Disclosed is a one-package inorganic binder composition comprising a powdery mixture of a powdery alkali metal silicate having a water solubility or water dispersibility, an alkali metal borate soluble in an alkaline aqueous solution and silicon polyphosphate.

BACKGROUND OF THE INVENTION 
(1) Field of the Invention: 
The present invention relates to a one-package inorganic binder 
composition. More particularly, the present invention relates to an 
inorganic binder composition which contains a binder component and a 
curing agent component in one package and which is used as a binder in 
various fields by addition of water on application. Especially, the 
present invention relates to an inorganic binder composition which is 
excellent in the storage stability though it is in the form of one package 
and also is excellent in the properties required for binders, such as the 
adhesive force and water resistance. 
(2) Description of the Prior Art: 
As the inorganic coating composition, there has been used a composition 
comprising as the main component a water-soluble silicate, such as 
so-called water glass. A water-soluble silicate such as water glass forms 
an aqueous solution having a high close contact property and a high 
adhesion, and this aqueous solution can easily be applied to a substrate 
to be bonded or coated. However, this aqueous solution is defective in 
that a long time is necessary for curing the coating, the form-retaining 
property or dimension stability of the coating is poor and so-called 
sagging is readily caused, and the resulting cured coating is insufficient 
in such properties as water resistance, weatherability and toughness. As 
means for improving these properties, there has widely been adopted method 
in which an acid or acidic salt is added as a curing agent to an aqueous 
solution of a water-soluble silicate. However, since this curing agent has 
a high reactivity with the silicate as the binder, premature gelation of 
the silicate or heterogeneous partial gelation is readily caused, the 
adaptability to the bonding or coating operation is not good, and the 
resulting cured coating is still insufficient in the water resistance, 
toughness and weatherability. 
As means for preventing premature or partial gelation in a binder 
composition comprising an alkali metal silicate binder and an inorganic 
phosphate curing agent, we previously proposed a method in which a curing 
agent composed mainly of silicon polyphosphate having a property of 
gradually releasing phosphoric acid or an alkali metal salt thereof is 
used as the curing agent to prolong the pot life of the binder composition 
(see the specification U.S. Pat. No. 4,018,616). 
This silicon polyphosphate type curing agent gives a much longer pot life 
to an alkali metal silicate binder than the conventional phosphoric acid 
type curing agent. However, this binder composition is defective in that a 
liquid (an aqueous solution of an alkali metal silicate) and a powder 
(silicon polyphosphate) should be metered independently and mixed on 
application. 
SUMMARY OF THE INVENTION 
We found that a powdery mixture comprising a powder of an alkali metal 
silicate, an alkali metal borate soluble in an alkaline aqueous solution 
and silicon polyphosphate is a one-package inorganic binder composition 
which can be used in various fields when the composition is mixed with 
water on application and which has an appropriate pot life and an 
appropriate self-curing property. 
It is therefore a primary object of the present invention to provide a 
one-package inorganic binder composition in which a binder component and a 
curing agent are co-present in the powdery form. 
Another object of the present invention is to provide a powdery one-package 
inorganic binder composition which has an excellent dispersibility in an 
aqueous medium and which has a relatively long pot life, a high binding 
property and a good self-curing property in the form of an aqueous 
dispersion. 
Still another object of the present invention is to provide a powdery 
one-package inorganic binder composition which can give a bonded structure 
excellent in the water resistance and heat resistance. 
A further object of the present invention is to provide a one-package 
inorganic binder composition which has an excellent storage stability 
though the composition comprises a binder component and a curing agent 
component in combination. 
In accordance with the fundamental aspect of the present invention, there 
is provided a one-package inorganic binder composition comprising a 
powdery mixture of a powdery alkali metal silicate having a water 
solubility or water dispersibility, an alkali metal borate soluble in an 
alkaline aqueous solution and silicon polyphosphate. 
The present invention is based on the finding that the above-mentioned 
powdery mixture of a powdery alkali metal silicate, an alkali metal borate 
and silicon polyphosphate is stably present in one package without loss of 
the water dispersiblity, binding property and self-curing property, when 
an aqueous medium is added to this powdery mixture, the above-mentioned 
premature gelation or partial gelation is not caused and the powdery 
mixture is easily and stably dispersed in the aqueous medium while showing 
an appropriate pot life, and the resulting aqueous dispersion is excellent 
in the binding property and self-curing property and gives a bonded 
structure prominently excellent in the water resistance and heat 
resistance.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The powdery alkali metal silicate used in the present invention is 
indispensable for attaining a high binding property, and powdery silicon 
polyphosphate is indispensable for keeping a good balance between the 
storage stability due to the property of gradually releasing phosphoric 
acid and the curing action. The powdery alkali metal borate to be combined 
with the foregoing two components is effective for preventing premature 
gelation or partial gelation in the form of not only a powdery mixture 
with other two components but also an aqueous dispersion and improving the 
water resistance of the resulting bonded structure, as compared with a 
binder composition comprising the above-mentioned powdery alkali metal 
silicate and silicon polyphosphate alone. The reason for this excellent 
action has not completely been elucidated, but it is believed that the 
alkali metal borate is basic and retards neutralization of the alkali 
metal silicate by silicon polyphosphate and when curing is effected by 
silicon polyphosphate, the boric acid component uniformly reticulates the 
entire silicate binder and is effective for providing a homogeneous cured 
structure excellent in the water resistance. 
As is seen from the foregoing description, it is important that the 
one-package binder composition of the present invention should comprise 
the powdery alkali silicate binder component, the silicon polyphosphate 
component having a property of gradually releasing phosphoric acid and the 
alkali metal borate component which is a weaker acid than phosphoric acid. 
Since these three components are contained in one package, the binder 
composition of the present invention is advantageous in that metering or 
mixing of these components is not necessary when the composition is 
finally used as a binder. 
The powdery alkali metal silicate that is used in the present invention is 
water-soluble or water-dispersible, and one having an M.sub.2 O/SiO.sub.2 
molar ratio of from 1/1.3 to 1/2.6 is preferred (M stands for an alkali 
metal). When an alkali metal silicate in which the M.sub.2 O/SiO.sub.2 
molar ratio is outside the above range is used as the binder component, 
the bonding strength tends to be reduced. Sodium silicate is especially 
suitable for attaining the objects of the present invention, but potassium 
silicate may also be used. The alkali metal silicate that is used in the 
present invention may contain water of hydration, so far as the alkali 
metal silicate is powdery. 
Any alkali metal borate can be used in the present invention, so far as it 
is soluble in an alkaline aqueous solution. For example, sodium borate and 
potassium borate are preferably used. The borate may be an anhydrous salt 
or a water-containing salt such as a trihydrate, pentahydrate, 
heptahydrate or decahydrate. 
The silicon polyphosphate that is used in the present invention comprises a 
phosphoric acid component and a silica component as indispensable 
components, and the phosphoric acid component is contained in the 
condensed form. Silicon polyphosphate having a P.sub.2 O.sub.5 /SiO.sub.2 
molar ratio of from 1/1.8 to 1/3.6, especially from 1/2.0 to 1/3.3, is 
preferred. If the molar ratio of the phosphoric acid component (P.sub.2 
O.sub.5) is too low and below the above range, the desired curing property 
cannot be obtained and the mechanical strength is reduced, and if this 
molar ratio is too high and exceeds the above range, when the composition 
is formed into an aqueous dispersion, premature gelation or partial 
gelation is caused. 
In order to prevent premature gelation or partial gelation and cure the 
alkali metal silicate binder uniformly and tightly, it is important that 
this silicon polyphosphate should have a property of gradually releasing 
the phosphoric acid component. In this connection, it is preferred that 
the initial dissolution quantity B, defined by the following formula, of 
the silicon polyphosphate that is used in the present invention be up to 
250, particularly up to 200, especially particularly up to 100, and that 
the average hydrolysis speed constant A, defined by the following formula, 
of the silicon polyphosphate be at least 0.2, especially 0.3 to 1.3: 
EQU Y=AX+B 
wherein X stands for the elapsed time (minutes), up to 120 minutes, of a 
sample solution formed by adding 1 g of the curing agent (silicon 
polyphosphate) in 100 ml of a 4 N aqueous solution of sodium hydroxide, 
and Y stands for the integrated amount (mg/100 ml) of phosphoric acid 
(P.sub.2 O.sub.5) dissolved in the sample solution. 
The process for the preparation of the gradually releasing phosphate type 
curing agent and the properties of this curing agent are described in 
detail in the abovementioned specification of U.S. Pat. No. 4,018,616. 
In the powdery binder composition of the present invention, it is preferred 
that the molar ratio of B.sub.2 O.sub.3 in the alkali metal borate to 
SiO.sub.2 in the powdery alkali metal silicate be in the range of from 
1/0.03 to 1/0.3, especially from 1/0.05 to 1/0.25, and that the molar 
ratio of P.sub.2 O.sub.5 in the silicon polyphosphate to the total alkali 
metal component (M.sub.2 O in which M stands for an alkali metal) in the 
composition be in the range of from 1/0.35 to 1/0.85, especially from 
1/0.3 to 1/0.8. If the molar ratio of the boric acid component (B.sub.2 
O.sub.3) is too low and below the above range, not only the water 
resistance but also the stability is reduced, and even if the molar ratio 
of the boric acid component is increased beyond the above range, no 
particular advantage is attained and the composition becomes economically 
disadvantageous. If the amount of the phosphoric acid component in the 
silicon polyphosphate is too all and below the above range, curing is 
insufficient or a desired bonding strength cannot be obtained, and if the 
amount of the phosphoric acid component is too large and exceeds the above 
range, partial gelation or premature gelation is caused and the bonding 
strength and water resistance tend to be reduced. 
In the powdery composition of the present invention, the particle size of 
each powdery component can be changed in a broad range. For example, since 
the powdery alkali metal silicate or alkali metal borate is easily soluble 
in water, it may have a considerably large particle size, so far as 
segregation is not caused. On the other hand, since the silicon 
polyphosphate is insoluble in water, it is preferred that the particle 
size of the silicon polyphosphate be smaller than 100 microns, especially 
smaller than 74 microns. 
The one-package binder composition of the present invention may be prepared 
by dry-blending the above components at the above-mentioned ratio and, if 
necessary, lightly pulverizing or granulating the mixture. The resulting 
composition is packed in a moisture-proof paper bag, an aluminum 
foil-laminated packaging member or a transportation container. 
The powdery composition of the present invention shows a prominently 
excellent storage stability in the moisture-intersected dry state. When at 
least one of the silicon polyphosphate and the alkali metal 
silicate-alkali metal borate mixture is coated in advance with an organic 
or silicate coating material soluble in an alkaline aqueous solution, even 
if the powdery composition is exposed to high humidity conditions, the 
composition shows an excellent storage stability over a very long period. 
Namely, this organic or silicate coating material prevents the silicon 
polyphosphate from having direct contact with the alkali metal silicate 
binder during the storage, and when the composition is dispersed in water, 
the organic or silicate coating material is dissolved in the alkaline 
liquid and does not inhibit the binding action of the alkali metal 
silicate or borate or the curing action of the silicon polyphosphate. 
In view of the moisture-resistance storage property and from the economical 
viewpoint, it is preferred that the organic or silicate coating material 
be used in an amount of 4 to 12% by weight, especially 5 to 11% by weight, 
based on the silicon polyphosphate or the alkali metal silicate-alkali 
metal borate mixture. 
An organic coating material which is rendered soluble by neutralization 
with an alkali and is relatively hydrophobic before neutralization and 
which shows a surface activating action (dispersibility improving action) 
when it is dissolved is preferably used. For example, higher fatty acids 
and resin acids such as stearic acid, palmitic acid, lauric acid and 
behenic acid are advantageously used. Furthermore, an alkali-soluble 
polymers such as a vinyl ether-maleic acid copolymer, an acrylic 
acid-acrylic acid ester copolymer, carboxymethyl cellulose, glue and 
casein can be used as the organic coating material. 
As the silicate coating material, there can be used calcium silicate, 
magnesium silicate, barium silicate and ehter silicates. 
The one-package inorganic binder composition of the present invention is 
mixed with an aqueous medium in an amount of 30 to 200 parts by weight, 
especially 35 to 90 parts by weight, per 100 parts by weight of the 
powdery composition, and the composition is applied to the intended use as 
the binder, though the preferred amount of the aqueous medium varies 
according to the intended use or the presence or absence of other additive 
components. 
Various assistants and additives may be incorporated into the one-package 
inorganic binder composition in the package in advance or when the 
composition is applied to the intended use. For example, assistants such 
as a curing assistant and additives such as a reinforcer, an agrregate, a 
pigment, an anchoring agent and an initial tack imparting agent may be 
incorporated in the powdery composition of the present invention. 
The inorganic binder composition of the present invention may be used 
singly or in combination with a known curing assistant. As the curing 
assistant, there can be mentioned, for example, metal oxides and 
hydroxides such as calcium oxide, magnesium oxide, zinc oxide, aluminum 
oxide, magnesium hydroxide, calcium hydroxide and aluminum hydroxide, 
metal silicofluorides such as aluminum silicofluoride, calcium 
silicofluoride and sodium silicofluoride, and metal phosphates such as 
aluminum phosphate and calcium phosphate. 
A fibrous reinforcer such as a staple, sliver, mat, woven fabric, non-woven 
fabric or net of glass fiber, rock wook, slag wool, asbestos, talc, carbon 
fiber or metal fiber may be used as the reinforcer. Furthermore, a finely 
divided reinforcer such as carbon black, glass powder, white carbon or 
siliceous sand may be used. As the filler or coating material, there may 
be used inorganic fillers and aggregates such as calcium silicate, 
magnesium silicate, barium silicate, kaolin, sintered clay, acid clay, 
activated clay, silicon dioxide, aluminosilicic acid, its salts, titanium 
dioxide, zirconium dioxide, alumina powder, barium sulfate, magnesium 
carbonate, magnesium oxide, calcium carbonate, zinc oxide, gypsum, sand, 
rock, stone and refractory mineral. Moreover, an organic filler such as a 
powdery phenolic resin, a powdery urea resin or carboxymethyl cellulose 
may be used. 
As the pigment, there can be used not only white pigments such as titanium 
dioxide and coloring pigments such as chrome yellow, red iron oxide, 
ultramarine, chrome green, mars violet and carbon black. 
Acidic, neutral and basic refractory aggregates may be used according to 
the intended use. For example, there can be mentioned Al.sub.2 O.sub.3 
-SiO.sub.2 type aggregates such as chamotte, agalmatolite, mullite, 
semi-silica aggregate and high-alumina aggregate (pearlite), SiO.sub.2 
type aggregates such as siliceous stone, Al.sub.2 O.sub.3 type aggregates 
such as corundum and electrofused alumina, MgO-SiO.sub.2 type aggregates 
such as forsterite, SiC type aggregates such as silicon carbide, graphite 
type aggregates, chrome aggregates, chrom-magnesite aggregates, 
magnesia-chrome aggregates, magnesia clinker, electrofused magnesia and 
sintered dolomite. These refractory aggregates may be used singly or in 
the form of a mixture of two or more of them. The refractory aggregate is 
subjected to the known particle size adjustment treatment and a refractory 
composition in which the content of coarse particles having a particle 
size of 1 to 5 mm is 10 to 70% by weight and the content of fine particles 
having a particle size smaller than 1 mm is 90 to 30% by weight is formed 
by appropriately mixing fractions. Of course, the aggregate may directly 
be pulverized to obtain a particle size distribution similar to the 
above-mentioned particle size distribution and the pulverized aggregate 
may be used without performing classification or the like. 
A paste or latex may be added to the powdery composition of the present 
invention to temporarily increase the initial tackiness of the aqueous 
dispersion. 
The kinds and amounts of the above-mentioned additives should be selected 
so that the operation adaptability of the final binder composition is not 
degraded. 
The binder composition of the present invention may be used for the 
production of various molded articles. For example, the binder composition 
of the present invention may be used in combination with a fibrous or 
finely divided reinforcer or filler and also with an aggregate as a 
binder, tackifier, adhesive or sticking agent for the production of 
various refractory molded structures such as roofing materials, interior 
and exterior decorative tiles, blocks, bricks, hollow wall members, 
partitioning materials, sound insulating materials, refractory coatings of 
iron materials for skyscrapers and other construction materials, furniture 
and fixtures such as tables and chairs table wares and other containers, 
various decorative articles, structural materials such as pipes, sheets, 
blocks, beams, columns and casings, various casting molds, definite and 
indefinite ceramic bricks and molded articlss of industrial wastes. 
Furthermore, the binder composition of the present invention is effectively 
used as an adhesive for producing integrated articles or bonded structures 
by bonding various ceramic products such as glass articles, bricks, 
slates, blocks and porcelains or metallic articles. 
Moreover, the binder composition of the present invention can valuably be 
used for the impregnation or surface treatment of bricks, porcelains, 
concrete products, gypsum boards, wooden articles, paper products and 
other fibrous products to render them incombustible or water-impermeable, 
or for formation of incombustible coatings on these articles. 
Still further, the binder composition of the present invention may be 
coated as an inorganic paint on various structures directly or after 
addition of fillers or pigments if necessary. 
In producing molded articles, bonded structures and coated structures by 
using the binder composition of the present invention, curing of the 
aqueous dispersion of the binder composition can be performed in the 
formal state or under application of heat and pressure. For example, the 
curing temperature is in the range of from room temperature to 200.degree. 
C., especially from room temperature to 150.degree. C. Curing is carried 
out under atmospheric pressure or under application of a pressure of up to 
about 10 Kg/cm.sup.2. Ordinarily, curing is performed in air, but if 
desired, curing may be conducted under a reduced pressure or in an inert 
atmosphere such as a nitrogen gas atmosphere. Carbon dioxide gas may be 
used as the curing atmosphere so as to shorten the curing time. 
An appropriate curing time is selected within a range of 2 minutes to 1 
week according to the curing temperature adopted, though the preferred 
curing time varies depending on the temperature and the kinds and amounts 
of the curing agent and curing assistant. For example, in the case where 
the binder composition of the present invention is used as a coating 
composition, it is sufficient if curing is conducted for 2 to 10 minutes. 
In case of from temperature curing of a bonded structure or a thick molded 
article, it sometimes is necessary to conduct curing for about 1 week to 
obtain a cured product having a complete mechanical strength. 
The present invention will now be described in detail with reference to the 
following Examples that by no means limit the scope of the invention. 
EXAMPLE 1 
Production of a powdery one-package inorganic binder will now be described. 
1-1. Powdery Sodium Silicate: 
Three commercially available powdery sodium silicates having a composition 
shown in Table 1 were used. 
TABLE 1 
______________________________________ 
Sample 
Composition (%) SS-1 SS-2 SS-3 
______________________________________ 
SiO.sub.2 50.5 51.4 53.0 
Na.sub.2 O 34.3 25.0 22.1 
SiO.sub.2 /Na.sub.2 O Molar Ratio 
1.52 2.12 2.48 
______________________________________ 
1-2. Powdery Water-Soluble Borate: 
Three alkaline aqueous solution-soluble borates having a molecular formula 
shown in Table 2 were used. 
TABLE 2 
______________________________________ 
Sample 
B-1 B-2 B-3 
______________________________________ 
Molecular 
Na.sub.2 B.sub.4 O.sub.7.10H.sub.2 O 
Na.sub.2 B.sub.4 O.sub.7.5H.sub.2 O 
K.sub.2 B.sub.4 O.sub.7.5H.sub.2 O 
Formula 
______________________________________ 
1-3. Powdery Silicon Polyphosphate: 
As the silicon polyphosphate, there were used 16 silicon polyphosphates 
prepared according to the methods disclosed in Japanese Patent 
Publications No. 40866/71 and No. 42711/71. 
With reference to each of the so-prepared 16 silicon polyphosphates, the 
SiO.sub.2 /P.sub.2 O.sub.5 molar ratio, the composition of other 
components (for example, Al.sub.2 O.sub.3, CaO and MgO) introduced from 
the starting materials and the average hydrolysis constant (a) and initial 
hydrolysis quantity (b) (ml) determined according to the method described 
below are shown in Table 3. 
Method for Determination of Average Hydrolysis Constant (a) and Initial 
Hydrolysis Quantity (b): 
In 100 ml of pure water was dispersed 1 g of the sample powder, and a 0.1 N 
aqueous solution of sodium hydroxide (NaOH) was added to the dispersion so 
that the pH value of the dispersion was maintained at 10.5. The amount 
(ml) of the 0.1 N aqueous solution of sodium hydroxide consumed for a 
predetermined elapsed time (minute) was measured, and the time (minute) 
was plotted on the abscissa and the amount (ml) of the 0.1 N aqueous 
solution of sodium hydroxide consumed was plotted on the ordinate. The 
formula (1) of Y=aX+b was determined from the obtained line, and the 
values of the average hydrolysis constant (a) and initial hydrolysis 
quantity (b) were obtained from the formula (1). 
Typical instances of the method for the production of silicon polyphosphate 
will now be described with reference to samples H-1 and H-2. 
Production of Sample H-1: 
Commercially available sodium silicate of the industrial grade (sodium 
silicate No. 3 specified by JIS, Na.sub.2 O=9.63%, SiO.sub.2 =28.9%, 
SiO.sub.2 /Na.sub.2 O molar ratio=3.1) was treated with a cation exchange 
resin to effect partial removal of sodium ions. The so-treated sodium 
silicate was diluted so that the concentration of the silicic acid 
component (SiO.sub.2) of sodium silicate was 0.25 mol/l, and the dilution 
was contacted with the cation exchange resin to remove sodium ions so that 
the pH value of the sodium silicate solution was 10.0. The recovered 
sodium silicate solution having a pH value of 10.0 comprised 1.72 g/100 ml 
of SiO.sub.2 and 0.091 g/100 ml of Na.sub.2 O and had an SiO.sub.2 
/Na.sub.2 O molar ratio of 19.5. Commercially available phosphoric acid of 
the industrial grade (first grade specified by JIS, 85.0% H.sub.3 PO.sub.4 
having a specific gravity of 1.69) was mixed with the sodium silicate 
solution having a pH value of 10.0 so that the SiO.sub.2 /P.sub.2 O.sub.5 
molar ratio was 2.2, and the mixture was heated and concentrated with 
stirring to obtain a dry product. The dry product was pulverized and was 
calcined at 950.degree. C. for 120 minutes in a rotary kiln. The calcined 
product was pulverized and classified by using a 200-mesh sieve to obtain 
powdery silicon polyphosphate (sample H-1). 
Production of Sample H-2: 
Easily reactive silicic acid was prepared from acid clay produced at 
Nakajo, Niigata, Japan (the dry product comprising 78.7% of SiO.sub.2, 
13.1% of Al.sub.2 O.sub.3, 0.57% of Fe.sub.2 O.sub.3, 3.50% of MgO, 1.13% 
of CaO and an ignition loss of 3.15%) according to the method disclosed in 
Japanese Patent Publication No. 2277/45. More specifically, 76.5 g, as 
calculated as the dry product, of the above acid clay (having a water 
content of 42.5%) was charged in a conical beaker having a capacity of 500 
ml, and 200 ml of an aqueous solution of sulfuric acid having a 
concentration of about 50% was added and the acid treatment was carried 
out at 90.degree. C. for 10 hours. The treated clay was washed with a 
dilute aqueous solution having a pH value of 1.0 according to the 
decantation method and then with water to remove the basic salts formed by 
the reaction. Thus, easily reactive silicic acid (the dry product 
comprising 92.46% of SiO.sub.2, 2.68% of Al.sub.2 O.sub.3, 0.24% of 
Fe.sub.2 O.sub.3, 0.13% of MgO, 0.13% of CaO and 3.38% of an ignition 
loss), which was a special silica gel, was recovered from the acid clay. 
This easily reactive silicic acid was mixed with the above-mentioned 
phosphoric acid of the industrial grade so that the SiO.sub.2 /P.sub.2 
O.sub.5 molar ratio was 3.0, and the mixture was stirred and granulated to 
form granules having a diameter of about 0.5 to about 2 mm. The 
granulation product was calcined at 250.degree. to 300.degree. C. for 
about 30 minutes in a rotary kiln and subsequently calcined at about 
700.degree. C. for about 30 minutes. Then, the calcined product was 
pulverized by using a hammer mill type pulverizer (supplied by Tokyo 
Atomizer K.K.) and classified by using a 200-mesh sieve to obtain powdery 
silicon polyphosphate (sample S-2). 
Other silicon polyphosphates shown in Table 3 were prepared according to 
the above-mentioned method adopted for production of sample H-1 or H-2 
while changing the starting materials of the silicic acid and phosphoric 
acid components and the preparation conditions (such as the SiO.sub.2 
/P.sub.2 O.sub.5 molar ratio, the calcining temperature and time, the 
presence or absence of calcination and the pulverization method). 
Incidentally, when a component other than silicic acid (for example, more 
than 1% of Al.sub.2 O.sub.3, CaO, MgO or the like) was contained in the 
starting material, the phosphoric acid component was added in an amount 
necessary for forming a normal salt with such basic component, as well as 
the phosphoric acid component added for reaction with silicic acid 
(SiO.sub.2) at a predetermined molar ratio. 
TABLE 3 
__________________________________________________________________________ 
Sample 
H-1 H-2 H-3 H-4 H-5 H-6 
__________________________________________________________________________ 
Starting Materials 
silicic acid sodium- 
AS AS AS AS * 
component removed 
sodium 
silicate 
phosphoric acid 
PA PA PA PA PA PA 
component 
other component 
-- Al.sub.2 O.sub.3, 
Al.sub.2 O.sub.3, 
Al.sub.2 O.sub.3, 
Al.sub.2 O.sub.3, 
-- 
CaO, CaO, CaO, CaO, 
MgO MgO MgO MgO 
Preparation Conditions 
SiO.sub.2 /P.sub.2 O.sub.5 molar ratio 
2.2 3.0 2.0 2.5 3.5 3.0 
calcination not effected 
effected 
effected 
effected 
effected 
effected 
calcining Temp. (.degree.C.) 
950 700 700 700 700 700 
calcining time (min) 
120 30 30 30 30 30 
pulverization atomizer 
atomizer 
atomizer 
atomizer 
atomizer 
Physical Property Values 
average hydrolysis 
0.035 0.026 0.031 0.029 0.015 0.030 
constant (a) 
initial hydrolysis 
1.5 0.8 1.4 1.1 0.6 0.8 
quantity (b) (ml) 
__________________________________________________________________________ 
Sample 
H-7 H-8 H-9 H-10 H-11 H-12 
__________________________________________________________________________ 
Starting Materials 
silicic acid aluminum 
calcium 
magnesium 
zeolite 4A 
silica gel 
AS 
component silicate 
silicate 
silicate powder 
phosphoric acid 
PA PA PA PA PA pyrophos- 
component phoric acid 
other component 
Al.sub.2 O.sub.3 
CaO MgO Na.sub.2 O, 
3% K.sub.2 O 
Al.sub.2 O.sub.3, 
Al.sub.2 O.sub.3 
added CaO 
MgO 
Preparation Conditions 
SiO.sub.2 /P.sub.2 O.sub.5 molar ratio 
3.0 3.0 3.0 3.0 3.0 3.0 
calcination effected 
effected 
effected 
effected 
effected 
effected 
calcining temp. (.degree.C.) 
700 700 700 700 700 700 
calcining time (min) 
30 30 30 30 30 30 
pulverization atomizer 
atomizer 
atomizer 
atomizer 
atomizer 
atomizer 
Physical Property Values 
average hydrolysis 
0.013 0.020 0.017 0.024 0.022 0.033 
constant (a) 
initial hydrolysis 
1.9 1.1 1.8 0.7 0.4 0.7 
quantity (b) (ml) 
__________________________________________________________________________ 
Sample 
H-13 H-14 H-15 H-16 HC-1 HC-2 HC-3 
__________________________________________________________________________ 
Starting Materials 
silicic acid AS AS AS AS AS AS AS 
component 
phosphoric acid 
potassium 
sodium PA PA PA PA PA 
component phosphate 
phosphate 
other component 
Al.sub.2 O.sub.3, CaO 
Al.sub.2 O.sub.3, CaO 
Al.sub.2 O.sub.3, 
Al.sub.2 O.sub.3, 
Al.sub.2 O.sub.3, 
Al.sub.2 O.sub.3, 
Al.sub.2 O.sub.3, 
MgO, K.sub.2 O 
MgO, Na.sub.2 O 
CaO, CaO, CaO, CaO, CaO, 
MgO MgO MgO MgO MgO 
Preparation Conditions 
SiO.sub.2 /P.sub.2 O.sub.5 molar ratio 
2.2 2.2 3.0 3.0 3.0 3.0 3.0 
calcination effected 
effected 
effected 
effected 
not not effected 
effected 
effected 
calcining temp. (.degree.C.) 
700 700 500 1000 400 1100 700 
calcining time (min) 
30 30 40 15 240 20 30 
pulverization 
atomizer 
atomizer 
atomizer 
atomizer 
atomizer 
atomizer 
120 minutes' 
pulverization 
in pot mill 
Physical Property Values 
average hydrolysis 
0.027 0.030 0.045 
0.020 
0.152 
-- 0.085 
constant (a) 
initial hydrolysis 
0.5 1.2 2.2 0.2 3.2 12.0 6.2 
quantity (b) (ml) 
__________________________________________________________________________ 
Note 
*commercially available silica gel powder of reagent grade 
AS: easily reactive silicic acid prepared from acid clay 
PA: phosphoric acid of the industrial grade 
atomizer: hammer mill type pulverizer 
HC: silicon phosphate other than silicon polyphosphate of the present 
invention 
Three comparative silicon phosphates (samples HC-1, HC-2 and HC-3) 
differing from the silicon polyphosphate of the present invention in the 
physical properties were prepared. 
Each of the silicon polyphosphates was coated with a predetermined amount 
of a fatty acid (for example, beef-tallow stearic acid) or barium silicate 
at the pulverizing step using a hammer mill type pulverizer at about 
80.degree. C. 
In the same manner as described above, each of the alkali metal 
silicate-alkali metal borates was coated with a fatty acid or barium 
silicate. 
1-4. One-Package Inorganic Binder: 
The powdery sodium silicate, alkali metal borate and silicon polyphosphate 
were homogeneously mixed to obtain an inorganic binder having a 
composition shown in Table 5, and a predetermined amount of water was 
added to the inorganic binder to form a homogenous paste. The bonding 
properties were tested according to methods described below to obtain 
results shown in Table 5. 
It was found that better results were obtained when the compositions and 
mixing ratios of the powdery sodium silicate, alkali metal borate and 
silicon polyphsophate were as shown in Table 4. 
TABLE 4 
______________________________________ 
Molar Ratio 
______________________________________ 
Composition of powdery 
SiO.sub.2 /Na.sub.2 O 
= 1.3 to 2.6 
sodium silicate 
Ratio of alkali metal borate 
B.sub.2 O.sub.3 /SiO.sub.2 
= 0.03 to 0.3 
to powdery sodium silicate 
Composition of silicon 
SiO.sub.2 /P.sub.2 O.sub.5 
= 1.8 to 3.6 
polyphosphate 
Ratio of silicon polyphosphate 
P.sub.2 O.sub.5 /Na.sub.2 O 
= 0.35 to 0.85 
to total sodium component in 
binder composition 
______________________________________ 
The amount of the fatty acid coated on silicon polyphosphate was 10% by 
weight unless otherwise indicated. Other coating amounts are described in 
Example 2. 
In order to evaluate the bonding effect of the inorganic binder of the 
present invention, the following tests concerning the bonding properties 
were carried out. 
(A) Measurement of Dispersibility and Gelation Time: 
An apparatus as shown in FIG. 1 was used for the measurement of the 
dispersibility and the gelation time. 
A vessel 1 having an inner capacity of about 160 ml, which was secured in a 
water bath 2 maintained at a predetermined measurement temperature 
(40.degree. C. unless otherwise indicated) was charged with 85 g of the 
sample powder, and 50 ml of water was added. A stirring vane 5 formed of 
stainless steel was put into the vessel and was rotated by a universal 
motor 3 (rated conditions: 100 V, 90 W, 4 poles, 50 Hz, 1.0 A, 3500 rpm) 
connected directly to the stirring vane. In advance, the voltage (direct 
current) was adjusted to 13.00 V in the state where the stirring vane was 
rotated under no load (any sample was not added in the vessel), and the 
rotation number was adjusted to 310 rpm under no load by a rotation 
adjusting knob 4 located in the upper portion of the motor while observing 
a rotation number meter. The torque T (Kg-m) under no load was calculated 
from the voltage, current and rotation number according to the following 
formula (2): 
##EQU1## 
wherein N stands for the rotation number (rpm), V stands for the voltage 
(volt) and I stands for the current (A). 
It was found that under no load, the torque T was in the range of from 
0.016 to 0.020 Kg-m. 
Water was added to the sample powder in the measuring vessel 1 and the 
stirring vane 5 was rotated to form a homogeneous paste. With the lapse of 
time, the viscosity of the paste was increased, the load current was 
increased, the rotation number was reduced, and the torque was hence 
increased. From the preliminary experiment results, the point at which the 
torque T was increased to 0.07 Kg-m was defined as the gelation point. The 
time required for arrival at this gelation point was checked and defined 
as the gelation time. 
For ordinary inorganic binders and the binder of the present invention, it 
is necessary that this gelation time should be more than 100 minutes at 
20.degree. C. and more than 30 minutes at 40.degree. C. 
When water was added to the sample powder and stirring was initiated, if 
the entire sample was formed into a homogeneous paste, it was judged that 
the dispersibility was good, and if an undissolved lump was formed or a 
heterogeneous state was produced when stirring was initiated, it was 
judged that the dispersibility was bad. Of course, a sample having a bad 
dispersibility cannot be a binder of the present invention. 
(B) Water Resistance: 
A product obtained by curing the paste in which the gelation time had been 
measured according to the above-mentioned method (A) was allowed to stand 
still at room temperature for 4 days, and the cured product was thrown 
into water and when a change of the shape such as cracking or breaking was 
not observed even after passage of at least 24 hours, it was judged that 
the sample had a water resistance. In other case, it was judged that the 
sample had no water resistance. 
(C) Bonding Force: 
The bonding force was tested according to the method of JIS K-6852. At 
first, a steel plate and an asbestos plate having a thickness of 0.5 cm 
were cut into rectangular test plates having a size of 30 cm.times.25 cm. 
The surface to be bonded of the steel plate was polished with abrasive 
paper #240 until the metallic luster was observed, and the polished 
surface was washed with trichloroethylene and dried. 
An adhesive paste having a composition shown below was coated in a 
thickness of about 2 mm over an area of 25 cm.times.25 cm on the 
rectangular asbestos test plate, and the rectangular steel test plate was 
placed on the coated asbestos plate and bonded thereto over an area of 25 
cm.times.25 cm so that the non-bonded ear portions (5 cm.times.25 cm) were 
located on both the opposite sides and the adhesive paste did not protrude 
from the bonded area. Six test pieces were prepared for each adhesive 
paste, and the compression strength test was conducted under the following 
three conditions: (1) the test piece was allowed to stand at room 
temperature (10.degree. to 30.degree. C.) for 3 days and the strength was 
measured (normal state strength), (2) the test piece described in (1) 
above was thrown into water (25.degree. C.) and taken out after passage of 
24 hours, and the strength was measured in the state where water adhered 
to the test piece (water-resistant strength), and (3) the test piece 
described in (1) above was exposed to a predetermined temperature and the 
strength was measured (heat-resistant strength). 
The strength was determined by using a compression breakdown strength 
tester. More specifically, both the ear portions of the bonded test piece 
were erected and a pressure was applied thereto, and compression was 
conducted until the bonded surface or the asbestos plate was broken down. 
The load (Kg/mm.sup.2) applied to the test piece until the bonded surface 
or asbestos plate was broken down was measured, and the normal state, 
water-resistant or heat-resistance bonding strength was determined from 
the measured load. 
TABLE 5 
__________________________________________________________________________ 
Run No. 5-1 5-2 5-3 5-4 5-5 5-6 5-7 5-8 5-9 5-10 
__________________________________________________________________________ 
Powdery Sodium Silicate 
kind SS-1 SS-2 SS-3 SS-2 
SS-2 
SS-2 
SS-2 
SS-2 
SS-2 
SS-2 
amount (g) 100 100 100 100 100 100 100 100 100 100 
Alkali Metal Borate 
kind B-2 B-2 B-2 B-1 B-3 B-2 B-2 B-2 B-2 B-2 
amount (g) 10 10 10 10 10 4 6 15 30 10 
Silicon Polyphosphate 
kind H-2 H-2 H-2 H-2 H-2 H-2 H-2 H-2 H-2 H-1 
amount (g) 70 70 70 70 70 70 70 100 120 70 
Amount (g) of Water Added 
100 100 100 100 100 100 100 120 140 100 
Dispersibility 
good good good good 
good 
good 
good 
good 
good 
good 
Gelation Time (min) 
34 36 39 36 34 35 34 37 38 36 
(torque = 0.07 Kg-m) 
Water Resistance 
good good good good 
good 
good 
good 
good 
good 
good 
Bonding Force (Kg/cm.sup.2) 
normal state 78 82 83 79 76 55 65 82 84 80 
water-resistant 
18 20 22 18 22 10 13 21 23 19 
__________________________________________________________________________ 
Run No. 5-11 5-12 5-13 5-14 
5-15 
5-16 
5-17 
5-18 
5-19 
5-20 
__________________________________________________________________________ 
Powdery Sodium Silicate 
kind SS-2 SS-2 SS-2 SS-2 
SS-2 
SS-2 
SS-2 
SS-2 
SS-2 
SS-2 
amount (g) 100 100 100 100 100 100 100 100 100 100 
Alkali Metal Borate 
kind B-2 B-2 B-2 B-2 B-2 B-2 B-2 B-2 B-2 B-2 
amount (g) 10 10 10 10 10 10 10 10 10 10 
Silicon Polyphosphate 
kind H-2 H-2 H-2 H-3 H-4 H-5 H-6 H-7 H-8 H-9 
amount (g) 110 85 51 70 70 70 70 70 70 70 
Amount (g) of Water Added 
120 110 90 100 100 100 100 100 100 100 
Dispersibility 
good good good good 
good 
good 
good 
good 
good 
good 
Gelation Time (min) 
32 34 37 35 37 38 32 33 34 32 
(torque = 0.07 Kg-m) 
Water Resistance 
good good good good 
good 
good 
good 
good 
good 
good 
Bonding Force (Kg/cm.sup.2) 
normal state 88 86 62 80 79 76 71 69 72 68 
water-resistant 
26 24 13 18 18 17 12 11 24 20 
__________________________________________________________________________ 
Run No. 5-21 5-22 5-23 5-24 5-25 5-26 5-27 5-28 5-29 
__________________________________________________________________________ 
Powdery Sodium Silicate 
kind SS-2 SS-2 SS-2 SS-2 SS-2 SS-2 SS-2 SS-2 SS-2 
amount (g) 100 100 100 100 100 100 100 100 100 
Alkali Metal Borate 
kind B-2 B-2 B-2 B-2 B-2 B-2 B-2 B-2 B-2 
amount (g) 10 10 10 10 10 10 10 10 10 
Silicon Polyphosphate 
kind H-10 H-11 H-12 H-13 H-14 H-15 H-16 H-2 H-2 
amount (g) 70 70 70 70 70 70 70 70 70 
Amount (g) of Water Added 
100 100 100 100 100 100 100 65 130 
Dispersibility 
good good good good good good good good good 
Gelation Time (min) 
29 31 35 36 36 34 34 22 39 
(torque = 0.07 Kg-m) 
Water Resistance 
good good good good good good good good good 
Bonding Force (Kg/cm.sup.2) 
normal state 64 68 81 83 84 77 80 88 55 
water-resistant 
10 12 22 22 22 18 20 25 23 
__________________________________________________________________________ 
5-C1 5-C2 5-C3 5-C4 5-C5 5-C6 
Run No. (comparison) 
(comparison) 
(comparison) 
(comparison) 
(comparison) 
(comparison) 
__________________________________________________________________________ 
Powdery Sodium Silicate 
kind SS-2 SS-2 SS-2 SS-2 SS-2 SS-2 
amount (g) 100 100 100 100 100 100 
Alkali Metal Borate 
kind B-2 B-2 B-2 B-2 B-2 B-2 
amount (g) 0 2 10 10 10 10 
Silicon Polyphosphate 
kind H-2 H-2 HC-1 HC-2 HC-3 H-2 
amount (g) 70 70 70 70 70 40 
Amount (g) of Water Added 
100 100 100 100 100 90 
Dispersibility 
good good bad bad bad good 
Gelation Time (min) 
34 35 15 5 4 40 
(torque = 0.07 Kg-m) 
Water Resistance 
no no no no no no 
(breakdown) 
(breakdown) 
Bonding Force (Kg/cm.sup.2) 
normal state 76 77 22 8 5 40 
water-resistant 
0 0 0 0 0 0 
__________________________________________________________________________ 
From the foregoing results, it will readily be understood that an adhesive 
composed of a homogeneous prepared by adding a predetermined amount of 
water to a one-package type powdery mixture comprising powdery sodium 
silicate, an alkali metal borate soluble in an alkaline aqueous solution 
and silicon polyphosphate has a water resistance and shows a high bonding 
force under various conditions, and that this adhesive is much superior to 
comparative adhesives in the water-resistance bonding strength. 
EXAMPLE 2 
The method for improving the shelf life of a powdery one-package type 
inorganic binder will now be described. 
When powdery sodium silicate containing a large amount of sodium ions and 
powdery silicon polyphosphate containing a large amount of phosphoric acid 
ions are mixed and stored in one package, reaction is caused between the 
acid and alkali metal components by the moisture in air before the 
intended bonding effect is exerted, whereby the bonding effect is reduced. 
As means for preventing occurrence of this undesirable phenomenon, theee 
was adopted a method in which stearic acid, which is a kind of a fatty 
acid, or barium silicate were selected as a coating agent for the powdery 
silicon polyphosphate, and stearic acid or barium silicate were mixed with 
and coated on the powdery silicon polyphosphate to impart a 
water-repelling property to the powdery silicon polyphosphate. 
The mixed powder was exposed to certain relative humidity conditions, and 
the effect of improving the moisture resistance of silicon polyphosphate 
and the bonding effect of the mixed powder as a one-package adhesive were 
examined to obtain results shown in Table 6. 
The composition of Run No. 5-2 described in Example 1 was selected as the 
standard one-package inorganic binder composition. More specifically, a 
mixture of 100 g of powdery sodium silicate SS-2, 10 g of sodium borate 
B-2 and 70 g of silicon polyphosphate H-2 was used as the standard binder 
composition. In silicon polyphosphate H-2, the amount coated of stearic 
acid was 10%, but in this Example, the amount coated of stearic acid was 
adjusted to 0, 3, 5, 10 or 12%, and the amount coated of barium silicate 
was adjusted to 0, 5 or 12%. 
Water was added in an amount of 100 g to 180 g of the binder composition, 
and the mixture was stirred to form a homogeneous paste. 
In order to evaluate the resistance of the shelf life to water contained in 
air, the sample was allowed to stand under certain relative humidity 
conditions and also allowed to stand at room temperature. 
In the former test method, the powdery sample was allowed to stand in a 
dessicator maintained at a temperature of 20.degree. C. and a relative 
humidity of 60% for a week. Then, the sample was taken out and the bonding 
effect was evaluated. 
In the latter test method, the powdery sample was filled in a paper bag and 
allowed to stand at a laboratory of the Technical Department, Mizusawa 
Plant, Mizusawa Industrial Chemicals, Ltd., residing at 21, Aza Tonoda, 
Oaza Nishime, Tsuruoka-shi, Yamagata-ken, Japan for 6 months from Dec. 1, 
1980 to May 31, 1981, and then, the sample was taken out and the bonding 
effect was evaluated. 
TABLE 6 
__________________________________________________________________________ 
Run No. 
6-1 
6-2 6-3 6-4 6-5 6-6 6-7 
__________________________________________________________________________ 
Amount (%) of Coating 
0 stearic 
stearic 
stearic 
stearic 
barium 
barium 
Material acid 3 
acid 5 
acid 10 
acid 12 
silicate 
silicate 
5 12 
Dispersibility 
just after mixing 
good 
good 
good 
good 
good 
good 
good 
20.degree. C., 60% 
bad 
bad good 
good 
good 
good 
good 
room temp., 6 months 
bad 
bad good 
good 
good 
good 
good 
Gelation Time (min) 
just after mixing 
35 35 36 39 40 37 40 
20.degree. C., 60% 
15 25 33 36 37 35 38 
room temp., 6 months 
15 30 34 37 38 35 38 
Water Resistance 
just after mixing 
good 
good 
good 
good 
good 
good 
good 
20.degree. C., 60% 
no no good 
good 
good 
good 
good 
room temp., 6 months 
no no good 
good 
good 
good 
good 
Bonding Strength (Kg/cm.sup.2) 
(normal state) 
just after mixing 
84 82 80 80 75 80 78 
20.degree. C., 60% 
45 62 75 80 75 80 78 
room temp., 6 months 
30 60 76 80 75 80 78 
__________________________________________________________________________ 
From the foregoing results, it will readily be understood that a powdry 
mixture of silicon polyphosphate not coated with stearic acid or barium 
silicate and sodium silicate and sodium borate shows a sufficient bonding 
effect just after mixing but with the lapse of time, the bonding effect is 
reduced by the influence of water contained in the atmosphere. It will 
also be understood that an adhesive composition comprising powdery silicon 
polyphosphate coated with stearic acid or barium silicate has a good shelf 
life if the amount coated of coating material is 4 to 12%. 
EXAMPLE 3 
Results obtained when the one-package inorganic binder was used as agents 
other than the adhesive will now be described. 
A. Binder for High Temperature Refractory Material: 
A so-called magnesia brick was prepared as an example of a repairing 
material for a high temperature refractory material or high temperature 
structure of a definite or indefinite shape by using the inorganic binder 
of the present invention. 
The powdery magnesia aggregate used had the following composition: 
______________________________________ 
Natural magnesia clinker (smaller 
61% by weight 
than 1 mm) 
Natural magnesia clinker (1 to 
6% by weight 
5 mm) 
Sea water magnesia clinker (passing 
28% by weight 
through 200-mesh sieve) 
Asbestos 1% by weight 
Kibushi clay (passing through 
4% by weight 
20-mesh sieve) 
______________________________________ 
To 100 parts by weight of the above aggregate was added to 20 parts by 
weight of the one-package inorganic binder (sample of Run No. 5-2 
described in Example 1, which comprised 100 parts of SS-2, 10 parts of B-2 
and 70 parts of H-2), and 12 parts by weight of water was further added. 
The mixture was sufficiently stirred and filled in a round mold frame (30 
mm in diameter and about 30 mm in height), and the mixture was 
compression-molded under a pressure of 10 Kg/cm.sup.2. The so-formed test 
piece for determination of the normal state strength was removed from the 
mold frame. Then, the test piece was heated and dried in an oven 
maintained at 200.degree. C. for 4 hours. Then, the test piece was 
naturally cooled to obtain a columnar test piece for determination of the 
strength under heating (30 mm in diameter and about 30 mm in height). The 
compression strength (Kg/cm.sup.2) of each test piece was measured. 
For comparison, 20 parts by weight of commercially available water glass 
(sodium silicate No. 3 specified by JIS, SiO.sub.2 concentration=25%) or 
20 parts by weight of powdery aluminum primary phosphate (Al.sub.2 
O.sub.3.3P.sub.2 O.sub.5.3H.sub.2 O) was similarly added as the binder, 
and a columnar test piece was compression-molded in the same manner as 
described above and the compression strength was determined. 
The obtained results are shown in Table 9. 
B. Cold or Hot Adhesive for High Temperature Refractory Material: 
A basic magnesia brick was selected and used as a high temperature 
refractory material base. 
An adhesive having a composition shown in Table 7 was selected and used as 
cold or hot adhesive for this basic magnesia brick base. 
TABLE 7 
______________________________________ 
Aggregate (powdery natural 
100 parts by weight 
magnesia powder passing through 
200-mesh sieve) 
Binder composition of 
100 parts by weight 
present invention 
Flux [powdery Mg(OH).sub.2 ] 
5 parts by weight 
______________________________________ 
The binder composition of the present invention shown in Table 7 comprised 
100 parts by weight of powdery sodium silicate SS-2, 10 parts by weight of 
sodium borate B-2, 70 to 120 parts by weight of silicon polyphosphate H-2 
and 80 to 110 parts by weight of water. 
The above ingredients were sufficiently mixed to form a homogeneous paste. 
When the composition was used as the cold adhesive, the paste was coated 
in a thickness of about 1 mm on a base brick test piece at room 
temperature, and another base brick test piece was placed on the coating 
to form a sandwich structure and effect bonding. After passage of 24 
hours, the structure was exposed to 1400.degree. C. for at least 15 
minutes and naturally cooled to room temperature, and the bonding strength 
was measured according to the above-mentioned method for determination of 
the compression strength. 
When the composition was used as the hot adhesive, a base brick test piece 
was placed in an electric furnace maintained at 1400.degree. C. to heat 
the test piece at 1400.degree. C. In the same manner as described above 
with reference to the cold adhesive, the adhesive paste was coated on 
another test piece, and the coated surface of the test piece was bonded to 
the test piece heated at 1400.degree. C. in the electric furnace in the 
horizontal posture. After passage of at least 15 minutes, the bonded 
structure was vertically erected. If the bonded test piece did not fall 
down and was kept bonded, the bonded structure was kept in the horizontal 
posture again and secured in this state. A platinum-rhodium wire was 
attached to the upper test piece and a spring balance was attached to the 
other test piece. The bonded test piece was pulled together with the 
spring balance, and the bonding strength at fracture of the bonded surface 
was measured from a scale of the spring balance. 
The obtained results are shown in Table 9. 
For comparison, the same commercially available water glass (No. 3 
specified by JIS) and powdery aluminum primary phosphate as described 
above were used, and the cold bonding strength and hot bonding strength 
were similarly measured. The obtained results are shown in Table 9. 
C. Inorganic Paint: 
An inorganic paint paste of the present invention having a composition 
shown in Table 8 was coated in a thickness of about 0.5 mm on steel and 
asbestos test pieces (same as described above with reference to the method 
for determination of the bonding strength), and the coated test pieces 
were allowed to stand still at room temperature (about 20.degree. C.) for 
one week and dipped in running water for 200 hours, and the coated 
surfaces were examined. When the state of the coated surface was not 
substantially different from the state before the treatment, it was judged 
that the water resistance was "good". When blister, scar or rust was 
observed on the coated surface, it was judged that the water resistance 
was "bad" and the sample could not practically be used. 
The obtained results are shown in Table 9. 
TABLE 8 
______________________________________ 
Powdery sodium silicate SS-2 
100 parts by weight 
Sodium borate B-2 10 parts by weight 
Silicon polyphosphate H-2 
40 parts by weight 
Asbestos 20 parts by weight 
Pigment (titanium oxide) 
60 parts by weight 
Water 200 parts by weight 
______________________________________ 
TABLE 9 
______________________________________ 
Normal Strength 
State under 
Composition Strength Heating 
Binder (8-1) 
(parts by weight) 
(Kg/cm.sup.2) 
(Kg/cm.sup.2) 
______________________________________ 
present SS-2 100 
invention B-2 10 560 2100 
H-2 70 
comparison water glass 420 1030 
comparison aluminum phosphate 
430 760 
______________________________________ 
Cold .fwdarw. Hot 
Hot 
Cold or Hot 
Composition Strength Strength 
Adhesive (8-2) 
(parts by weight) 
(Kg/cm.sup.2) 
(Kg/cm.sup.2) 
______________________________________ 
present SS-2 100 
invention B-2 10 82.0 24.7 
H-2 120 
comparison water glass 0 0 
comparison aluminum phosphate 
0 0 
______________________________________ 
After 200 
Inorganic Composition Hours' 
Paint (8-3) 
(parts by weight) 
Dipping 
______________________________________ 
present SS-2 100 
invention B-2 10 good 
H-2 40 
comparison water glass bad 
comparison aluminum phosphate 
bad 
______________________________________ 
From the foregoing results, it will readily be understood that the 
one-package inorganic binder composition of the present invention can 
effectively be used as a molding binder for a high temperature refractory 
material, a cold or hot adhesive for a high temperature refractory 
material and an inorganic paint. 
EXAMPLE 4 
An embodiment in which an inorganic or organic assistant is added to the 
one-package inorganic binder of the present invention will now be 
described. 
Commercially available reagents and industrial chemicals shown in Table 10 
were selected and used as powdery assistants. 
TABLE 10 
______________________________________ 
Sample No. Assistant 
______________________________________ 
10-1 calcium silicate (CaSiO.sub.3) 
10-2 calcium phosphate (3CaO.P.sub.2 O.sub.5) 
10-3 aluminum phosphate (Al.sub.2 O.sub.3.3P.sub.2 O.sub.5.3H.sub.2 
O) 
10-4 sodium silicofluoride (Na.sub.2 SiF.sub.6) 
10-5 aluminum hydroxide [Al(OH).sub.3 ] 
10-6 magnesium hydroxide [Mg(OH).sub.2 ] 
10-7 asbestos 
10-8 talc 
10-9 powdery phenolic resin (resol type) 
10-10 powdery urea resin 
______________________________________ 
The mixing ratio (parts by weight), the intended use and the effect of each 
assistant are shown in Table 11. 
The effects in the respective uses were evaluated according to the methods 
described in Examples 1 through 3. The respective ingredients of the 
inorganic binder composition of the present invention were as shown in the 
preceding Tables. 
TABLE 11 
__________________________________________________________________________ 
Inorganic Binder 
and Composition 
Assistants and Amounts 
Run No. 
Use (parts by weight) 
(parts by weight) 
Effect 
__________________________________________________________________________ 
11-1 normal temperature 
SS-2 50 calcium silicate 
3 water-resistant 
curing type bonding strength 
water-resistant 
B-2 6 calcium phosphate 
3 of 42 Kg/cm.sup.2 
adhesive H-2 26 sodium silicofluoride 
12 
11-2 normal temperature 
SS-2 50 calcium silicate 
3 water-resistant 
curing type 
B-2 7 calcium phosphate 
3 bonding strength 
water-resistant 
H-2 30 sodium silicofluoride 
12 
of 60 Kg/cm.sup.2 
adhesive aluminum hydroxide 
6 
talc 12 
asbestos 6 
11-3 heat-curing type 
SS-2 50 sodium silicofluoride 
18 
gelation time of 45 
water-resistant 
B-2 7 calcium silicate 
2 minutes and water- 
adhesive H-2 30 resistant bonding 
strength of 65 Kg/cm.sup.2 
11-4 anti-oxidant type 
SS-2 40 phenolic resin 
70 
effective for preven- 
binder for high tem- 
B-2 4 tion of oxidation at 
perature material 
H-2 35 800-1000.degree. C. 
11-5 anti-oxidant type 
SS-2 40 urea resin 70 
effective for preven- 
binder for high tem- 
B-2 3 tion of oxidation at 
perature material 
H-2 35 800-1000.degree. C. 
11-6 hot adhesive 
SS-2 50 magnesium hydroxide 
10 
hot strength of 
B-2 5 aluminum phosphate 
10 
29.0 Kg/cm.sup.2 
H-2 50 
__________________________________________________________________________ 
From the foregoing results, it will readily be understood that when an 
inorganic or organic assistant is added to the inorganic binder of the 
present invention according to the intended use (for example, as a 
water-resistant adhesive, a binder or a hot adhesive), the bonding effect 
can further be enhanced. 
The combinations of the assistants shown in this Example are given only by 
way of example, and as is obvious to those skilled in the art, various 
modifications and changes may be made to these combinations.