the compound of the
formula 1 may be a condensate of only one kind of such a monomer or
may be a condensate of two or more of the above-exemplified
monomers.
[0034] The primitive role of the unhydrolyzable substituent
(R.sub.4) in the compound of the formula 1 is to give a softness to
a coated layer and, if a water repelling property is to be given to
the coated layer as well, R.sub.4 is an alkyl group. Generally, in
an organic substituent, the more the carbon numbers, the more the
organic property or the water repelling property but, when the
carbon numbers are too much, strain is resulted in the coated layer
due to a steric hindrance causing a deterioration in the layer
strength. Accordingly, it is preferred to decide the carbon numbers
of the alkyl group and also the type and the quantity of each
monomer constituting the compound (condensate) of the formula 1 by
carrying out a preliminary manufacturing test, etc. by referring to
the Examples, etc. of the specification of the present application.
Incidentally, it is also possible to give a water repelling
property to the coated layer by adding a compound of the formula 2
or 3 which will be mentioned later and, therefore, it is not
essential that R.sub.4 in the compound of the formula 1 is an alkyl
group.
[0035] With regard to a catalyst for hardening and solidifying the
compound of the formula 1, any commonly-used catalyst may be used
without particular limitation. In the case of an acid catalyst, the
examples are hydrochloric acid, nitric acid, sulfuric acid,
phosphoric acid, formic acid and acetic acid. In the case of a
basic catalyst, the examples are ammonia, tetramethylammonium
hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, ethanolamine,
diethanolamine and triethanolamine. When such a common catalyst is
used, water of reaction is made to coexist for
hardening/solidifying the compound of the formula 1.
[0036] As such, the coating solution provided by the present
invention contains a compound of the formula 1, a catalyst and
water of reaction. When it is used in a common way, there is no
particular problem but, when it is preserved for a long term, there
is a problem that the coating solution is apt to become a gel due
to the water of reaction. In order to solve that, it is recommended
to use a hydrolyzable organometallic compound as a catalyst instead
of the above-mentioned conventional catalyst. When the hydrolyzable
organometallic compound is used, the coexistence of the water of
reaction is not necessary and that is favorable in view of
stability for a long-term preservation.
[0037] When an organometallic compound is mixed with a compound of
the formula 1 and the resulting coating solution is applied to a
fiber material such as paper, it absorbs moisture on the paper or
moisture (damp) in the air and the organometallic compound
hydrolyses by itself. At that time, a network is formed with the
compound of the formula 1 whereby the compound of the formula 1 is
hardened/solidified. Examples of he organometallic compound which
is preferably used in the invention of the present application are
those containing titanium, zirconium, aluminum or tin. To be more
specific, tetrapropoxy titanate, tetrabutoxy titanate, tetrapropoxy
zirconate, tetrabutoxy zirconate, tripropoxy aluminate, aluminum
acetylacetonate, dibutyltin diacetate and dibutyltin dilaurate.
[0038] Further, an organic solvent may be added to the coating
solution of the invention of the present application so that the
compound of the formula 1, the catalyst and water of reaction which
is needed in some cases are homogeneously mixed. Examples of the
organic solvent used for such an object are alcohol compounds. To
be more specific, methanol, ethanol, propanol, isopropanol,
butanol, pentanol and hexanol may be exemplified. It is also
possible to adjust the viscosity and the drying speed of the
coating solution by controlling its adding amount.
[0039] With an object of such a control, it is particularly
preferred to use an organic solvent having high viscosity and
boiling point such as glycols (for example, ethylene glycol,
propylene glycol, diethylene glycol, polyethylene glycol,
dipropylene glycol and polypropylene glycol) and cellosolves (for
example, methoxyethanol, propoxyethanol, butoxyethanol,
methoxypropanol, ethoxypropanol, propoxypropanol and
butoxypropanol) either solely or jointly. It goes without saying
that the already-mentioned alcohol may be added together with the
above-mentioned one or more organic solvent (s) having high
viscosity and boiling point. When an object is to adjust the
viscosity and the drying speed of the coating solution, the same
effect can be achieved not only by the above-mentioned organic
solvent but also by a surface-active agent.
[0040] Especially in the case of the above-mentioned glycols and
cellosolves, they have hydroxyl groups in a molecule and,
therefore, they may be introduced into a network of the siloxane
bond formed by the condensation reaction of the compound of the
formula 1. Since glycols and cellosolvs have an organic property,
there is an increase in the organic property of the resulting
coated layer or, in other words, there is an increase in the
organic property of the coated material as a result of such an
introduction.
[0041] In the method for the manufacture of a coated material
according to the invention of the present application, a fiber
material is cut at first, then processed in an optional size and
shape and applied with the above-mentioned coating solution of the
invention of the present application. With regard to a specific
method of application, there is no particular limitation and it may
be carried out, for example, by dipping a fiber material in a
coating solution, by applying a coating solution to a fiber
material or by spraying a coating solution to a fiber material.
[0042] In the invention of the present application, a coated
material can be manufactured using, for example, a product prepared
by making the fiber of a bark into paper followed by drying, a
high-class hand-made Japanese paper, an ordinary Japanese paper,
western paper or yuzen paper (Japanese printed paper) manufactured
by a machine, fiber made from nonwoven fabric or an ordinary cloth
as a fiber material. When a fiber material is subjected to a
certain pretreatment before applying a coating solution, bonding of
the fiber material surface to the coated layer can be made
reinforced as compared with that which is not subjected to the said
pretreatment.
[0043] An example of such a pretreatment is that a fiber material
is dipped for about 30 minutes in isopropyl alcohol having a purity
of as high as about 98%, then allowed to stand at a high
temperature of about 100.degree. C. to completely dry and, after
that, irradiated with ultraviolet ray for about 30 minutes.
[0044] When a coating solution is applied to a fiber material which
is or is not subjected to the certain pretreatment as mentioned
above, the compound of the formula 1 is hydrolyzed and a siloxane
bond (Si--O--Si) is formed via a reaction as shown in (1) to (3) of
the following reaction formulae 1.
[0045] Reaction Formulae 1:
[0046] (1) Si--OR+H.sub.2O.fwdarw.Si--OH+ROH
[0047] (2) Si--OH+HO--Si.fwdarw.Si--O--Si+H.sub.2O
[0048] (3) Si--OH+RO--Si.fwdarw.Si--O--Si+ROH
[0049] The bonding energy of Si--O in the resulting siloxane bond
(Si--O--Si) as such is 106 kcal/mol while the bonding energy of
C--C bond which is a typical bond in organic compounds is 82.6
kcal/mol. It is therefore understood that the coated layer of a
glassy quality having a siloxane bond produced by hydrolysis of a
compound of the formula 1 has far more thermally stable bond as
compared with organic compounds. Due to the said thermally stable
bond, the coated layer which is formed by the invention of the
present application becomes excellent in terms of heat resistance
and abrasion resistance and, as a result, it is possible to
manufacture a coated material having excellent resistance to heat
and to abrasion.
[0050] When the coating solution of the invention of the present
application contains the above-mentioned organometallic compound
(such as tetrabutoxy titanium) as a catalyst, the reactions of (1)
to (3) in the above reaction formulae 1 proceed even when water of
reaction is not contained in the coating solution and, to be more
precise, the reaction at that time is as shown in (4) and (5) in
the following reaction formulae 2.
[0051] Reaction Formulae 2:
[0052] (4) Ti--Or+H.sub.2O.fwdarw.Ti--OH+ROH
[0053] (5) Ti--OH +RO--Si.fwdarw.Ti--O--Si
[0054] As a result of introduction of the Ti--O bond into the
coated layer as mentioned above, resistance to heat and to abrasion
can be further improved as compared with a coated layer solely
comprising a siloxane bond. When an organometallic compound is used
as a catalyst as such, it is not necessary that water of reaction
is made to coexist and, in addition, resistance of the coated layer
to heat and to abrasion can be further improved whereby resistance
of the coated material to heat and to abrasion can be far
stronger.
[0055] In the invention of the present application, a coating
solution containing a compound of the formula 2 in addition to the
compound of the formula 1 is used and, as a result, it is possible
to newly add a property of the compound of the formula 2 such as an
organic property or to potentiate a property such as an organic
property as compared with the coated material manufactured without
the use of the above-mentioned coating solution. The compound of
the formula 2 which is added with such an object is a compound
where three of the four substituents are hydrolyzable while the
remaining one is an unhydrolyzable substituent.
[0056] In the formula 2, R.sub.5, R.sub.6 and R.sub.7 may be same
or different and each is a monomer comprising hydrogen or an alkyl
or alkenyl group having 1-10 carbon(s); a bond of R.sub.5O,
R.sub.6O and R.sub.7O with Si is an oligomer comprising a siloxane
bond; and R.sub.8 is an alkyl or alkenyl group having 1-10
carbon(s) or a phenyl group which may contain an epoxy group or a
glycidyl group in its molecule.
[0057] Specific examples of the compound of the formula 2 are
vinyltrimethoxysilane, phenyltrimethoxysilane,
.gamma.-(methacryloxypropy- l)trimethoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane,
aminopropyltrimethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltrimethoxys- ilane,
vinyltriethoxysilane, phenyltriethoxysilane,
.gamma.-(methacryloxypropyl)triethoxysilane,
.gamma.-glycidoxypropyltriet- hoxysilane,
aminopropyltriethoxysilane and vinyltris(.beta.-methoxyethoxy)-
silane as well as condensates of about 2 to 10 molecules
thereof.
[0058] Incidentally, the compound of the formula 2 may be two or
more kinds of such monomers. When a condensate of two or more
molecules is used as the compound of the formula 2, that may be a
condensate of two or more of such monomers.
[0059] It is also possible in the invention of the present
application that a coating solution to which a compound of the
formula 3 is further added is used in addition to a coating
solution containing a compound of the formula 1 or a coating
solution containing both compounds of the formulae 1 and 2 whereby
a property of the compound of the formula 3 such as an organic
property is newly given or a property such as an organic property
is potentiated as compared with a coated material which is
manufactured without the use of it.
[0060] The compound of the formula 3 is a compound where, among the
four substituents, two are hydrolyzable substituents while other
two are unhydrolyzable substituents. In the formula 3, R.sub.9 and
R.sub.11 may be same or different and each is a monomer comprising
a hydrogen atom or an alkyl or alkenyl group having 1-10 carbon(s);
bond of R.sub.9O and R.sub.11O with Si is an oligomer comprising a
siloxane bond; and R.sub.10 and R.sub.12 each is an alkyl or
alkenyl group having 1-10 carbon(s) or a phenyl group having an
epoxy group or a glycidyl group in its molecule.
[0061] Specific examples of the compound represented by the formula
3 are dimethyldimethoxysilane, dimethyldiethoxysilane,
diethyldimethoxysilane, diethyldiethoxysilane,
diphenyldimethoxysilane, diphenyldiethoxysilane,
methylvinyldimethoxysilane and methylvinyldiethoxysilane as well as
condensates comprising about 2-10 molecules thereof. Incidentally,
the compound of the formula 3 may be two or more kinds of such
monomers. When a condensate of two or more molecules is used as the
compound of the formula 3, that may be a condensate of two or more
of such monomers.
[0062] When any of the compounds of the formula 2 and formula 3 as
mentioned above is added to a coating solution, it is possible to
increase an organic property of the coating solution while, when
both compounds of the formulae 2 and 3 are added to the coating
solution, the organic property of the coated layer can be further
improved and, as a result, a water repelling property, etc. of the
coated material can be further improved as well.
[0063] It is preferred that, in general, the compound of the
formula 2 and/or the compound of the formula 3 are/is added to the
coating solution in such an amount that the total amount does not
exceed 50% of the compound of the formula 1 which is the main
component of the coating solution. When the total adding amount
exceeds that range, bonding with the compound of the formula 1
which is the main component does not well take place when the
coating solution is applied to a fiber material whereby there is
possibility that the strength of the coated layer is insufficient.
Accordingly, in the case of actual addition of the compound of the
formula 2 and/or the compound of the formula 3, it is recommended
that, taking the fact that the strength of the coated layer lowers
depending upon the adding amount into consideration, the addition
is kept minimum after elucidating the adding amount by which the
object can be achieved as a result of a preliminary manufacturing
test, etc. by referring to the Examples of the specification of the
present application.
[0064] The primary role of the unhydrolyzable substituents
(R.sub.8, R.sub.10 and R.sub.12) in the compound of the formula 2
and the compound of the formula 3 is to give softness to the coated
layer and, since they are organic substituents such as an alkyl
group, they also play a role of giving a water repelling property
to the coated layer. Generally, in the organic substituents, the
more the carbon numbers, the more the organic property or the water
repelling property while, when the carbon numbers are too many, a
strain is resulted in the coated layer due to a steric hindrance
causing a lowering of the strength of the layer. Accordingly, it is
recommended that the carbon numbers of the organic substituent and
the type and the quantity of each of the monomers constituting the
compound of the formula 2 and/or the compound of the formula 3
(condensate) are elucidated after carrying out a preliminary
manufacturing test, etc. by referring to the Examples, etc. of the
specification of the present application.
[0065] A siloxane bond which has a strong resistance to heat and to
abrasion is, on the other hand, the so-called "hard" bond as well.
Due to the said "hardness", it is possible to give a resistance to
abrasion to a fiber material such as paper upon application to the
said material. However, a fiber material such as paper is
characteristic by its softness and a coated material is sometimes
requested to have the softness as same as paper, etc. which is a
material therefor.
[0066] In a sol-gel coating solution which has been commonly used
already, tetraalkoxysilane (Si(OR).sub.4) or an oligomer thereof is
used as a starting material. When a coated layer is formed by its
complete hydrolysis reaction ((1) to (3) in the already-mentioned
formula 1), all of the four bonds of silicon atom form a network of
a hard siloxane bond giving a layer which is as hard as ceramics
but is fragile without softness and, therefore, it has been
practically impossible to manufacture a coated material where the
softness of paper, etc. is well utilized.
[0067] According to the invention of the present application
however, a compound of the formula 1 where one of the four
substituents for silicon atom is not hydrolyzable is used as a main
component of the coating solution whereby the above problem is
solved. Moreover, according to the invention of the present
application, a compound of the formula 2 and the compound of the
formula 3 having one and two unhydrolyzable substituent(s)
respectively are added to the coating solution whereby it is
possible to further increase the softness, etc.
Detailed Description of Preferred Embodiments
[0068] The invention of the present application will now be further
illustrated by way of the following Examples although those
Examples are just examples and they are not intended to limit the
invention of the present application.
EXAMPLE 1
Manufacture of Alkoxysilane Condensates
[0069] A methyltrimethoxysilane condensate (MTM), an
ethyltrimethoxysilane condensate (ETM) and a methyltriethoxysilane
condensate (MTE) were synthesized as follows.
[0070] (1) Synthesis of MTM.
[0071] To a 500-ml three-necked flask were added 181 g of
methyltrimethoxysilane, 50 g of methanol and 18 g of pure water
followed by well stirring. Then 2 g of 61% nitric acid were added,
the mixture was heated to reflux for 3 hours with stirring and,
after completion of the reaction, methanol was removed by making
the inner part of the reactor vacuum with heating. The MTM prepared
as such is mainly composed of trimer to tetramer according to a gas
chromatographic analysis.
[0072] (2) Synthesis of ETM.
[0073] To a 500-ml three-necked flask were added 200 g of
ethyltrimethoxysilane, 50 g of methanol and 18 g of pure water
followed by well stirring. Then 2 g of 61% nitric acid were added,
the mixture was heated to reflux for 7 hours with stirring and,
after completion of the reaction, methanol was removed by making
the inner part of the reactor vacuum with heating. The ETM prepared
as such is mainly composed of trimer to tetramer according to a gas
chromatographic analysis.
[0074] (3) Synthesis of MTE.
[0075] To a 500-ml three-necked flask were added 273 g of
methyltriethoxysilane, 50 g of ethanol and 18 g of pure water
followed by well stirring. Then 2 g of 61% nitric acid were added,
the mixture was heated to reflux for 12 hours with stirring and,
after completion of the reaction, methanol was removed by making
the inner part of the reactor vacuum with heating. The MTE prepared
as such is mainly composed of trimer to tetramer according to a gas
chromatographic analysis.
EXAMPLE 2
Preparation of Coating Solution and Manufacture of Coated
Material
[0076] (1) Preparation of Coating Solution.
[0077] Alkoxysilane condensates synthesized in Example 1 were used
and 17 kinds of coating solutions of the invention of the present
application as shown in Table 1 containing the condensate as a main
component (hereinafter, they will be referred to as the coating
solution 1 to 17, etc. by citing the number given in Table 1) were
prepared. For comparison, 4 kinds of coating solutions as shown in
Table 2 containing methyl methoxysilane monomer as a main component
(hereinafter, they will be referred to as the comparative coating
solution 1 to 12, etc. by citing the number given in Table 2) were
prepared.
[0078] (2) Manufacture of Coated Material.
[0079] On Jun. 21, 2000 in the laboratory of the applicant company
of the present application (room temperature: 25.degree. C.;
humidity: 70%), the applicant of the present application applied 29
kinds, in total, of the coating solutions mentioned in the above
(1) to a fiber material whereupon coated materials were prepared.
At first, plural yuzen paper sheets (Japanese paper on which a
pattern is printed) were prepared as fiber materials and the said
yuzen paper was dipped in each of the coating solutions for 30
seconds. After that, in order to prevent the deformation of the
yuzen paper by heat, drying was started at 60.degree. C.,
temperature was gradually raised up to 100.degree. C. in the final
stage so that the said yuzen paper was completely dried whereupon
the coated materials (yuzen paper) of the invention of the present
application were manufactured.
EXAMPLE 3
Evaluation of the Coated Materials (Yuzen Paper)
[0080] Succeeding to Example 2, the coated materials manufactured
as such were subjected to evaluation tests for light transmitting
property, mechanical strength, water repelling property and flame
retarding property as follows. In Tables 1 and 2, each of the
evaluated results was checked as a whole and given by a double
circle, a single circle, a triangle or a cross which stands for
very good, good, poor or very poor, respectively. With regard to
the coated materials manufactured by the use of the coating
solution 5 of the present application of Tables 1 and 2 and by the
use of a comparative coating solution of Japanese Patent No.
3020934, each of the evaluated results is given by a double circle
(better) or by a single circle (inferior) in Table 3.
[0081] With degree to a horizontal firing test, a detailed result
for the coated material manufactured by the use of the coating
solution 5 of the present application is shown in Table 4.
1TABLE 1 Coating Compound 1 Compound 2 or 3 Solvent(s) Catalyst
Solution Name Amt (g) Name Amt (g) Name(s) Amt (g) Name Amt (g)
Result 1 MTM 19.0 -- -- isopropyl alcohol 2.0 (BuO).sub.4Zr 0.8 o
ethylene glycol 2.0 2 MTM 19.0 -- -- isopropyl alcohol 2.0
(BuO).sub.4Ti 0.8 o ethylene glycol 2.0 3 MTM 19.0 -- -- isopropyl
alcohol 2.0 Bu.sub.2Sn(AcO).sub.2 0.8 oo ethylene glycol 2.0 4 MTM
14.0 .gamma.-Glycidoxypropyl trimethoxysilane 5.0 isopropyl alcohol
2.0 Bu.sub.2Sn(AcO).sub.2 0.8 oo 5 MTM 14.0 Phenyl trimethoxysilane
5.0 isopropyl alcohol 2.0 Bu.sub.2Sn(AcO).sub.2 0.8 oo 6 ETM 19.0
-- -- isopropyl alcohol 2.0 (BuO).sub.4Zr 0.8 o ethylene glycol 2.0
7 ETM 19.0 -- -- isopropyl alcohol 2.0 (BuO).sub.4Ti 0.8 o ethylene
glycol 2.0 8 ETM 19.0 -- -- isopropyl alcohol 2.0
Bu.sub.2Sn(AcO).sub.2 0.8 oo ethylene glycol 2.0 9 ETM 14.0
.gamma.-Glycidoxypropyl trimethoxysilane 5.0 isopropyl alcohol 2.0
Bu.sub.2Sn(AcO).sub.2 0.8 oo 10 ETM 14.0 Phenyl trimethoxysilane
5.0 isopropyl alcohol 2.0 Bu.sub.2Sn(AcO).sub.2 0.8 oo 11 MTE 19.0
-- -- isopropyl alcohol 2.0 (BuO).sub.4Zr 0.8 o ethylene glycol 2.0
12 MTE 19.0 -- -- isopropyl alcohol 2.0 (BuO).sub.4Ti 0.8 o
ethylene glycol 2.0 13 MTE 19.0 -- -- isopropyl alcohol 2.0
Bu.sub.2Sn(AcO).sub.2 0.8 oo ethylene glycol 2.0 14 MTE 14.0
.gamma.-Glycidoxypropyl trimethoxysilane 5.0 isopropyl alcohol 2.0
Bu.sub.2Sn(AcO).sub.2 0.8 oo 15 MTE 14.0 Phenyl trimethoxysilane
5.0 isopropyl alcohol 2.0 Bu.sub.2Sn(AcO).sub.2 0.8 oo 16 MTM 14.0
Dimethyl dimethoxysilane 5.0 isopropyl alcohol 2.0
Bu.sub.2Sn(AcO).sub.2 0.8 oo 17 MTM 14.0 Pure water 5.0 isopropyl
alcohol 10.0 61% HNO.sub.3 0.1 o BuO: butoxy AcO: acetate
[0082]
2TABLE 2 Coating Compound 1 Compound 2 Solvent(s) Catalyst Solution
Name Amt (g) Name Amt (g) Name(s) Amt (g) Name Amt (g) Result 1
Methyl trimethoxysilane 21.0 -- -- isopropyl alcohol 2.0
(BuO).sub.4Zr 0.8 .DELTA. ethylene glycol 2.0 2 Methyl
trimethoxysilane 21.0 -- -- isopropyl alcohol 2.0 (BuO).sub.4Ti 0.8
.DELTA. ethylene glycol 2.0 3 Methyl trimethoxysilane 21.0 -- --
isopropyl alcohol 2.0 Bu.sub.2Sn(AcO).sub.2 0.8 .DELTA. ethylene
glycol 2.0 4 Methyl trimethoxysilane 15.0 .gamma.-Glycidoxypropyl
5.0 isopropyl alcohol 2.0 Bu.sub.2Sn(AcO).sub.2 0.8 .DELTA.
trimethoxysilane 5 MS-51 19.0 -- -- isopropyl alcohol 2.0
(BuO).sub.4Zr 0.8 .DELTA. ethylene glycol 2.0 6 MS-51 19.0 -- --
isopropyl alcohol 2.0 (BuO).sub.4Ti 0.8 x ethylene glycol 2.0 7
MS-51 19.0 -- -- isopropyl alcohol 2.0 Bu.sub.2Sn(AcO).sub.2 0.8 x
ethylene glycol 2.0 8 MS-51 14.0 .gamma.-Glycidoxypropyl 5.0
isopropyl alcohol 2.0 Bu.sub.2Sn(AcO).sub.2 0.8 x trimethoxysilane
9 ES-40 19.0 -- -- isopropyl alcohol 2.0 (BuO).sub.4Zr 0.8 x
ethylene glycol 2.0 10 ES-40 19.0 -- -- isopropyl alcohol 2.0
(BuO).sub.4Ti 0.8 x ethylene glycol 2.0 11 ES-40 19.0 -- --
isopropyl alcohol 2.0 Bu.sub.2Sn(AcO).sub.2 0.8 x ethylene glycol
2.0 12 ES-40 14.0 .gamma.-Glycidoxypropyl 5.0 isopropyl alcohol 2.0
Bu.sub.2Sn(AcO).sub.2 0.8 x trimethoxysilane BuO: butoxy AcO:
acetate MS-51: oligomer of tetramethoxysilane (average degree of
polymerization: 3-4) ES-40: oligomer of tetraethoxysilane (average
degree of polymerization: 4-5)
[0083]
3TABLE 3 Water Light Flame Repelling Transmitting Retarding Coating
Solution Property Property Property Result Coating Solution 5 of
the .smallcircle..smallcircle- . .smallcircle..smallcircle.
.largecircle..smallcircle. .smallcircle..smallcircle. Present
Application Comparative Coating .smallcircle. .smallcircle.
.largecircle..smallcircle. .smallcircle. Solution (Japanese Patent
No. 3020934)
[0084]
4TABLE 4 Result of Horizontal Firing Test Time Until Arriving at
100 mm Burning Rate mm/min Blank 20 21 20 215.8 7.5 g/m.sup.2 38 40
37 112.8 15 g/m.sup.2 56 54 50 81.1
[0085] (1) Evaluation of Light Transmitting Property.
[0086] In the evaluation of the light transmitting property, coated
materials were manufactured using rubbed paper prepared by rubbing
the Japanese paper, rakusui paper prepared by dropping water drops
onto the Japanese paper, small wood chip paper prepared by
assembling small chips of wood and paperboard comprising corrugated
cardboard in addition to the yuzen paper used in Example 2 and they
were subjected to the evaluation.
[0087] The evaluation was carried out by observing each of the
manufactured coated materials by naked eye under illuminating with
a light box from the bottom and then luster, degree of coloration,
transparency, etc. were evaluated. The result was that the surface
of the coated material manufactured from yuzen paper using a
coating solution of the present application was translucent with
luster since the coating solution itself was colorless and
transparent whereby the color of the yuzen paper used as a material
was dark and the white part in the yuzen paper was translucent with
luster having a white color. On the other hand, in the case of the
comparative coating solution, since the coating solution itself is
yellow, the white part of the yuzen paper was translucent with
luster having a bit yellow color.
[0088] In the case of a coated material manufactured from a rubbed
paper using the coating solution of the present application, it was
translucent having luster as a whole. In the case of the coated
material manufactured from rakusui paper, the white part was also
translucent with luster with a white color like the rubbed paper.
In the case of the coated materials manufactured from small wood
chip paper and from paperboard, they were also translucent as a
whole, had increased luster and showed dark color as a whole.
[0089] From the result of the above evaluations, it was noted that,
in the coated materials manufactured by the use of the coating
solution of the present application, translucency with luster was
given and further that the color became dark as a whole.
[0090] (2) Evaluation of Mechanical Strength.
[0091] The coated material manufactured from rubbed paper for which
an evaluation for a light transmitting property was carried out was
bent by hand and it was observed by naked eye whether the coated
membrane was detached whereby the hardness (mechanical strength) of
each of the coated layer was evaluated. In the case of the coated
material manufactured by the use of the comparative coating
solution, the coated layer on the surface was detached in all cases
when the rubbed paper was bent. On the other hand, in the case of
the coated material manufactured by the use of the coating solution
of the present application, there was no case where the surface was
detached even when the paper was bent.
[0092] The above result means that, in the coated layer produced by
the comparative coating solution, detachment was resulted because
of a low softness while the coated layer produced by the coating
solution of the present application had far more softness as
compared with the above showing an increase in mechanical strength
as a whole. That is presumably because the main component (the
compound of the formula 1) contained in the coating solution, the
silane compound(s) added thereto (the compound(s) of the formula 2
and/or the formula 3), the catalyst, etc. were hydrolyzed and
polycondensed on the rubbed paper and came into very fine areas of
the rubbed paper during the course of formation of the coated layer
by polymerization whereupon they were mechanically entangled by a
physical bonding to the paper fiber, organic moieties were
hydrophobically bonded each other or hydroxyl groups of cellulose
which is a main component of the paper were chemically bonded with
the silane compound and, as a result, the mechanical strength
increased. Chemical reaction of hydroxyl groups of cellulose with
silane compound is assumed to be as follows. 5
[0093] (3) Evaluation of Water Repelling Property.
[0094] Evaluation of a water repelling property was carried out in
accordance with "Test Method for Paper and Water Repellency of
Paper (JIS P 8137)". First, a test piece of not shorter than 300 mm
length and 200 mm width having no fold, wrinkle, unevenness, etc.
was prepared according to JIS P 8110 (Method for Preparation of
Test Paper) from a coated material manufactured from yuzen paper
and then subjected to a pretreatment according to the condition
mentioned in JIS P 8111 (Pretreatment of the Test Paper).
[0095] A testing apparatus as shown in FIG. 1 was used, the above
test piece was placed on a test piece installing surface 2 of 350
mm length, 200 mm width and 45.degree. slope which was able to
smoothly and flatly fix the above test piece, an end of a burette 3
containing distilled water of 20.+-.1.degree. C. was made apart 10
mm from the test piece in a vertical direction and adjusted so as
to make the length of the water drop which was able to flow on the
said test piece 1 about 300 mm, then one water drop was dropped
from the said burette 3 and the state of the flowing was observed.
The result was that, in the case of the coated material
manufactured by the use of the coating solution of the present
application, all water drops completely fell down and the water
repellency was judged to be R10. On the other hand, in the case of
the coated material manufactured by the use of the comparative
coating solution, although the water repellency was judged to be
R10, because of the drops having smaller particle sizes fell down
more smoothly and, therefore, it was judged that the product
manufactured by the use of the coating solution of the present
invention was better.
[0096] (4) Evaluation of Flame Retarding Property.
[0097] (a) Horizontal Firing Test.
[0098] The coated material manufactured by the invention of the
present application is used as a building material such as stained
glass, cover and shade for desk lamp, protecting material for outer
wall and wall paper, shoji paper, etc. for interior decoration. In
view of the above, an evaluation was carried out whether it had a
flame retarding property requested to building materials. In the
flame retarding test, a horizontal firing test and a vertical
firing test were carried out as follows in accordance with a UL
standard [a standard regulated by the Underwriters' Laboratories
organized by the U.S. Fire Insurance Committee concerning fire
prevention, electric safety, theft prevention, etc. and an
UL-listed label is given to a product which meets with requirements
of the UL standard].
[0099] In carrying out the firing test, "7.5 g/m.sup.2" where 7.5 g
of a coating solution were impregnated per m.sup.2 of yuzen paper
and "15 g/m.sup.2" where 15 g of a coating solution were
impregnated per m.sup.2 of yuzen paper were manufactured in a
method as shown in the above Example 2 and they were cut in a size
of 125.+-.5 mm length, 13.0.+-.0.3 mm width and about 0.18 mm
thickness to prepare a test piece. In the meanwhile, yuzen paper
which was not dipped in any of coating solutions was cut in the
same size to prepare a "blank" test piece. Each of those test
pieces was subjected to a pretreatment by allowing to stand for 48
hours at the temperature of 23.+-.2.degree. C. and the humidity of
not higher than 50.+-.5%.
[0100] Non-ventilated chamber, enclosure, hood for laboratory,
device where methanol of an industrial grade (the lowest purity:
98%) is supplied to a burner of 100.+-.10 mm length and 9.5.+-.0.3
mm inner diameter together with a regulator and a flow meter, clock
device (precision: 1 second), manometer having a precision to an
extent of 0.01 mm and ring stand having a clamp, etc. for
supporting the test piece were prepared and, in a horizontal firing
test (according to 94HB of the UL standard), lines were formed at
the positions of 25 mm and 100 mm from the firing end of the each
of the prepared test pieces.
[0101] After that, a 20-mesh wire net in a size of 125 mm.times.125
mm was placed at the predetermined height of the ring stand making
the surface horizontal and another end of firing ends in the
longitudinal direction of the test piece was fixed by a clamp at
the height position with a predetermined interval from the upper
end of the wire net. The burner was ignited at the position which
was far from the test piece, a gas flow, etc. were adjusted so that
no yellow flame was formed and the height of the flame became
20.+-.1 mm and the flame of the burner was applied for 30 seconds
under such a condition that the flame of the burner covered the
position of 6.+-.1 mm from one end of the test piece.
[0102] When burning of the test piece arrived at the 25-mm line
within 30 seconds, the burner was kept away therefrom and, when the
burning still continued, the burning time in the horizontal
direction from the 25-mm line to the 100-mm line of the test piece
was measured for three times.
[0103] When the flame retarding property was evaluated as above,
the coated material manufactured by the use of the coating solution
of the present application showed better result in the horizontal
firing test as compared with the coated material manufactured by
the use of the comparative coating solution. Among the measured
results, that (in detail) of the horizontal firing test for the
coated material manufactured by the use of the coating solution 5
of the present application is as shown in Table 4. In the
measurements of each test piece in Table 4, "Time by seconds Until
Arriving at 100 mm" means the time from the flame was contacted
until it arrived at the 100-mm line (measuring time for three times
from the first to the third runs) and "Burning Rate" is the rate
(mm/minute) calculated from the mean value of the above three
measuring times. Incidentally, when the flame went out until
arriving at the 100-mm line, the position was calculated by means
of a proportional allotment from the 100 mm.
[0104] As shown in Table 4, the result of the horizontal firing
test was that the "time by seconds until 100 mm" was 20, 21 and 20
seconds for the "blank" test piece (the flame went out at 73 mm in
that case), 38, 40 and 37 seconds for the "7.5 g/m.sup.2" test
piece (the flame went out at 72 mm in that case) and 56, 54 and 50
seconds for the "15 g/m.sup.2" test piece (the flame went out at 72
mm in that case) at measurement for three times. The "burning rate"
was 215.8 mm/minute for the "blank" test piece, 112.8 mm/minute for
the "7.5 g/m.sup.2" test piece and 81.1 mm/minute for the "15
g/m.sup.2" test piece.
[0105] As mentioned above, the "7.5 g/m.sup.2" test piece needed
1.5-fold or more time for burning to an extent of the 100-mm
position as compared with the "blank" test piece and, in the case
of the "15 g/m.sup.2" test piece, 2-fold or more time was needed.
Thus, the "burning rate" of the coated material manufactured by the
invention of the present application showed such a very good
evaluating result that, in the case of the "7.5 g/m.sup.2" test
piece, the rate was not more than 3/5 of the "blank" test piece
and, in the case of the "15 g/m.sup.2" test piece, the rate was not
more than 2/5 of the "blank" test piece.
[0106] (b) Vertical Firing Test.
[0107] In the vertical firing test (in accordance with the UL
Standard 94V-0), the test pieces used in the above (a) were used.
First, a "7.5 g/m.sup.2" test piece applied with a noncombustible
agent and a "15 g/m.sup.2" test piece applied with a noncombustible
agent were prepared and an upper end of each of them was fixed by a
clamp of the above-mentioned ring stand where the longitudinal
direction of the test piece was made vertical. A burner was
adjusted so as to make the flame height 20.+-.1 mm and then placed
at the position where the upper end of the flame was 10 mm below
the center of the edge of the lower end of the test piece and the
flame was applied for 10 seconds. After that, the burner was kept
away at least 150 mm from the test piece and the first test for the
afterflaming time was carried out. When the afterflame ended, the
burner was placed again at the position 10 mm below the center of
the edge of the lower end, the flame was applied for 10 seconds and
the burner was kept away at least 150 mm from the test piece
whereupon the second test for the afterflaming time was measured
and, at the same time, the aftersmoking time at that time was
measured as well.
[0108] In the coated material manufactured by the use of the
coating solution of the present invention, the afterflaming time in
both the first and the second runs was not longer than 10 seconds,
the sum of the afterflaming time for the first and the second runs
was not longer than 50 seconds and the sum of the afterflaming time
for the second run and the aftersmoking time was not longer than 30
seconds. Thus the better result was obtained as compared with the
coated material manufactured by the use of the comparative coating
solution.
[0109] (5) Result of Evaluation.
[0110] It is noted from Table 1 where a coated layer was formed by
the compound of the formula 1 that the said compound is a very
excellent component for giving various properties such as light
transmitting property, water repelling property, mechanical
strength and flame retarding property to paper which is a fiber
material. It is also noted that, when the compound of the formula 2
or 3 is added to the coating solution in addition to the compound
of the formula 1, the above-mentioned various properties were
further improved as compared with the coating solution containing
the compound of the formula 1 only (coating solutions of the
present application 4, 5, 9, 10 and 14-16).
[0111] From the comparison of Table 1 with Table 2 and also from
Table 3, it is noted that the coated material manufactured by the
invention of the present invention is superior to the
conventionally known coated materials. Incidentally, in the
conventional coating solution, there is no improvement in various
properties such as light transmitting property, water repelling
property, mechanical strength and flame retarding property even
when the compound of the formula 2 or 3 is added thereto unlike the
coating solution of the invention of the present application. It is
further noted that the monomer of the compound of the formula 1 is
unable to result in the effect which is achieved by the invention
of the present application.
[0112] From Table 4, it is noted that the coated materials
manufactured by the invention of the present application have an
excellent resistance to heat and an excellent flame retarding
property.
[0113] The invention of the present application is that a fiber
material is coated with a condensate where, among four substituents
of silicon atom as shown in the formula 1, one is substituted with
a substituent R.sub.4 which is not hydrolyzable and is not
participated in a polycondensation of the compounds whereupon there
is manufactured a coated material having appropriate strength, good
light transmitting property, good water repelling property and
softness and, further resistance to abrasion and flame retarding
property (resistance to heat).
[0114] Therefore, in accordance with the invention of the present
application, it is now possible, as will be apparent from the
description of the Examples, to provide a coated material where the
property of softness of fiber material available at hand such as
Japanese paper, western paper and cloth is well utilized and,
further, the above-mentioned various characteristics are given
thereto. There is further advantage that such various
characteristics given to those coated materials can be adjusted
relatively easily by the persons who carry out the operation by
appropriately selecting and adjusting, for example, the selection
and the amount of the organometallic compound catalyst used as a
catalyst, the selection and the amount of the compound(s) of the
formula 2 and/or the formula 3 and the applying amount of the
coating solution.
[0115] In the invention of the present application, a coated
material is manufactured by applying a coating solution. Therefore,
unlike the conventionally used materials such as paraffin paper
which have high light transmitting property and excellent water
repelling property but have been available only by means of
production in factories, there is an advantage that the material
which is present at hand and available easily such as a common
paper material can be given with strength, light transmitting
property, water repelling property, flame retarding property and
resistance to abrasion together with utilizing the softness
inherent thereto.
[0116] In addition, as compared with a rayon shoji paper or the
like which has been used as a shoji paper in shoji houses, hotels,
inns, etc. due to its toughness, the coated material manufactured
by the invention of the present application has advantage that it
hardly generates static electricity whereby dust is hardly attached
thereto, that it has more water repelling property than a rayon
shoji paper whereby its cleaning by wet cloth or the like is
possible and that, even when water is absorbed therein as a result
of washing, it does not detach from the adhered part.
[0117] Thus, unlike the special shoji paper represented by a rayon
shoji paper, the coated material manufactured from a common shoji
paper according to the invention of the present application does
not use chemical substances such as rayon, acrylate and vinyl
chloride and, therefore, an advantage that static electricity is
not generated and dust is hardly attached can be achieved. In the
conventional special shoji paper, it darkens by adsorption of the
dust around that during the use for a long term and is to be
replaced by a new one with some intervals while, in the case of the
shoji paper according to the coated material manufactured by the
invention of the present application, it does not darken even when
used for a long term and the interval for replacement can be made
significantly longer.
[0118] Further, when the coated material manufactured by the
invention of the present application is compared with that which is
manufactured by the conventional sol-gel solution, there is no need
of using a silane coupling agent and, therefore, the reaction for
the formation of the coated layer does not become non-uniform
whereby there is an advantage that the strength of the coated layer
does not lower. Still further, since synthesis of the compound of
the formula 1, etc. is easy, there is another advantage that, as
compared with the case of the use of the conventional compounded
organic/inorganic materials, it is possible to provide a coated
material at far lower cost.
[0119] In a comparison with the product mentioned in the Japanese
Patent No. 3020934, the coating solution of the invention of the
present application contains neither boron ion nor halogen ion and,
therefore, there is an advantage that neutralization of the paper
is not resulted and a long-term preservation of the coating
solution and the coated material is possible. Further, there is an
additional advantage that, since the coated layer of the coated
material manufactured by the invention of the present application
is not formed only by a network of a hard siloxane bond, it has
both certain hardness and softness and shows a high mechanical
strength. Moreover, because of nonuse of boron ion and halogen ion
in the coating solution and the manufacturing method according to
the invention of the present application, there is a further
advantage that disposal of the solution after use is easier than
the case where the above ions are used.
[0120] The coated material manufactured using, for example, a
colored paper as a fiber material according to the present
invention may, for example, be used as it is or, after sticking on
a common transparent glass, used as a window glass like stained
glass or as a shade, etc. for a desk lamp resulting in a good
beautifulness. Especially when it is made into a shade, etc.
utilizing the Japanese paper which is able to express the
traditional beautifulness of paper from ancient times in Japan, it
is possible to provide a material which has beautifulness and
characteristics inherent to the paper itself and also shows a high
water repelling property and a high water-resisting/waterproofing
property.
[0121] In addition, the coated material manufactured by the
invention of the present application has the above-mentioned
various characteristics as compared with the conventional paper
and, therefore, various products using that are durable even for
the use during a long term. For example, when a coated material is
manufactured from shoji paper, its thickness is kept not more than
about 1 mm and coated layers are formed on both sides of the paper
whereby it is possible to provide a very economical shoji paper
which is tough and hard to burn, shows an excellent water repelling
property and is able to be repeatedly used by washing if stained.
Although a coated material manufactured from shoji paper is better
than the conventional ones, it may be damaged by a shock, etc.
However, unlike a simple glass, its fragments are not scattered
and, therefore, it has a high safety and contributes to the demand
for barrier-free houses as a result of an aging society in recent
years.
[0122] Since the coated material manufactured by the invention of
the present application is covered by a very stable coated layer,
there is an advantage that evaporation of chemical substances
(which are used in constructing the houses) from inside which has
been received public attention in recent years is little.
Accordingly, when the said coated material is used for the product
which is used in the house such as wall paper and shoji paper, it
is possible to prevent or reduce the allergy occurring in human
body.
[0123] Further, in accordance with the manufacturing method of the
invention of the present application, not only the degree of the
various properties given to the coated layer but also the thickness
of the said coated layer can be freely adjusted and, therefore,
when it is used, for example, for a product which is used in
outdoor being exposed to weather or for interior decoration such as
wall paper, it is possible to manufacture and provide an optimum
coated material by adjusting the type and the amount of each
compound upon necessity.
* * * * *