JPH04280850A - Cementing composition and its use - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a hydraulic cementing composition containing a water-soluble alkaline silicate solution and a specified hardening agent of anhydrous boron phosphate, and its uses. Polymers with a main chain of siloxane bonds, which have excellent acid resistance and heat resistance, can be used even at room temperature.
The present invention relates to a cementing composition with good workability that is applied to binders, coating materials, solidified bodies, and structures formed at temperatures of 220° C. or lower, and uses thereof.

0002

BACKGROUND OF THE INVENTION Hitherto, Portland cement, alumina cement, and even gypsum have been widely used as inorganic hydraulic cementing materials. However, Portland cement and gypsum have calcium as their main component and are not acid resistant, and since both of these cementing materials are hydrated hardened materials, they are sensitive to heat and have poor heat resistance. On the other hand, cementing materials whose main component is alkali silicate, represented by water glass (hereinafter, alkali silicate may be abbreviated as "water glass"), have a siloxane bond ( -Si-O-)
It is expected to be used in solidified materials, binders, adhesives, etc. that require acid resistance and heat resistance. However, this water glass cementing material has various drawbacks as described below and has not been widely used.

There are three types of water glass curing mechanisms: air drying type, hydraulic type and reaction type. Among these, the reaction type is commonly applied. In this reaction type, by adding a curing agent to water glass or heating it, the silanol groups of water glass are dehydrated and condensed to create siloxane (-Si).
Refers to the type that forms a polymer with -O-) bonds. The polymer cured product produced by this dehydration condensation is suitable for use as various solidified products, binders, binders, coating materials, and the like.

[0004]Currently commercialized water glass cementing materials are composed of three components: water glass liquid is used as a glue agent, and a hardening agent and filler (aggregate, functional agent, etc.) are added to this. It is common for there to be. Therefore, during construction, these three materials are mixed and kneaded to form a paste or mortar prior to construction. However, water glass cementing materials generally have a poor balance between their workability and the early development of various physical properties of the resulting cured product. That is, a cementing material with good workability has a slow early development of various physical properties in the resulting hardened product, and a cementing material with a fast early development of various physical properties in the resulting hardened product has poor workability. Therefore, much research has been conducted on water glass cementing materials to improve this point, particularly regarding curing agents and curing conditions, and various improvement techniques have been proposed.

[0005] Some of these research results are summarized and reported in "Inorganic Adhesives" [Japan Adhesive Association Journal 12 394 (1976)]. U.S. Patent No. 2662022 (1953) as a self-hardening type alkali silicate composition.
), there is an example of an acid-resistant mortar made of water glass using sodium silicofluoride as a hardening agent (Kiln Association 69 2).
84 (1961) is known. Further, as an example of a cementing composition comprising a combination of modified water glass and inorganic phosphate, Japanese Patent Publication No. 53-109558
No., Special Publication No. 56-6387, Special Publication No. 68-5
8306 and JP-A-57-32277. Furthermore, examples of using boric acid as a hardening agent for water glass include Japanese Patent Publication No. 47-4464, and examples of using boric acid salts include Japanese Patent Application Laid-open No. 48-44325. Further, JP-A-50-54619 discloses an example in which a fired mixture of borates, phosphates, etc. is used as a hardening agent for water glass.

[0006]

Problems to be Solved by the Invention The cured product obtained by curing water glass in a reactive manner has several drawbacks because the alkali component of water glass coexists in the cured product. Moreover, the alkaline components coexisting in the cured product are
Since it has high water solubility and high activity, coexisting alkali ions tend to be easily eluted when the cured product is immersed in water. Therefore, once the cured product produced by the reaction type is brought into contact with water, the siloxane bonds forming the cured product tend to be easily redissolved by the alkali ions eluted at this time, and as a result, the cured product becomes weaker. It turns into In addition, the alkali ions dissolved in water easily react with carbon dioxide gas in the atmosphere to produce alkali carbonate as a by-product, which tends to cause so-called whitening or efflorescence in the cured product, reducing its commercial value.

In addition to the above-mentioned problems, in order to commercialize as a cementing material a material in which water glass is reacted at room temperature to form a polymer and is made into a cured product that is endowed with water resistance, etc., the following steps are necessary. The problems mentioned above have not yet been technically solved. (A) The viscosity of water glass itself is inherently high, making it difficult to mix additive materials such as hardeners. If the water glass viscosity is lowered by water dilution, etc., a strong cured product cannot be obtained. The rate of the (B) reaction type reaction is determined by the dehydration condensation reaction of silanol groups that occurs upon neutralization of the alkali of water glass and the acid of the curing agent. However, during actual construction, it is necessary for the mixture of alkali and acid to maintain a mortar-like or liquid state for a certain period of time (at least during the construction work) without starting the dehydration condensation reaction so that the construction work can be performed. In other words, during the construction work, the mixture of alkali (water glass) and acid (hardening agent) does not cause dehydration condensation reaction and maintains a liquid viscosity that is easy to work with, and after construction, the dehydration condensation reaction quickly progresses and the whole It is necessary to obtain a homogeneous cured product, and there is no technology that satisfies both of these requirements in a well-balanced manner under one condition. (C) The reaction rate of silanol group dehydration condensation is determined by temperature, and a temperature difference of 10° C. greatly affects the cured product produced. Therefore, in on-site construction under natural conditions, workability is extremely limited due to temperature. There is no technology to absorb this temperature effect.

[0008] As described above, water glass cementing materials have several basic drawbacks and require many restrictions on the range of use and construction conditions. Therefore, it has been used only in places where other materials cannot compensate, for example where heat resistance or acid resistance is particularly required. but,
In this case as well, it is used only as a compromise product with conditions such as sacrificing workability, sacrificing the time required to develop various resistances, or giving up on construction at room temperature and applying temperature treatment. is the current situation.

In fact, compounds generally proposed as hardening agents for water glass are compounds that are acidic or highly soluble in water because of the need to promote and complete the dehydration condensation reaction of silanol groups. For example, the proposed phosphate easily hydrolyzes in water and has strong acid activity. Therefore, when such a hardening agent is brought into contact with water glass, gelation occurs at the contact site, making it difficult to maintain a mixture of water glass and hardening agent in a homogeneous liquid state suitable for construction work for a certain period of time. On the other hand, phosphates that do not undergo hydrolysis do not have the ability to condense the silanol groups of water glass. This phenomenon also occurs when boric acid or borate salts are used as hardeners.

As described above, the cured product has the ability to harden alkali silicate, maintains a homogeneous liquid state for a certain period of time at the initial stage when it is mixed into water glass, and has excellent resistance to various properties after application. A curing agent that forms this has not yet been developed. Furthermore, there is no example of a boric acid compound being applied as a hardening agent for water glass for this purpose. In addition, commercially available boron phosphate produced by combining boric acid and phosphoric acid has an aqueous suspension pH of 1, as shown in the examples below.
It is small in size and exhibits strong acidity. Therefore, as in the case of the above-mentioned phosphate, it instantly gels when it comes into contact with water glass, making it impossible to obtain a homogeneous liquid mixture that is stable for at least a certain period of time, making it unsuitable as a hardening agent for water glass. It is.

[0011] Therefore, in order to maintain a liquid state of a mixture of water glass and a hardening agent for a certain period of time using conventional techniques, a compound designed to slow down the reaction rate with water glass is selected as a hardening agent. , and research on its improvement has been conducted. However, even if the pot life of the mixture can be secured by slowing down the reaction rate of the curing agent with water glass, such a curing agent cannot complete the dehydration condensation reaction of the silanol groups required next at room temperature. When doing so, the reaction rate becomes extremely slow and it takes a long time to complete the cured product.
Under these conditions, it is impractical. As described above, conventional alkali silicate cementing compositions have poor balance in terms of workability and time required to develop various resistances, and are not satisfactory cementing materials in the art.

0012

OBJECTS OF THE INVENTION The purpose of the present invention is to solve the above-mentioned problems, to enable at least room-temperature reaction type construction, to quickly form a cured polymer with siloxane bonds at room temperature after construction, and to cure the cured product. The object of the present invention is to provide an alkali silicate cementing composition that exhibits various resistances in an extremely short period of time and is suitable for uses such as coating materials, binders, solidified bodies, and structures. To achieve this, it is necessary to technically complete the following themes. (1) The reaction of the mixture of alkali silicate and curing agent is suspended for the time required for construction work (usually at least 60 minutes), causing gelation, increasing liquid viscosity, or progressing polymerization. It must maintain a homogeneous paste or mortar-like consistency without any smearing. (2) After construction at the target location, immediately store at room temperature (up to 2
Develop physical properties such as water resistance within 4 hours). (3) The formed cured product can eliminate the harmful effects of coexisting alkaline components and maintain long-term resistance without weakening or whitening. In order to solve the above-mentioned problems with water glass-based cementing materials and achieve the purpose of the present invention, the present inventors
Through repeated experiments and research, we have arrived at the present invention.

[0013]

[Means for Solving the Problems] The present invention has been proposed to achieve the above object, and has an important technical feature in that the specified boron phosphate is selected as the curing agent. are doing. That is, according to the present invention, in a cementing composition containing a water-soluble alkaline silicate solution, an inorganic curing agent, and, if necessary, a filler, the inorganic curing agent has an ignition loss of 5% by weight or less; and 5% by weight aqueous suspension having a pH in the range of 1.8 to 8.5, and a cementing composition using finely powdered anhydrous boron phosphate having the chemical formula BPO4.

Further, according to the present invention, there is provided a cementing composition in which anhydrous boron phosphate as the inorganic curing agent contains an alkaline earth metal corresponding to at least 20% by weight on an oxide basis. Further, according to the present invention, the inorganic curing agent is prepared in advance in a wet state with a liquid combination of one or more selected from water, surfactants, and coupling agents in an amount of 20% by weight or less. A cementing composition is provided. Furthermore, according to the present invention, the alkaline component of the aqueous alkali silicate solution has the formula M2O(M
is an alkali metal element), and the M2O 100
A cementing composition is provided in which the inorganic curing agent is blended in an amount of 30 to 400 parts by weight per part by weight. Further according to the invention, the filler has a particle size of 2
Provided is a cementing composition that is a combination powder of one or more selected from fillers, pigments, and volume materials having a size of 0.00 microns or less.

Further, according to the present invention, the binder or coating material is obtained by curing the cementing composition at a temperature of 220° C. or lower including room temperature to form a cured polymer having siloxane bonds as the main chain. provided. Furthermore, according to the present invention, 100 to 900 parts by weight of one or more combination ingredients selected from aggregates, reinforcing materials, and molded bodies are added in advance to 100 parts by weight of the cementing composition. 22.
A solidified body or structure is provided in which a cured polymer having siloxane bonds as a main chain is integrated as a binder by curing at a temperature of 0° C. or lower.

[0016]

[Function] As pointed out above, in order for an alkali silicate cementing composition to be actually applied as an inorganic coating material, paint, adhesive, etc., (1) the composition must be in the form of a homogeneous liquid that is easy to work with; It is essential to solve three points at the same time: (2) to quickly develop water resistance etc. after construction, and (3) to eliminate the harmful effects of coexisting alkaline components and have excellent resistance. It is. The first condition to meet these demands is that as mentioned above, the curing agent used will gel the water glass at the initial stage of contact with the water glass, which will increase the liquid viscosity of the mixed composition and make it non-uniform. Such things should not happen.

Generally, boron phosphate is produced by evaporating a mixed aqueous solution of phosphoric acid and boric acid and heating the residue, or by heating boric acid and diammonium hydrogen orthophosphate. This boron phosphate is a rare example in which boron is bound to phosphoric acid as a cation, and the crystal has a modified cristobalite-type structure. Moreover, when this boron phosphate is suspended in water, it hydrolyzes and the pH
Shows acidity of 1 or less. This chemical formula is BPO4・nH
2O (n=3, 4, 5, 6). In addition, the anhydrous product obtained by dehydrating the crystal water of boron phosphate has strong hygroscopicity and is a compound that easily deteriorates. This will be described in the present example below, and is easily understood from the fact that if this anhydrous material is left in a room at room temperature for 20 days, it will absorb about 25% of moisture. As described above, commercially available boron phosphate is susceptible to deterioration and also easily causes a gelation reaction when it comes into contact with water glass, making it impossible to secure a homogeneous liquid that can be applied to the cementing composition of the present invention. It is unsuitable as a hardening agent for materials.

The present inventors have repeatedly conducted research and experiments to find that fine powder boron phosphate has a loss on ignition of 5% by weight or less, and 5% by weight or less.
A hydraulic cementing composition using a curing agent specified as a compound exhibiting a pH range of 1.8 to 8.5 in weight percent of an aqueous suspension can be prepared as a composition satisfying the above three conditions. I gained new knowledge. It has also been found that this composition is suitable for uses such as inorganic coating materials, paints, binders, adhesives, solidified bodies, and structures. In addition, the present inventors have determined that, as a method for preparing the anhydrous boron phosphate specified above, when heat treatment is performed with or without addition of an alkaline earth metal compound, the raw material boron phosphate contains It has been found that while the free acid content is fixed or removed, the phosphoric acid content can be dehydrated and condensed by this heat treatment to become a polyphosphate, which is a compound that undergoes extremely slow hydrolysis.

Although it is not clear why the fine powdered anhydrous boron phosphate specified in the present invention can be used as a curing agent that satisfies the above three conditions, it is not clear why the fine powder anhydrous boron phosphate specified in the present invention can be used as a curing agent that satisfies the above three conditions. Judging from the results of the examples, etc., it can be inferred as follows. That is, the anhydrous boron phosphate of the present invention does not contain crystal water or free acids (phosphoric acid or boric acid), has a small ignition loss of 5% by weight or less, and also contains boric acid, which is difficult to hydrolyze. Because it is converted into a polyphosphate, the rate of hydrolysis in water is extremely slow and it does not exhibit strong acidity with a pH of less than 1.8. Therefore, it seems possible to suppress the gelation reaction of the silica component at the initial stage of contact with the alkaline silicate solution, and to maintain the mixture as a homogeneous liquid that is workable.

[0020] Furthermore, silica sol has an isoelectric point near pH 2, and maintains a stable sol state near this pH value.
It is generally known that silica sol will gel no matter which side the pH value shifts to. The anhydrous boron phosphate of the present invention has a pH of 1.
Since this pH range is adjusted to a range of 8 to 8.5, the overlap between this pH range and the stable range of silica sol is also thought to be the reason why a stable homogeneous liquid can be maintained in the early stage of mixing.

Next, the anhydrous boron phosphate of the present invention is once added to the alkali silicate solution to form a stable homogeneous liquid, and then the boron phosphate is slowly hydrated with the alkali component of the alkali silicate and water. Start disassembly. Thereafter, hydrolysis progresses rapidly, and the boric acid and phosphoric acid produced here play an important role as catalysts for the dehydration and condensation of the silanol groups possessed by the alkali silicate, and the dehydration and condensation of the silanol groups accelerates exponentially. It is believed that this will enable the completion of polymers with siloxane bonds efficiently in a short period of time. Moreover,
The polymer produced here has a structure of strong siloxane bonds, and therefore exhibits excellent physical properties such as acid resistance and heat resistance.

What is more important in the present invention is that boric acid and phosphoric acid, which play an important role as dehydration condensation catalysts for silanol groups, play a dual role to neutralize the alkaline components contained in the alkali silicate solution. Since it is blended in a sufficient amount of acid, it plays the role of forming a salt with the alkaline component that coexists in the cured product, and fixing this alkaline component. Therefore, in the present invention, it is possible to prevent various adverse effects caused by the coexistence of alkali ions as described above.

Furthermore, according to the present invention, coloring property, In addition to modifying and changing the surface properties, it is possible to further strengthen the structure of the cured product by the produced polymer, provide stable physical properties with respect to various resistances, and improve its functionality.

The cementing composition of the present invention as described above can be applied directly to a target location at room temperature, and the applied material exhibits excellent resistance. In particular, this construction composition has a structure made of a polymer with siloxane bonds as its main chain, so even when applied to areas exposed to heat, it can be used at temperatures ranging from room temperature to high temperatures (e.g. 80
Exhibits excellent heat resistance against various temperature gradients up to 0°C.

Furthermore, what is important for the present invention is that in addition to the property that the composition of the present invention is excellent in heat resistance, the composition does not contain any organic components such as organic solvents.
The reason is that there are no risks such as the generation of harmful odors during construction or the generation of toxic gases during heating. Therefore, the composition of the present invention saves resources and can be highly evaluated in terms of safety.

The composition of the present invention can be usefully used in various places due to the above-mentioned advantages, but for example, it can be used as a coating for high heat-resistant members such as tunnels of transportation systems, underground malls, flues of thermal power plants, and furnaces. materials, paints, joints, hardening materials, binders such as adhesives,
Furthermore, it can be suitably used as solidified bodies and structures required for fire-resistant building materials and structures. In addition, with recent changes in the natural environment, materials used for outdoor buildings are required to be resistant to acids such as acid rain and acid fog, and the composition of the present invention can be used as a coating material or adhesive for these materials. Moreover, it can be suitably used as a structure or a solidified body.

[0027]

DETAILED DESCRIPTION OF THE INVENTION The anhydrous boron phosphate fine powder of the present invention is obtained by heating industrially produced commercially available boron phosphate, etc. as a raw material in a temperature range of 110 to 900°C, preferably 400 to 800°C. It is prepared by processing to remove the water of crystallization in the raw materials, remove free acids (phosphoric acid, boric acid) contained in the raw materials, and grind and classify as necessary. As a result, the physical properties of the boron phosphate powder prepared here were as follows: the ignition loss was 5% by weight.
In the following, it becomes possible to control the pH of the 5% by weight aqueous suspension in the range of 1.8 to 8.5, preferably in the range of 2.2 to 6.0.

If the heating temperature at this time is lower than 110°C, water of crystallization remains in the compound, making it impossible to reduce the loss on ignition of boron phosphate to within 5% by weight. Also, the pH of a 5% by weight aqueous suspension cannot be maintained at 1.8 or higher. On the other hand, when the heating temperature is 900° C. or higher, the obtained boron phosphate is difficult to hydrolyze in water, becomes an inactive compound, and is difficult to become an acid catalyst for the dehydration condensation of alkali silicate, which is the object of the present invention.

A more preferred method for preparing the anhydrous boron phosphate powder of the present invention is to mix an alkaline earth metal component in an amount equivalent to at least 20% by weight based on the oxide with the raw material boron phosphate in advance, and then heat-treat the powder. A method can be adopted. As a result, it became possible to inactivate the free phosphoric acid and boric acid contained in the raw material boron phosphate without volatilizing them, and the pH of the 5% by weight aqueous suspension was reduced to 1.8 to 8. in the range of .5, preferably 2
．． It becomes possible to control the temperature within the range of 2 to 8.0. The alkaline earth metal components to be mixed include oxides and hydroxides of magnesium, calcium, barium, etc.
Carbonates, phosphates, borates, organic acid salts, etc. can be mentioned. In particular, boron phosphate prepared using a barium salt is suitable for ensuring a long working life of the cementing composition.

A further preferable method for preparing the anhydrous boron phosphate powder of the present invention is to prepare the anhydrous boron phosphate powder of 20% by weight or less in advance, considering that the anhydrous boron phosphate of the present invention does not show strong acidity when it comes into contact with water as described above. A method can be adopted in which a liquid modifier such as water, a surfactant, a coupling agent, etc. is blended into boron phosphate in an amount of 100% to keep the boron phosphate in a wet state. As the liquid modifier such as a surfactant or coupling agent used here, a neutral or basic surfactant that is resistant to alkaline solutions, a silane coupling agent, a titanium coupling agent, etc. can be selected.

[0031] Phosphate, which is a curing agent that has been used conventionally,
When borates are mixed with alkali silicate after water has been mixed in advance, the phosphates and borates are immediately hydrolyzed by the added water, resulting in free phosphorus. Since acid and boric acid are generated, the alkali silicate gels instantly, making it impossible to obtain a homogeneous liquid that can be used for construction work. However, even if the anhydrous boron phosphate of the present invention is mixed with a liquid modifier such as water in advance to make it into a dry, paste-like, or plastic-like wet state, the boron phosphate in the wet state is converted into silicate. Even if it comes into contact with alkali, it will not cause problems such as gelation immediately.
Moreover, it is possible to improve the mixability of the cementing composition and the subsequent construction workability, and is suitable for the present invention.

The alkali silicate solution used in the present invention can be made from either powder or liquid alkali silicate, which is commonly called water glass. The powdered alkali silicate may be any water-soluble or water-dispersible alkali silicate, and the liquid alkali silicate may be an approximately 50% aqueous solution of powdered alkali silicate or a diluted solution thereof. For the purpose of the present invention, M2O・nS
Represented by the compositional formula of iO2・mH2O (where M is an alkali metal such as lithium, potassium, or sodium), n
An alkali silicate having m in the range of 1 to 4 and m in the range of 12 to 24 can be selected at any time depending on the intended use of the cementing composition, its application, construction conditions, etc. At this time, when the number n is smaller than 1, the alkali component is too large and a cementing composition with excellent water resistance cannot be obtained. Furthermore, when the number n is greater than 4, good formation of a polymer with siloxane bonds cannot be expected, and a cured product with high strength cannot be obtained. The number n can be appropriately selected from the above range depending on the intended use and workability required of the present cementing composition.

As the alkali metal species of the alkali silicate, sodium is preferred because it is easily available and inexpensive. In particular, water glass (JIS standard product), which is a solution of sodium silicate, is suitable. However, depending on the field and purpose of use of the cementing composition, as well as the required physical properties of the cured product, alkali silicate, which is a silicate containing potassium or lithium alone or in combination with an alkali metal including sodium, may be used. liquid can be used. The concentration of alkaline silicate solution is silica (
The amount can be appropriately selected from the range of 10 to 33% by weight based on SiO2) depending on the field of use and purpose of the cementing composition, the required physical properties of the cured product, etc.

Furthermore, in the present invention, in order to improve various physical properties such as the pot life and the strength of the cured product of the cementing composition, a borate (for example, sodium borate, zinc borate) is added to the alkaline silicate solution used in advance. etc.) or a modified alkaline silicate solution to which a silicofluoride (for example, sodium silicofluoride, etc.) has been added and cured can be used. In addition, in order to improve the pot life and workability of the cementing composition, as well as the physical properties of the cured product, it is possible to use a complex modified alkaline silicate solution to which surfactants, polysiloxanes, and resins are added. can.

In the cementing composition of the present invention, the alkaline component of the alkali silicate solution is expressed on the basis of the oxide of M2O (M is an alkali metal component), and fine powder of anhydrous boron phosphate is added per 100 parts by weight of M2O. 30 as a hardener
It can be blended in an amount of from 400 parts by weight, preferably from 50 to 300 parts by weight. When the proportion of the curing agent added to the alkaline silicate solution is less than 30 parts by weight per 100 parts by weight of M2O, the expected physical properties of the cured product of the cementing composition cannot be obtained. Further, even if the blending ratio is 400 parts by weight or more, it cannot be expected that the various physical properties of the cured product will be particularly improved.

In the present invention, as a curing agent for alkali silicate, a specified fine powder of anhydrous boron phosphate is used as the main curing agent. For this purpose, a compound commonly used as a hardening agent for water glass can be used in combination with the hardening agent of the present invention as a hardening aid. Examples of suitable curing aids include oxides (ZnO, MgO, C
aO, Al2O3, etc.), hydroxides (Mg(OH)2,
Al(OH)3 etc.), fluorosilicate (Na2S
iF6, K2SiF6, BaSiF6, etc.), phosphates (Ca3(PO4)2, Mg2P2O7・8H2O, A
lPO4, Al(H2PO4)3, Zn3(PO4)
3.SiP2O7 etc.) Silicates (Al2O3・nSi
Fine powder natural products such as O2, MgO, nSiO2, etc.
You can choose from synthetic products, refined products, and fired products, either singly or in combination of two or more. These hardening aids are used in an amount of 50% by weight based on the main hardening agent, anhydrous boron phosphate.
It can be blended in amounts up to.

The cementing composition of the present invention may contain powders of fillers, pigments, volume materials, etc., which are powders of 200 microns or less, depending on the physical properties, functionality, workability, purpose of use, etc. required for the cured product. The body can be mixed and used as a filler. These fillers should be added within a range that does not impair workability or physical properties, for example, 0.1 to 80 parts by weight per 100 parts by weight of a mixture consisting of alkali silicate and anhydrous boron phosphate.
They can be used alone or in combination of two or more in an amount of 0% by weight.

An example is shown below. As a filler,
Powders of metals and alloys such as stainless steel, silicon and iron,
Glass powder, ceramic powder, diamond powder, silicon oxide (silica sand powder, silica powder, silica powder, silica fume, etc.), fused alumina powder, magnesia powder, calcium carbonate, zircon sand, various clays (bentonite, smectite, gyrome, kibushi clay) refined products such as), fired clay (
calcined products of bauxite, montmorillonite, kaolin, etc.), gypsum, calcium phosphate, magnesium phosphate, barium sulfate, aluminum fluoride, calcium silicate,
Magnesium silicate, barium silicate, barium carbonate,
It can be suitably selected from powders with a particle size of 200 microns or less, such as barium hydroxide, aluminum silicate, talc, fly ash, etc., and used after conducting preliminary experiments if necessary.

Pigments include inorganic colored pigments such as titanium dioxide, Bengara, chromium oxide, yellow lead, carbon black, and ultramarine, as well as silica-based white carbon, alumina, zinc oxide, magnetic iron oxide, boron nitride, silicon carbide, Inorganic functional pigments such as various clay powders can be used depending on the purpose.

[0040] Volume materials include various mica, asbestos, flaky metal powder, inorganic fibers such as glass fiber, rock wool, natural mineral fiber, and carbon fiber, as well as silica, silica sand, and waxite having various particle size distributions and shapes. , feldspar, chamotte, mullite, alumina, dolomite, magnesia, zirconia, calcia, zircon, carbon, graphite, carbide, nitride, and other heat-resistant refractory powders with a particle size of 200 microns or less. can do.

[0041] Each of the above-mentioned fillers is pulverized, classified, and mixed, taking into account the purpose of use of the cementing composition, and giving due consideration to its properties such as particle size structure, pore volume, specific surface area, and water absorption. It is important to use materials that have been subjected to , sintering, refining, etc. alone or in combination of two or more. Further, it is important to handle these fillers with sufficient care for the water content they contain. Generally, if the filler contains water, it must be removed in advance or coated or sintered to prevent water absorption. Furthermore, depending on the workability and purpose of use, powders in which these fillers are surface-treated with various coupling agents, surfactants, etc. can also be used.

[0042] The cementing composition of the present invention includes physical properties and workability of the cementing composition in order to improve various performances such as dispersibility, impregnating property, antifoaming property, fluidity, and applicability of the composition. Various surfactants and organic compounds, such as coupling agents, silicone compounds, resins, etc., may be added and blended in advance within a range that does not impair properties.

[0043] Since the cementing composition of the present invention is of a reactive type, the alkaline silicate liquid part and the powder part such as a hardening agent should be mixed as much as possible immediately before construction to ensure workability. It is preferable to take this into account. The mixing method is
Mixers commonly used in various construction industries such as the civil engineering industry, cement industry, concrete industry, and paint industry, such as mortar mixers, agitators, and mixers, differ depending on the content of the cementing composition and the purpose of use. A method capable of obtaining a homogeneous liquid state can be adopted by selecting an appropriate method from among , homogenizer, etc. Taking into account the weather and environmental conditions during mixing and work, the materials (liquid and powder parts) before mixing are cooled or warmed to the desired temperature conditions before use. You can also.

The cementing composition of the present invention in the form of mortar, paste or liquid mixed into a homogeneous liquid state is
Construction can be carried out according to the purpose and use by methods commonly used in the industry, such as spraying, spraying, brushing, roller, troweling, pouring, mounding, patching, etc. can do.

In the present invention, the cementing composition of the present invention is used as a binder, and aggregates, reinforcing materials,
It is possible to provide a solidified body or a structure by integrating molded bodies and the like. The aggregate, reinforcing material, and molded body preferably used at this time can be appropriately selected from the following materials having a particle size of 200 microns or more. These materials are
To form an integrated solidified body or structure by contacting it in an amount that does not impair the purpose of use, workability, various physical properties, etc., for example, 100 to 900 parts by weight per 100 parts by weight of the cementing composition. Can be done.

[0046] Suitable aggregates, reinforcing materials, molded bodies, etc. having a particle size of 200 microns or more used in the present invention include, for example,
Various aggregates can be used, such as silica, silica sand, waxite, feldspar, chamotte, mullite, alumina, dolomite, magnesia, zirconia, calcia, zircon, carbon, graphite, carbide or nitride. In addition, artificially manufactured glass beads, glass flakes, metal flakes,
Perlite, various synthetic lightweight aggregates, powdered or granular artificial aggregates made from industrial waste such as slag and fly ash, etc. can be used. Furthermore, wood, bamboo,
Plant fibers, flaky or fibrous metals, inorganic fibers such as glass fibers, rock wool, natural mineral fibers, carbon fibers, and organic fibers such as stables, fabrics, slivers, nets, nets, mats, and woven fabrics. , fibrous reinforcing materials such as nonwoven fabrics, and molded bodies can also be used. Furthermore, a molded body made of the above-mentioned aggregates or the like can also be used.

[0047] Although the above aggregates, reinforcing materials, molded bodies, etc. used in the present invention have various particle size structures and shapes,
They can be appropriately selected and used depending on the purpose of use and required physical properties. Furthermore, depending on the construction work and purpose of use, materials that have been previously treated with various coupling materials, surfactants, resins, etc. may also be used.

[0048] There are various methods for forming the cementing composition of the present invention into a solidified body or structure integrated with a binder for these aggregates, reinforcing materials, molded bodies, etc. There is a method in which the cementing composition of the present invention is mixed together with materials, molded bodies, etc. and then cured as a whole in a certain formwork or container, or furthermore, aggregates, reinforcing materials, molded bodies, etc. are mixed in advance in a formwork or a container. There is a method in which the composition of the present invention is placed in a container, and then the mixed and liquefied composition of the present invention is poured into the container to be cured and integrated. These methods can be selected and adopted as appropriate depending on the purpose, application, environmental conditions, etc.

In order to use the cementing composition of the present invention as a binder or coating material, or as a solidified body or structure, fillers, pigments, bulking materials, aggregates, and reinforcement may be added as necessary. This is possible by curing the material, molded body, etc. at a temperature of 220° C. or lower, including room temperature, to form a cured polymer having siloxane bonds as the main chain. but,
220℃ depending on the specified purpose and construction conditions.
It is also possible to perform construction under the following conditions such as heating, pressurization, deaeration, and dehydration. Further, if desired, it is also possible to perform the construction under reduced pressure in an inert gas atmosphere such as nitrogen gas. It is also possible to perform construction in a carbon dioxide atmosphere that is active against alkali silicates.

When the cementing composition of the present invention is used as a material for mass production on a manufacturing factory line, etc., conditions suitable for the purpose can be selected from among the above construction conditions and adopted. Generally, in order to improve product productivity, it is preferable to carry out the work under conditions such as heating, pressure, deaeration, and dehydration.

[0051] The objects to which the cementing composition of the present invention is used as a binder, coating material, solidified body, structure, etc. are not particularly limited, but may be applied to the following places: Examples include objects and objects. Parts, various materials, structures, various devices, floors, walls, blocks, etc. made of paper, pulp, metals such as iron, alloys such as stainless steel, rocks, glass, plaster, ceramics, slag, asphalt, wood, fibers, etc. flue, chimney, furnace and furnace surroundings,
Surfaces of roads, tunnels, bridges, building materials, buildings, etc.; Also, surfaces of ingots and equipment that require lot marking; Also, objects to be impregnated include various fabrics, molded bodies, structures, honeycomb bodies, etc. made of the above materials. can be cited as useful construction sites and objects, respectively.

[0052] Furthermore, the cementing composition of the present invention includes:
It can be usefully used as a material for repair, ground treatment, pretreatment, hole filling material, finishing material, mounting material, anti-slip material, etc. at each of the above locations. Furthermore, the composition of the present invention may be blended with various ceramic materials, fibrous materials, abrasive materials, wear-resistant materials, various inorganic compounds, etc., and applied to materials that meet various needs such as water resistance, heat resistance, fire resistance, acid resistance, etc. It can also be used as a solidifying agent, processed material, adhesive, binder, joint material, etc. for various materials similar to those mentioned above, such as chemical factories, food factories, plating factories, etc.
It can be applied to hot springs, cafeterias, hotel kitchens, flues, drains, building materials, etc.

Furthermore, since the cementing composition of the present invention has better fluidity than Portland cement, etc., it can be used as a pouring and hardening material for various molding materials.
It can also be used as a pouring repair material for damaged parts of refractory furnace materials, chimneys, boilers, structures, etc.
amorphous) or industrial waste molded into a specific shape,
For example, it can be usefully used as an injection solidification material for processing and disposing of solid radioactive waste disposed of from nuclear power plants and the like.

Furthermore, the cementing composition of the present invention can be used as an anchoring material for structures and equipment such as tanks, towers, and buildings, as well as in places where embedding and plastic patching materials are required in each of the above-mentioned fields. It can also be usefully used as a fixed cement material.

[0055]

According to the present invention, the hydraulic alkaline silicate cementing composition can be used as a coating material, a binder, a solidified product,
When used for structures, etc., it is possible to perform at least a room-temperature reaction type construction, and after construction, a polymer cured product consisting of nonflammable siloxane bonds is formed immediately at room temperature, and this cured product quickly acquires various resistances. Materials that can be effectively expressed,
It can be secured using materials and methods that are resource-saving and environmentally friendly, and can be provided as a highly safe product with excellent water resistance, heat resistance, acid resistance, etc.

[0056]

[Examples] The present invention will be explained below with specific examples. First, the method for preparing the anhydrous boron phosphate hardening agent of the present invention and its physical properties will be explained, and then the cementing process using this boron phosphate will be explained. The properties of this composition will be explained with application examples of the composition. Application examples include types that form relatively thin films as coating materials such as paints and adhesives,
Two types will be explained: a type that forms a unified structure or solidified body as a flooring material, injection solidified material, etc. This example shows only a part of the test results in the construction field to which the composition of the present invention can be applied.

I. Preparation of hardening agent Using commercially available industrial boron phosphate powder (sample number C-1: manufactured by Yoneyama Chemical Co., Ltd.) as a raw material, this boron phosphate was
C. for 60 minutes, and then passed through a 325 mesh sieve to prepare anhydrous boron phosphate powder (sample number A-1) of the inorganic curing agent of the present invention. In addition, the commercially available reagent barium carbonate (BaCO3) was used as the starting material for boron phosphate.
After adding 3% by weight and homogeneously dispersing it in a dry process,
Anhydrous boron phosphate powder (sample number A-2), which is an inorganic curing agent, doped with barium was prepared by heat treatment at ℃ for 60 minutes and passing through a 325 mesh sieve. In addition, using the anhydrous boron phosphate powder (sample number A-1) prepared by the above method as a raw material, 5% by weight of a silane coupling material (SR-2402 manufactured by Dow Corning Toray Industries), which is an oligomer of methylmethoxysilane, was added. Anhydrous boron phosphate paste (sample number A-3) was prepared by adding 8% by weight of the aqueous solution containing the mixture and kneading and mixing. In addition, boron phosphate (sample number C-1) used as a raw material as a comparative hardening agent
and zinc phosphate powder (commercial reagent:
Sample number C-2) and silicon phosphate (manufactured by Mizusawa Chemical Co., Ltd., sample number C-3) were selected. As described above, the physical properties of three types of samples of the present invention and three types of samples serving as comparative examples were measured using the test methods shown below, and the results are also shown in Table 1.

II. Test method for physical properties Loss on ignition: The sample is brought to a constant weight at 800°C, and the weight loss at this time is expressed as weight (%). pH of 5% by weight aqueous suspension: Take an amount of sample equivalent to 5% by weight in 200 ml of purified water (ion-exchanged water), stir at 20°C for 60 minutes, and measure the liquid pH at this time using a pH meter (Hitachi). - Measured using Horiba Model N-5). Moisture absorption rate: Approximately 10 g of sample powder was left standing in a desiccator at 20°C and relative humidity of 80% for 20 days, and expressed as weight increase rate (%) during this period. Main compound: Measured by X-ray diffraction using powder method, and identified the main compound. Initial reactivity with water glass: JIS standard product No. 3 water glass (SiO2 27.0%, Na2O 9.5%,
Molar ratio 2.9) 20g of powder sample in 100ml
was added and stirred for 10 minutes, and the mixture was immediately filtered through a 40-mesh wire mesh, and the amount of the mixture remaining on the wire mesh was measured in %. In this case, if the mixture maintains a homogeneous liquid state, almost 100% of the mixture passes through the wire mesh and there is no residual amount on the wire mesh, but if the mixture forms a gel or has a high viscosity, The remaining amount % on the wire mesh increases. It was determined that the initial reactivity of the hardening agent and water glass increased in proportion to the amount remaining on the wire mesh, and that workability was not ensured.

As a result, commercially available boron phosphate used as a comparative example had a large loss on ignition, and the pH of the 5% aqueous suspension was 1.
Low as below. Therefore, the initial reactivity with water glass, which is an alkali silicate, is extremely high, and a homogeneous liquid state that can be used as a cementing composition cannot be obtained at all. Moreover, the moisture absorption rate for 20 days is as high as about 25%, indicating that it is an unstable compound. In addition, the comparative examples of silicon phosphate and zinc phosphate exhibit physical properties similar to those of anhydrous boron phosphate, but their main crystal forms are silicon pyrophosphate and zinc phosphate, respectively, and their initial reactivity is low and construction work is possible. Although a homogeneous liquid was formed, the pH of the 5% aqueous suspension was low and the mixture with water glass rapidly (within 10 minutes) after mixing.
It was in a liquid state that increased the viscosity of the liquid and reduced workability.

In contrast, the anhydrous boron phosphate of the present invention has a small ignition loss of 5% by weight or less, regardless of the presence or absence of barium doping, and the pH of the 5% aqueous suspension is 2.
．． The pH of the 5% aqueous suspension of boron phosphate doped with barium is as high as 7.8.
In addition, the moisture absorption rate for 20 days was low at about 5% or less, and the initial reactivity with water glass was zero. Further, the boron phosphate paste of the present invention, which is prepared by moistening the powder of anhydrous boron phosphate with an aqueous solution containing a silane coupling agent, also has zero initial reactivity. Therefore, it is well understood that the cementing composition of the present invention using anhydrous boron phosphate as a hardening agent first forms a homogeneous liquid state at the initial stage of mixing and can be applied during construction.

III. Other materials used in the application examples The composition of the alkaline silicate solution used is shown in Table 2, and the contents of the types of fillers and aggregates are shown in Table 3. Note that the selection and blending ratio of each material are indicated for each applied composition. Example 1 In this example, an example will be described in which a cementing composition using anhydrous boron phosphate as a hardening agent and a mixed paste prepared by stirring and mixing the composition shown in Table 4 is applied to a coating material. In addition, an example using zinc phosphate and silicon phosphate as a hardening agent will be explained as a comparative example. Evaluation as a coating material coating material was performed using the test method shown below. The results are also shown in Table 4.

Test method as paint for coating material: (1)
Pot life: 50 ml of the mixed paste was placed in a 180 ml paper container and left at 20±3°C, and the time until the paste lost its fluidity was defined as the pot life. Although the pot life measured by this test method tends to be longer than the actual pot life that can be coated, this method was adopted in this example for convenience.

(2) Time until water resistance develops The test plate coated on a steel plate was immersed in tap water at 20°C for 30 minutes at regular intervals, starting immediately after the application, and the coated surface of the test plate was touched with a finger. The time until there was no more rubbing, peeling, or detachment of the coated material was defined as the time for developing water resistance (h).

(3) Coating Appearance The appearance of the test plate coated on the steel plate was visually observed, and test plates with no bubbles, blisters, cracks, peeling, or unevenness were evaluated as good.

(4) Using a test plate coated on acid-resistant plate glass, JIS K 540
In accordance with the test method described in 7.5 of 0, a sulfuric acid solution with a concentration of 20% by weight kept at 20°C was selected and immersed in this sulfuric acid solution for 30 days, and the coated surface showed no swelling, bubbles, peeling, etc. A test plate with no holes, softening, or elution was considered to have acid resistance.

(5) Using a test plate coated on a heat-resistant steel plate, it was exposed to an electric furnace maintained at 600°C for 20 minutes in accordance with the test method described in JIS K 5400, and then allowed to cool at room temperature. However, a test plate with no blistering, cracking, peeling, etc. on the coated surface and a strong coating film was considered heat resistant.

(6) Adhesion Using a test plate coated on a steel plate, use a cutter knife to create a 1.0 mm grid pattern on the coated surface according to the grid test method described in 6.15 of JIS K 5400. JIS K
Evaluation score (0 to 10) described in 6.15 of 5400
) was displayed as a score evaluation.

[0068] As a result, the alkaline silicate cementing composition using anhydrous boron phosphate as a hardening agent can secure the time required for construction work in a homogeneous paste state, and can be used for various purposes in about one day after application. It is well understood that it is a material that exhibits resistance and has excellent resistance such as heat resistance and acid resistance, and can be effectively applied as an inorganic paint or coating material without any adverse effects such as bad odor.

Example 2 In this example, an example will be described in which a cementing composition using anhydrous boron phosphate as a hardening agent is used as a binder by stirring and mixing the composition shown in Table 5 to form a mixed paste. Note that a composition using zinc phosphate as a curing agent will be explained as a comparative example. Evaluation as a binder was performed using the test method shown below. The results are also shown in Table 5.

Test method as a binder: (1). Pot life of mixed paste The pot life was determined using the same test method as for coating materials. (2). The time required for the mixed pest to develop water resistance The time (h) for the development of water resistance was determined using the same test method as for the coating material. (3). Evaluation was performed using the same test method as for the cured appearance coating material. (4). It was evaluated using the same test method as for acid-resistant coatings. (5). According to the test method described in the same way as for heat-resistant coating materials, 400
A test plate that is exposed to an electric furnace maintained at ℃ for 20 minutes, then allowed to cool at room temperature, and has no blisters, cracks, or peeling on the cured body, and the cured body is in a robust state is considered to be heat resistant. did. (6). Compressive strength: Pour the mixed paste into a rectangular mold (2 x 2 x 8 cm) according to the method described in JIS A 1108,
After leaving it at room temperature for 24 hours, it was demolded and JIS A 1
The compressive strength (kg/cm2) was determined using a compression tester according to the method described in No. 132. (7). The mixed paste was poured into a mold made to measure 40 x 40 x 15 cm on an adhesive steel plate, and cured for 7 days at 25°C to prepare a test piece that was adhered to the steel plate. Next, in accordance with the Ministry of Construction's Building Research Institute's adhesion testing method, the testing machine attachment is glued with epoxy resin adhesive, and the test machine's hydraulic pressure is used to pull it upward to ensure the bond between the adhered object and the test solidified object. The adhesive strength (kg/cm2) was measured from the load (P) when the surfaces were peeled off.

As a result of the above, the alkali silicate cementing composition using anhydrous boron phosphate as a hardening agent can secure the time necessary for construction work in a homogeneous paste state, and can be used in various applications in about one day after construction. It has excellent resistance to heat, acid resistance, strength, and adhesion, and can be effectively applied as a binder to various binders, adhesives, solidifying materials, repair materials, etc. without causing any adverse effects such as bad odors. It is well understood that the material is

Example 3 In this example, the cementing composition of the mixed paste (sample number 2-2) used in example 2 using anhydrous boron phosphate as a hardening agent was solidified (sample number 3-1). An example of application to a structure (sample number 3-2) will be explained. The solidified body and the structure were prepared by the method shown below, and their evaluation was performed by the test method shown below. The results are shown below.

Test method for solidified body and structure:
(1). Pot life The pot life was determined using the same test method as for coating materials. (2). Time to develop water resistance The time to develop water resistance (h
). (3). Evaluation was performed using the same test method as for the cured appearance coating material. (4). It was evaluated using the same test method as for acid-resistant coatings. (5). Evaluation was performed using the same test method as in the case of heat-resistant binders. (6). Compressive strength was evaluated using the same test method as in the case of binders. (7). It was evaluated using the same test method as in the case of adhesive binders.

For preparation as a solidified material, a mixed aggregate of 2 kg of artificial aggregate particles (Pamco No. 3 to 6) and 1 kg of No. 5 silica sand was selected as the aggregate, and the mixed aggregate prepared in Example 2 was added to this mixed aggregate. 1 kg of paste (sample number 2-2) was added and stirred to obtain a mortar-like mixture flooring material. This flooring material was applied smoothly to a thickness of 5 mm on a concrete floor by troweling. The physical properties of the flooring material prepared here were evaluated using the above test method. The results were as follows: pot life: 50 minutes, physical property development time: 24 hours, hardening time: good, acid resistance: yes, heat resistance: yes, compressive strength (Kg/cm2): 3
80 and adhesiveness (Kg/cm2) of 20, it is well understood that the present cementing composition can be applied as a flooring material with excellent resistance such as heat resistance and acid resistance with good workability.

To prepare the structure, a cylindrical molded product (15φ x 15mm) of powdered inorganic compound salts (a mixture of sodium sulfate and calcium sulfate) produced as a by-product as industrial waste was set in an oil can (20 liters). The mixture paste prepared in Example 2 (Sample No. 2-2) was injected into the filling and hardened, and the whole was filled. It has an integrated structure. The compressive strength of a test piece of a structure consisting of an injection-hardened industrial waste molded body and a reinforcing body left at room temperature for 7 days was measured, and the result was 370.
(Kg/cm2). As a result of the above, using this cementing composition, aggregate,
It is well understood that when poured into an aggregate of reinforcing agents, molded bodies, etc., and cured, the whole exhibits excellent physical properties such as heat resistance as an integrated structure.

[0076]

[0077]

[0078]

[0079]

[0080]

Claims (7)

[Claims] Claim 1: A water-soluble alkali silicate solution and an inorganic curing agent;
Furthermore, in a cementing composition containing a filler as necessary, the inorganic curing agent has a loss on ignition of 5.
% by weight or less, and the pH of the 5% by weight aqueous suspension is 1.8.
A cementing composition characterized in that it uses finely powdered anhydrous boron phosphate having a chemical composition formula of BPO4 in a range of from 8.5 to 8.5. 2. The cementing composition according to claim 1, wherein the inorganic curing agent contains an alkaline earth metal in an amount of at least 20% by weight, based on the oxide, in anhydrous boron phosphate. 3. The inorganic curing agent is prepared in advance in a wet state with a liquid combination of one or more selected from water, surfactants, and coupling agents in an amount of 20% by weight or less. 3. The cementing composition according to 1 or 2. 4. The alkaline component of the aqueous alkali silicate solution is represented by the formula M2O (M is an alkali metal element), and the inorganic curing agent is 30% per 100 parts by weight of M2O.
Claim 1 wherein the compound is blended in a proportion of 400 to 400 parts by weight.
4. The cementing composition according to any one of items 3 to 3. 5. The filler according to claim 1, wherein the filler is a combination powder of one or more selected from fillers, pigments, and volume materials having a particle size of 200 microns or less. Cementing composition. 6. The cementing composition according to any one of claims 1 to 5 is cured at a temperature of 220° C. or lower, including room temperature, to form a cured polymer having siloxane bonds as the main chain. A binder or coating material characterized by: 7. 100 parts by weight of the cementing composition according to any one of claims 1 to 5, containing one or more combination materials selected from aggregates, reinforcing materials, and molded bodies. is added in advance in the range of 100 to 900 parts by weight, and is cured at a temperature of 220°C or lower, including room temperature, to integrate a cured polymer having siloxane bonds as a main chain as a binder. A solidified body or structure.