JPH11246261A - One pack powdery alkali silicate composition, paste-like alkali silicate solidifying agent using the composition, treatment of industrial waste and polymer product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali silicate compsn. which does not need a complicated in-situ mixing process, which is homogeneous and has enough hardness, which can maintain the fluidity and usable time required for building work, which can prevent efflorescence and which shows improved water resistance. SOLUTION: Four powdery components described below are homogeneously mixed in one pack state. The four components are a powdery alkali silicate which is soluble in water and is expressed by M2 O.SiO2 .qH2 O, wherein M is one alkali metal element of Li, Na and K, a powdery barium salt expressed by BaO.rSiO2 .sH2 O having a soluble content of barium ion in an alkali soln., a powdery silicon phosphate expressed by tSiO2 .P2 O5 having slow-releasing property of the phosphate component, and a reactive powdery aluminum oxide hydrate expressed by Al2 O3 .uH2 O. The components are mixed in such a manner that to 100 pts.wt. of the alkali silicate, the barium component, phosphate component and aluminum component are mixed by 0.1 to 10 pts.wt., 1 to 40 pts.wt., and 10 to 50 pts.wt., respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkali silicate composition in which an alkali silicate is mixed.
The present invention relates to an alkali silicate composition suitable for an adhesive or the like, a paste-like alkali silicate-based solidifying material using the same, a method for treating industrial waste, and a polymer product.

[0002]

2. Description of the Related Art Originally, ceramics, ceramics, bricks, glass, and the like are widely used as inorganic polymer products which have undergone a heating step in the field of ceramic products and pottery. As a cold hardening inorganic hydraulic hardening material that does not undergo a heating step, Portland cement, alumina cement, gypsum and the like are generally widely used. However, since ceramic products require heating, the place of production is limited, and Portland cement and gypsum do not have acid resistance due to the calcium component as a main component, and they are hydrated, so they cannot be heated. There was a drawback that it was brittle and had poor heat resistance.

[0003] In order to solve these difficulties, there is an inexpensive liquid alkali silicate represented by water glass (hereinafter, alkali silicate is simply referred to as water glass as appropriate), and the bonding form thereof is a siloxane bond (-Si- Since O-) is mainly used, it has been widely used for a long time as a solidification material in construction and civil engineering fields, a raw material of silica gel, a solidified material requiring acid resistance and heat resistance, a binder, an adhesive and the like. .

[0004] The curing mechanism of the liquid alkali silicate is classified into an air-drying type, a hydraulic type, and a reaction type, and the reaction type is most commonly applied. In this reaction type, a curing agent is added to an alkali silicate to cause a dealkalization reaction, and a silanol group is dehydrated and condensed to form a polysiloxane (—O—Si
-O-) refers to a type that forms a polymer having a bond. The polymer produced by the dehydration condensation is suitable as an inorganic polymer for various solidified substances, binders, binders, coating materials, coating materials and the like.

[0005] A typical example of an alkali silicate-based solidifying material that has been commercialized in the past is composed of liquid water glass as a gluing agent (main agent), a curing agent, an aggregate, and a filler. Generally, at the time of construction, these three are once mixed and kneaded on site to prepare a paste or mortar, and then subjected to construction.

Here, the above-mentioned alkali silicate solidified material has the following problems. Hereinafter, these will be sequentially described. On-site mixing In other words, labor saving is the most important issue in on-site work, but it is practically impossible to produce a one-part product in the form of a solution consisting of a mixture of an alkali component and an acidic component. In addition, a complicated process of mixing two raw materials, an alkali silicate solution and a curing agent, on site is essential. Strength Generally, when sulfuric acid or hydrochloric acid, which is a strong acid, is added to and brought into contact with an alkali silicate solution, a silicate gel is preferentially generated at a contact portion between the alkali silicate solution and the strong acid. Therefore, when the alkali silicate solution as the main agent and the silicon phosphate as the curing agent are directly mixed on site, an inhomogeneous mixture of the gel-like portion and the liquid portion is inevitably formed because phosphoric acid is a strong acid. It is not possible to form a mixed paste which is formed and homogeneously diffuses the silicon phosphate throughout the alkali silicate solution. As a result, it is not possible to expect sufficient hardness with uniform physical properties in the resulting solid.

Ensuring the pot life Even if the heterogeneous "porridge" state produced as described above is forcibly mixed by stirring to form an apparently homogeneous paste, the paste in this state is obtained. In this case, the homogeneity is simulated, and unlike the homogeneous “Omoyu” state, the “Omoyu” state cannot be formed by stirring. In fact, this "porridge" -like paste rapidly thickens, and it is not possible to secure the fluidity and the pot life required for the construction work. Therefore, the construction work is extremely restricted.

Whitening Phenomenon When an inorganic polymer composed of a siloxane bond is produced by a condensation reaction of an alkali silicate with a silanol group, an alkali component of the alkali silicate is liberated from the polysiloxane bond due to the condensation reaction of the polymerization, and becomes unreactive. It becomes stable and reacts with carbon dioxide gas in the air on the surface of the solidified body, causing a whitening phenomenon of by-producing white powdered alkali carbonate (for example, sodium carbonate).

[0009] In a solidified body formed by applying a water-resistant alkali-based solidifying material to a room-temperature construction, an alkali component may remain free in the solidified body. In this case, if there is contact with water (for example, Since the liberated alkali component dissolves and decomposes the siloxane bond (by absorbing the moisture in the air), the solidified product tends to collapse, and it becomes difficult to maintain the solidified product. for that reason,
Poor water resistance and cannot withstand outdoor use.

[0010] There are many studies for improving the above-mentioned problems (1), in particular, about curing agents and curing conditions.
Development techniques have been proposed.

For example, Japanese Patent Publication No. 58-58306 and Japanese Patent Publication No. 1-53 mainly correspond to the above.
No. 230, Japanese Patent Publication No. 2-1791, Japanese Patent Publication No. 2-1791,
No. 56299, etc., which disclose a one-packed inorganic binder composition based on a powdery alkali silicate. Among the above, particularly corresponding to the above, Japanese Patent Publication No. 1-53230, Japanese Patent Publication No. 2-1791, and Japanese Patent Publication No. 2-56299 disclose a powdery one-pack inorganic binder composition. The flowability of the paste slurry is improved by using a crystalline or amorphous barium silicate powder specially manufactured under the conditions specified for the product (heat treatment at a high temperature of 700 ° C. or higher) as a curing retarder. It is disclosed that the working time can be secured while maintaining the workability. Of the above, those corresponding to the above are, for example, JP-B-53-242.
No. 06 discloses a water glass composition containing a curing agent having a specified release property of phosphoric acid.

In addition to the above publications, a self-hardening type alkali silicate composition is disclosed in US Pat. No. 2,660,022, and a cured composition comprising a combination of a modified water glass solution and an inorganic phosphate is particularly preferred. 53-242
No. 12, JP-B-53-109558, JP-B-56-6387, JP-B-57-42581, and the like, and further disclosed in JP-B-53-2420.
No. 6 discloses various silicon phosphates effective for alkali silicate in detail. Further, an example of using sodium fluorosilicate as a curing agent as an acid-resistant mortar made of water glass is disclosed in Kerkyo 69284 (1961).

[0013]

However, the above-mentioned prior art still has the following problems. That is, the above-described conventional technology solves some of the above-mentioned problems, but none of them can solve all of the above problems at the same time. In particular, Japanese Patent Publication No. Sho 5 corresponding to the above
No. 8-58306, Japanese Patent Publication No. 1-53230,
Japanese Patent Publication No. 2-1791 and Japanese Patent Publication No. 2-56299 attempt to supply an alkali silicate-based solidifying material in a one-packed powder form. Due to being packed, the shelf life of the storage shelf is not stable, and the workability of the paste after mixing with water is strict, and the concrete commercialization has not been achieved. In addition, for example, in Japanese Patent Publication No. Hei 2-1791, it is necessary to use a specially manufactured crystalline or amorphous custom-made raw material (= barium metasilicate), so that the product cost rises.

In addition, Japanese Patent Publication No.
In JP-A-53230, JP-B-2-1791, and JP-B-2-56299, even when workability is ensured, the hardening is delayed, and the manifestation of the solidified body hardness is delayed. May not be exhibited early.

Further, in the above-mentioned prior art, a fixed amount of water is blended with a powdered alkali silicate composition to obtain a paste-like solidifying material or a treating agent, or a process in which the paste-like solidifying material or the like is used alone or in combination. As a product,
Furthermore, there is no disclosure about a specific use that can be applied as an adhesive polymer product which is a coating material or an adhesive.

A first object of the present invention is to solve all of the above-mentioned problems, that is, to eliminate a complicated on-site mixing step, to have a uniform and sufficient hardness, to obtain a fluidity and a usable amount necessary for construction work. It is an object of the present invention to provide an alkali silicate composition capable of securing time, preventing a whitening phenomenon, and improving water resistance, a paste-like alkali silicate-based solidifying material using the same, a method for treating industrial waste, and a polymer product. is there. A second object of the present invention is to provide an alkali silicate composition which can prevent the development of the hardness of the solidified body from being too late, and can quickly develop the hardness, a paste-like alkali silicate-based solidifying material using the same, and industrial waste. And a polymer product.

Note that some terms used in the present specification are defined as follows for clarity.

"Inorganic polymer": water is added to and mixed with the powdery alkali silicate composition according to the present invention, and a polysiloxane bond formed by bonding silicon (Si) and oxygen (O) is formed as a main chain. Polymer compound. This inorganic polymer is a nonflammable, super-weather-resistant, stain-resistant, and chemical-resistant polymer, and is clearly different from flammable organic polymers composed of bonds such as carbon (C) and hydrogen (H). Be distinguished.

"Paste-like alkali silicate solidifying material":
The paste prepared by adding and mixing a certain ratio of water to the powdery alkali silicate composition according to the present invention maintains viscosity for which the workability is secured for a certain period of time, and various materials [soil, sand, various Quarrying, various waste powders / molded articles (including low-level radioactive waste), etc.].

[Industrial waste treatment method]: The paste-like alkali silicate-based solidifying material according to the present invention is used as an industrial waste having a specific shape (industrial waste, low-level radioactive waste, etc.) and a primary treated product thereof. Is injected into a predetermined container in which is stored, and is opened to at least room temperature to form an inorganic polymer, and the industrial waste or the like is fixed in the predetermined container.

"Inorganic polymer product": A paste prepared by adding and mixing water to the powdery alkali silicate composition of the present invention can be used alone in a predetermined shape (lump, film, sheet, film, thin plate, fiber) , A cord, a bar, a bar, a powder, a sphere, a sand, a foam, a specific shape, etc.) to form a molded solidified body, and to be used for various purposes.

"Adhesive polymer product": A paste prepared by adding and mixing water to the powdery alkali silicate composition according to the present invention forms an inorganic polymer while adhering to the surface or inner surface of various substrates. A product that fulfills its intended function.
Specific examples include paints, base materials, sealers, coating materials, protective materials, adhesives, sealing materials, gaskets,
Products such as jointing agents, putties, hardening materials, caulking materials, potting materials, cementing materials, anchor materials, binders, and cured products are exemplified.

"Composite product": A paste prepared by adding and mixing water to the powdery alkali silicate composition of the present invention can be used for various metals, concrete, ceramics, clay, rocks, cement, gypsum, gypsum, slag, and sand particles. , Aggregate, body pigment, glass, brick, enamel, wood / bamboo, paper, fiber /
Shape maintaining material composed of cloth, plastic, asphalt, reclaimed industrial waste, etc. (for example, lump, granule, powder, net, net, woven / non-woven fabric, plate, film,
(Sheets, membranes, containers, packages, honeycombs, pipes, structures, etc.), and forms an inorganic polymer in an integrated state and is used for various purposes. Specific examples include composite glass, film, sheets, building materials,
Products that are effective for roofing materials, furniture, gardening goods, soundproofing materials, sound absorbing materials, heat insulating materials, heat insulating materials, containers, tools, parts, devices / equipment, specific structures, and the like.

"Polymer product": A generic term for the above-mentioned "inorganic polymer product", "adhesive polymer product" and "composite product".

"Alkali-soluble component of barium ion (Ba ²⁺ )": A solution obtained by stirring and dispersing 10 g of powdered barium salt in 100 ml of 1N caustic soda solution at 25 ° C. for 10 minutes, and then filtering the sample solution. Barium ion (Ba ²⁺ )
And the amount (%) of barium (Ba) eluted in a 1N caustic soda solution with the barium element (Ba) amount in the sample taken as a reference (100).

"Sustained release of phosphoric acid": The initial amount of phosphoric acid eluted in the sample solution represented by the following formula (*) is 200 or less, and the average hydrolysis rate constant α is 0.2. It refers to a state within the above range. Y = αX + β (*) where, X: Elapsed time (minutes) up to 120 minutes of a sample solution in which 1 gram of powdered silicon phosphate was stirred and dispersed in 100 ml of 4N caustic soda at 25 ° C. Y: Eluted cumulative amount of eluted phosphoric acid (P ₂ O ₅ ) (mg / 100ml)
"Poorly soluble sulfate compound in alkali solution": 10 g of the sulfate compound was stirred and dispersed in 100 ml of 1N caustic soda solution at 25 ° C. for 60 minutes, and the sample solution was filtered to remove sulfate (SO ₄ ²⁻ ) in the solution. the quantified, of sulfate collected in the sample (SO ₄ ^2-) a reference (100) to 1N sodium hydroxide solution sulfate ion eluted stirred after dispersion for 60 minutes in a (SO ₄
^2- ) ^{Calculate the} amount (%) and elute sulfate (SO ₄ ^2- )
The case where the amount (%) is 50% or less is regarded as poorly soluble.

[0027]

Means for Solving the Problems (1) In order to achieve the above object, the present invention provides a method of uniformly mixing powdery four components of alkali silicate, barium salt, silicon phosphate, and aluminum oxide hydrate. In the powdered one-pack alkali silicate composition filled in a one-pack state, the alkali silicate is one of the alkali metal elements of Li, Na, and K, M, 1.2 to 3.2. the number of p, the number of 0.5 to 1.5 as _{q, M 2 O · pSiO 2} · qH 2 in water represented by O-soluble powdery alkali silicate one or more of It is composed of a combination, wherein the barium salt is
Assuming that a number of 4.0 or less is r and a number of 9.0 or less is s, Ba
O · rSiO ₂ · sH is composed of a single or two or more kinds of powdery barium salt having a soluble component in an alkaline solution of a barium ion represented by ₂ O, the silicon phosphate is 1. Assuming that the number from 0 to 8.0 is t, tS
It is composed of powdered silicon phosphate having a sustained release property of phosphoric acid represented by iO ₂ · P ₂ O ₅ alone or in combination of two or more thereof.
When the number of 0.5 to 5.0 is u, it is composed of reactive powdery aluminum oxide hydrate represented by Al ₂ O ₃ .uH ₂ O, and these powdery alkali silicates; Powdered barium salt, powdered silicon phosphate, and powdered aluminum oxide hydrate are based on 100 parts by weight of powdered alkali silicate.
Powdered barium salt, powdered silicon phosphate, and powdered aluminum oxide hydrate each contained 0.1 to 10 parts by weight,
-40 parts by weight, and 10-50 parts by weight.

In the present invention, a barium element is specified from alkaline earth metals, and a compound containing the barium element is converted into an inexpensive barium salt compound having a soluble component in an alkaline solution. By mixing with the alkali silicate composition of the pack (hereinafter referred to as powder composition), a paste prepared by adding and mixing water to the powder composition (hereinafter referred to simply as paste) is applied. In addition, the fluidity and the pot life required for the construction work can be secured. In addition, this can suppress a partial rapid gelation reaction (partial gelation) occurring at a contact portion between the alkali silicate solution and the acidic component as a curing agent. That is, when barium ions (Ba ²⁺ ) coexist in the paste, unlike when alkaline earth metal ions other than the barium element soluble in the alkaline solution are coexisted in the paste, necessary for the construction work. Liquidity and pot life can be secured. This is because barium ion, unlike other alkaline earth metal ions, has a slow reaction rate of silicate formation with alkali silicate, and has a buffering action that can suppress rapid dealkalization reaction. This has the function of suppressing the rate of polymerization at the time of the condensation of the compound to suppress an increase in paste viscosity. In addition, since it contains barium ions as described above, the acidic component of the curing agent to be blended in the powdery composition must be an acidic component that can follow up the behavior of barium ions shown in the paste, If the acidic component of the curing agent reacts with the alkali silicate before the barium ion starts to behave, uniform solidified body formation cannot be expected. Therefore, in the present invention, powdery silicon phosphate having a sustained release property of phosphoric acid, which gradually releases protons in an alkaline solution, is adopted as a curing agent. This suppresses partial condensation of the silicate, slows down the condensation reaction, causes polymerization of homogeneous siloxane bonds without forming a heterogeneous silicate gel, and the resulting solidified product has a higher molecular weight. The resulting polymer is compacted, the polymer strength shifts to high strength, and the formation of an inorganic polymer is effectively achieved. Furthermore, by mixing inexpensive aluminum hydroxide into the composition of the present invention as an aluminum oxide hydrate having excellent reactivity with an alkali component, it is in an unstable state because it is separated and separated by condensation of silanol groups. The alkali component is immobilized, whereby the whitening phenomenon that occurs on the surface of the solidified product of the inorganic polymer generated from the powdery composition can be suppressed, and excellent water resistance can be imparted to the generated inorganic polymer product. That is,
The paste prepared from the powdery composition of the present invention, the role of silicon phosphate as the above-mentioned acidic component, and the role of the above-mentioned barium ion, which effectively derives the role of the above-mentioned acidic component, make it possible to form a hydroxide. A synergistic effect is given to the role of aluminum, and the chemical phenomena that occur here are combined. By the synergistic effect of these three roles, a homogeneous and high-hardness solidified inorganic polymer is effectively produced and applied. As a result, since the aluminum hydroxide is blended into the powdery composition to prepare the paste, the alkali component which is separated and is in an unstable state due to the formation of polysiloxane bond is coexisted with silica and water. Reacts with aluminum oxide to produce sodalite, a precursor of zeolite, and can fix the free-separated alkali components, suppressing the whitening phenomenon and effectively exhibiting various properties such as water resistance. It is possible to do. Further, by filling the powdery four components of alkali silicate, barium salt, aluminum oxide hydrate, and silicon phosphate in a one-pack state, a complicated on-site mixing step can be eliminated. Here, as described above, these four powdery components exhibiting a synergistic effect (a powdery alkali silicate soluble in water, a barium salt soluble in an alkaline solution, a phosphoric acid having a sustained release property of phosphoric acid) Silicon and reactive aluminum oxide hydrate), when constituting a one-pack composition in powder form, an acidic component (in the present invention, silicon phosphate) should coexist in a one-pack in an alkaline component. Therefore, this one-pack product must ensure stable shelf life without reacting during storage. In the present invention, as described above, aluminum hydroxide is blended in the powdery composition, and by functioning to prevent direct contact between the acidic component and the alkaline component, these are regarded as a one-pack product. In this case, the sustainability of the phosphoric acid content of the silicon phosphate is maintained, and the workability of the paste prepared by adding water is also ensured, and the storage and management can be stably performed.

For the constants in each equation, p is 1.2
By the above, it is possible to prevent the curing rate from being too large due to an excessive amount of the alkali component, to prevent the whitening phenomenon from occurring, and to prevent the water resistance from decreasing. By setting p to 3.2 or less, Good utilization of the silicic acid contained in the formation of the produced polymer can be ensured, and a solid having high hardness can be reliably obtained. Further, by setting q to be 0.5 or more, it is possible to prevent the solubility of the powdery alkali silicate in water from being impaired, and to ensure effective use of the alkali silicate. By setting the content as described below, it is possible to prevent the deliquescence of the powdered alkali silicate, thereby reducing the storage stability of the powdered one-pack product and impairing shelf life. Further, by setting r to be 4.0 or less, the activity of barium ions can be reliably and effectively utilized. Further, by setting s to 9.0 or less, it is possible to prevent the storage stability of the barium salt in a one-pack product from being impaired. Further, by setting t to 1.0 or more, it is possible to prevent the stability as silicon phosphate from being lacked due to deliquescent, and to further set t to 8.0 or less, the content of phosphoric acid is reduced. It reliably prevents the amount from decreasing and the function as an acidic component curing agent from deteriorating. Furthermore, by setting u to 0.5 or more, it is possible to prevent the reactivity with alkali silicate or the like from becoming poor and preventing the function as an alkali-immobilizing component from being sufficiently exhibited, and to reduce u to 5.0 or less. By doing
It is possible to eliminate the possibility that aluminum oxide hydrate cannot be maintained in a fluffy powder state and cause trouble during storage of a one-pack product.

Regarding the mixing ratio of each component, by mixing the barium salt in an amount of 0.1 part by weight or more with respect to 100 parts by weight of the alkali silicate, the fluidity of the produced paste is ensured only for the time required for the working life. Can be secured,
Also, by mixing the barium salt in an amount of 10 parts by weight or less, it is possible to prevent the curing speed of the solidified material from becoming too slow and impairing the practicality of commercializing the inorganic polymer. Also, by mixing silicon phosphate in an amount of 1 part by weight or more with respect to 100 parts by weight of the alkali silicate, it is ensured that the rate of formation of the solidified product is reduced and the inorganic polymer having predetermined performance cannot be formed. In addition, by mixing silicon phosphate in an amount of not more than 40 parts by weight, it is possible to reliably prevent the fluidity and pot life required for the construction work from becoming difficult to obtain and impairing the practicality of the inorganic polymer. it can.
Further, by mixing 10 to 50 parts by weight of aluminum oxide hydrate, the alkali component released to the inorganic polymer can be fixed, and the occurrence of whitening and the like can be reliably prevented.

Further, in addition to the above, the barium salt powder to be adopted only needs to have a soluble content of barium ions in an alkaline solution. Or inexpensive barium hydroxide which is produced in large quantities as an industrial raw material. The aluminum oxide hydrate to be adopted at the same time may be, for example, inexpensive aluminum hydroxide powder which is mass-produced as an industrial material. Therefore, since the powdery composition of the present invention can be constituted by selecting and blending easily available and inexpensive general-purpose materials, there is also an effect that inorganic polymer products can be supplied at low cost.

(2) In the above (1), preferably,
In addition to the powdered alkali silicate, the powdered barium salt, the powdered silicon phosphate, and the powdered aluminum oxide hydrate, 1 is selected from the group of powdered sulfates that are hardly soluble in an alkaline solution.
A sulfate compound comprising a species or a combination of two or more species is further homogeneously mixed, and the sulfate compound is based on 100 parts by weight of the powdery alkali silicate.
It is mixed so as to be in the range of 0.1 to 10 parts by weight. The present invention reduces the fluidity and pot life of the paste by coexisting a barium salt having a soluble component in an alkaline solution in the paste and coexisting silicon phosphate having a sustained release of phosphoric acid. However, the hardening of the paste is hindered due to this securing, and it may be difficult to quickly develop various physical properties (hardness, water resistance, heat resistance, etc.) of the solidified product. Therefore, by blending a sparingly soluble sulfate compound in an alkali solution in the powdery composition, the sulfate group in the sulfate compound dissolves in the alkali during the time period after construction, and coexists with barium. It can react to form insoluble barium sulfate and stop the behavior of barium ions. As a result, the action of the barium salt formulated to ensure the fluidity of the paste and the pot life is stopped immediately after the completion of the construction, and the curing reaction speed is rapidly accelerated. Early expression can be promoted.

(3) In the above (1), preferably, in addition to the above-mentioned powdered alkali silicate, powdered barium salt, powdered silicon phosphate and powdered aluminum oxide hydrate,
An alkali borate comprising one or a combination of two or more water-soluble powdery borates is further homogeneously mixed, and the alkali borate is added to 100 parts by weight of the powdery alkali silicate. , 40 parts by weight or less. Strain energy is generated by shrinkage when siloxane polymer is generated from alkali silicate,
The lack of shelter in a regular matrix can cause cracks and cracks in the polymer. Therefore,
By mixing a water-soluble alkali borate, an alkali salt of boric acid, as a buffer zone component, a relief area for this strain energy can be provided, and cracks and cracks can be prevented.

(4) In the above item (1), preferably, in addition to the powdered alkali silicate, the powdered barium salt, the powdered silicon phosphate, and the powdered aluminum oxide hydrate,
An alkali silicofluoride consisting of one or a combination of two or more water-soluble powdery fluorosilicon compounds is further homogeneously mixed, and the alkali silicofluoride is
It is mixed so as to be 10 parts by weight or less based on 100 parts by weight of the alkali metal silicate. This ensures the fluidity and pot life of the paste, controls the curing rate of the inorganic polymer, and improves the physical properties such as the strength and water resistance of the solidified product, while further improving the adhesion to various substrates. be able to.

(5) In the above (1), preferably, in addition to the powdered alkali silicate, the powdered barium salt, the powdered silicon phosphate, and the powdered aluminum oxide hydrate,
A filler composed of one or a combination of two or more selected from pigments, functionalities, activators, fillers and the like is further homogeneously mixed, and the filler is 100% of the above-mentioned powdered alkali silicate. It is mixed so as to be 8000 parts by weight or less with respect to parts by weight.

(6) In the above (1), preferably, in addition to the powdered alkali silicate, the powdered barium salt, the powdered silicon phosphate and the powdered aluminum oxide hydrate,
An additive consisting of one or a combination of two or more selected from a surfactant, an organic compound, a resin, a modifier and the like is further homogeneously mixed, and the filler is the powdered alkali silicate. 0.01 to 20 parts by weight per 100 parts by weight of
It is mixed to be in the range of parts by weight.

(7) In order to achieve the above object, the present invention provides an alkali silicate, a barium salt, a silicon phosphate,
And the powdered four components of aluminum oxide hydrate are homogeneously mixed, and in the powdered one-pack alkali silicate composition filled in a one-pack state, the alkali silicate is:
M represents one of the alkali metal elements of Li, Na, and K;
The number of 1.2 to 3.2 p, the number of 0.5 to 1.5 as q, the soluble powdered alkali silicate in water represented by _{M 2 O · pSiO 2 · qH} 2 O The barium salt is composed of BaO.rSi, where r is a number of 4.0 or less and s is a number of 9.0 or less.
The barium ion represented by O ₂ · sH ₂ O is composed of a powdery barium salt having a soluble component in an alkaline solution alone or in combination of two or more kinds thereof.
Where t is a number of 1.0 to 8.0 and t is a powdery silicon phosphate having a sustained release property of phosphoric acid represented by tSiO ₂ · P ₂ O ₅ alone or in combination of two or more kinds; The aluminum oxide hydrate is composed of reactive powdery aluminum oxide hydrate represented by Al ₂ O ₃ .uH ₂ O, where u is a number from 0.5 to 5.0. Powdered alkali silicate, powdered barium salt, powdered silicon phosphate, and powdered aluminum oxide hydrate are powdered alkali silicate 1
With respect to 00 parts by weight, powdered barium salt, powdered silicon phosphate, and powdered aluminum oxide hydrate were respectively
0.1 to 10 parts by weight, 1 to 40 parts by weight, and 10 to 50 parts by weight
Parts by weight, and 27 to 100 parts by weight based on 100 parts by weight of the alkali silicate composition.
It is used for polymer products by being mixed with water by weight to form a polymer having a polysiloxane bond as a main chain.

(8) In order to achieve the above object, preferably, in the above (1) to (7), the powdery one-pack alkali silicate composition and water are mixed, and There is provided a paste-like alkali silicate-based solidifying material in which the water is mixed in a range of from 27 parts by weight to 47 parts by weight with respect to 100 parts by weight of the powdery one-pack alkali silicate composition. Unlike the hydration-type cement-based solidifying material, such a solidifying material is composed of a polysiloxane-bonded main chain, and is not only non-flammable but also heat-resistant. Effective as a solidifying material.

(9) In order to achieve the above object, preferably, in the above (8), after the paste-like alkali silicate-based solidifying material is poured into a container containing waste,
A method for treating waste, wherein the waste is immobilized in the container by opening the polymer in an atmosphere of 5 to 300 ° C. to form a polymer having a polysiloxane bond as a main chain. Is done.

(10) In order to achieve the above object,
Preferably, in the above (1) to (7), the water is 27 parts by weight based on 100 parts by weight of the powdered one-pack alkali silicate composition and water. The mixture is mixed so as to be in the range of not less than 47 parts by weight to form a paste.
A polymer product which is produced by forming a polymer having a polysiloxane bond as a main chain by opening the polymer product in an atmosphere.

(11) In the above (10), preferably, the polymer having the polysiloxane bond as a main chain is formed alone.

(12) In the above (10), preferably, a polymer having the above-mentioned polysiloxane bond as a main chain is formed on the surface of the substrate to be adhered to cover the surface of the substrate. Perform painting or bonding.

(13) In the above (10), preferably, the paste is integrated with a target shape maintaining material and released into an atmosphere at 5 to 300 ° C., and the polysiloxane bond is used as a main chain. The composite is formed by forming the polymer in a state integrated with the shape maintaining material.

[0044]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Some embodiments according to the present invention will be described below.

(I) Alkali Silicate Composition First, an embodiment of an alkali silicate composition will be described as a first embodiment according to the present invention. The alkali silicate composition according to the present embodiment includes, as essential components, a powdered alkali silicate, a powdered barium salt, a powdered silicon phosphate, and a reactive powdered aluminum oxide hydrate. In the following (1) to (6), the embodiment will be described in detail for each component.

(1-1) Powdered Alkali Silicate The alkali silicate composition according to the present embodiment is prepared by first forming a skeleton component forming a main chain of a polymer comprising siloxane bonds as water represented by the following average composition formula. Powdery alkali silicate soluble in water.

M ₂ O.pSiO ₂ .qH ₂ O where M: any one of Li, Na and K alkali metal elements 1.2 ≦ p ≦ 3.2 0.5 ≦ q ≦ 1.5 As the alkali metal species M of the alkali silicate, sodium Na is preferred because it is easily available and inexpensive. Therefore, sodium silicate powder is preferred. However, depending on the field of use and purpose of use of the inorganic polymer, and the required workability and solidified physical properties, etc., potassium K or lithium Li is used alone as the alkali metal species, or a combination of alkali metals including sodium. A composite powder of alkali silicates can be appropriately selected and used.

At this time, p can be appropriately selected from the above range according to the use and workability required for the inorganic polymer. However, when p is less than 1.2, there is a tendency that the amount of the alkali component is too large to delay the curing speed, develop a whitening phenomenon, or become a solid inorganic polymer having poor water resistance. When p is greater than 3.2,
Good utilization of the silicic acid contained in the formation of the produced polymer cannot be expected, and a solid having high hardness tends not to be obtained. Therefore, in general, it is preferable that p is in the range of 1.2 to 3.2, and it is more preferable that p is in the range of 2.5 to 3.0. Similarly, q can be selected at any time according to the purpose of use, use, and construction conditions of the inorganic polymer. However, when q is larger than 1.5, deliquescent occurs in the powdery alkali silicate, and the preservability of the powdery one-pack product is deteriorated, and the shelf life of the powdery composition of the present embodiment is impaired. Not. On the other hand, when q is smaller than 0.5, the solubility of the powdery alkali silicate in water is impaired, and the alkali silicate cannot be effectively used. Therefore, it is preferable that q is in the range of 0.5 to 1.5.

(1-2) Powdered Barium Salt Next, the alkali silicate composition of the present embodiment is prepared by adding water to the powdery composition and mixing the paste with the fluidity necessary for the work. In order to secure a service life, a powdery barium salt having a soluble component in an alkaline solution is provided as a stabilizing component of the resulting paste. The barium salt may be a barium salt having a soluble content in an alkaline solution among powdered barium salts represented by the following composition formula.

[0050] _{BaO · rSiO 2 · sH 2 O} ... However, "the soluble in an alkaline solution", which is defined here r ≦ 4.0 s ≦ 9.0 was defined earlier, 1 N sodium hydroxide solution And the amount of barium ion (Ba ²⁺ ) dissolved into

Accordingly, when the paste is prepared by adding and mixing water to the powdery composition and applying the paste, the fluidity and the pot life required for the work can be secured. In addition, this can suppress a partial rapid gelation reaction (partial gelation) occurring at a contact portion between the alkali silicate solution and the acidic component as a curing agent. That is, barium ions (B
When a ²⁺ ) coexists in the paste, unlike when alkaline earth metal ions other than the barium element soluble in the alkaline solution coexist in the paste, the fluidity required for the construction work and the availability Time can be secured. This is because barium ion, unlike other alkaline earth metal ions, has a slow reaction rate of silicate formation with alkali silicate, and has a buffering action that can suppress rapid dealkalization reaction. This has the function of suppressing the rate of polymerization at the time of the condensation of the compound to suppress an increase in paste viscosity.

Here, it is preferable that the soluble portion of the powdery barium salt in the alkaline solution is 10% or more.
When barium silicate having a solubility in an alkaline solution of 10% or less is adopted in the present embodiment, it is not expected that the paste of the present embodiment will have sufficient fluidity and pot life required for the work. On the other hand, with a barium salt having a solubility of 90% or more in an alkaline solution, the fluidity and the pot life of the paste of the present embodiment are ensured, but the curing time is prolonged. In addition, when a sulfate compound as a curing accelerator described later is used, a large amount of the compound is required, which undesirably impairs proper production of the inorganic polymer.

In general, barium salts satisfying the above-mentioned soluble contents in an alkaline solution, easily obtainable and inexpensive, include:
Chemical formula Ba (OH) _2.
Barium hydroxide represented by 8H ₂ O is preferred. It is also effective to adopt barium oxide of the formula BaO. However, since the amount of the soluble component in the alkaline solution can be controlled and the adjustment of the fluidity and the pot life of the paste of the present embodiment can be managed, the barium silicate in which barium ion activity is mildly exhibited in the present embodiment Is preferred. As the barium silicate, a mixture of barium hydroxide and reactive silicic acid as raw materials is used at a low temperature (preferably 1%).
(200-200 ° C.) The simple powdered barium silicate having a soluble content of 10% or more in an alkaline solution prepared by the treatment controls the fluidity, the pot life and the curing time of the paste in this embodiment. This is preferable because it can be performed. In this case, the simple powdered barium silicate must have r in the composition formula of not more than 4.0, and if it is more than 4.0, the activity of barium ions cannot be used effectively. Further, the number of s in the composition formula needs to be not more than 9.0, and if it is more than 9.0, the storage stability of the barium salt in the one-pack product according to the present embodiment is not ensured, and thus the You cannot reach the purpose of the form.

These barium powders having a soluble content in the alkaline solution are added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the powdery alkali silicate as a skeleton component. Is preferred. If the amount is less than 0.1 part by weight, it is difficult to secure the fluidity of the resulting paste for the time required for the working life. On the other hand, if the amount is more than 10 parts by weight, the working pot life is sufficient, but the curing speed of the solidified product is extremely slow, and the practicality of commercializing the inorganic polymer tends to be impaired.

(1-3) Powdered Silicon Phosphate The alkali silicate composition according to the present embodiment further comprises, as a curing agent component, barium ions which ensure stable shelf life in a one-pack package and coexist in the paste. And powdered silicon phosphate having a sustained release of phosphoric acid in the paste to play a role in the joint work with aluminum hydroxide. The silicon phosphate may be any powdered silicon phosphate having a sustained release of phosphoric acid represented by the following composition formula.

TSiO ₂ · P ₂ O _5, where 1.0 ≦ t ≦ 8.0 The “sustained release of phosphoric acid content” defined here means that 5 minutes of the sample solution defined above has elapsed. Of the initial phosphoric acid is 200 or less, and the average hydrolysis rate constant α is in the range of 0.2 or more.

That is, since the powdery composition according to the present embodiment contains barium ions described in the above (1-2), the acidic component of the curing agent to be blended follows the behavior of barium ions shown in the paste. When the acidic component of the curing agent reacts with the alkali silicate before the behavior of the barium ion starts, a homogeneous solidified product cannot be expected. Therefore, by adopting a powdery form of silicon phosphate having a sustained release property of phosphoric acid that gradually releases protons in an alkaline solution as a curing agent, partial condensation of silicate is suppressed, and the condensation reaction is performed. Is slowed down. As a result, a polymer consisting of homogeneous siloxane bonds occurs without generating a heterogeneous silicic acid gel, and the solidified product is induced into a polymer having a higher molecular weight. The strength shifts, and the formation of the inorganic polymer is effectively achieved.

The silicon phosphate is desirably a stable compound having a sustained release of phosphoric acid in the paste and not easily hydrolyzed in an alkaline solution. Therefore, the adopted silicon phosphate has t in the composition formula from the viewpoint of controlling the sustained release of phosphoric acid well.
Needs to be in the range of 1.0 to 8.0, and is preferably fired in a temperature range of 500 to 1200 ° C. When t is smaller than 1.0 and calcined at 700 ° C. or lower, it tends to show deliquescence and lack stability as silicon phosphate. Also, t is greater than 8.0,
When it is baked at 1200 ° C. or more, the content of phosphoric acid decreases, and the function as an acidic component curing agent becomes poor.

The powdered silicon phosphate is used in order to more reliably withstand direct contact with the alkali component in powder form and to ensure stability during storage and sustained release of phosphoric acid. It is more preferable to pre-treat the surface with a coating agent known in the art. As the coating agent in this case, an organic fatty acid (such as stearic acid) or a fatty acid salt (such as calcium stearate or barium stearate) soluble in an aqueous alkaline solution, and a coupling agent (organosiloxane monomer or polymer silane, titanium cup, etc.) Ring agent) by a predetermined method.
It is preferable that the coating is performed in the range of 01 to 6%.

The hardening agent component powdery silicon phosphate having a sustained release property of phosphoric acid is compounded in an amount of 1 to 40 parts by weight based on 100 parts by weight of the powdered alkali silicate as the skeleton component. Is preferably performed. If the amount is less than 1 part by weight, the rate of formation of the resulting solid is low, and the formation of an inorganic polymer having the desired performance of the present embodiment cannot be expected. On the other hand, if the amount is more than 40 parts by weight, it is difficult to obtain the fluidity and pot life required for the construction work, and the practicality of the inorganic polymer tends to be impaired.

(1-4) Aluminum oxide hydrate The alkali silicate composition in the present embodiment is:
Reactive aluminum oxide hydrate is provided as a component for immobilizing an alkali component in order to prevent a whitening phenomenon and a deterioration in water resistance that may occur when an inorganic polymer is generated from an alkali silicate. The aluminum oxide hydrate may be any aluminum oxide hydrate represented by the following composition formula.

Al ₂ O ₃ .uH ₂ O where 0.5 ≦ u ≦ 5.0 By this, the alkali component which is separated and separated by the condensation of silanol groups and is in an unstable state is immobilized. It can suppress the whitening phenomenon that occurs on the surface of the solidified product of the inorganic polymer formed from the powdery composition, and can impart excellent water resistance to the formed inorganic polymer product. That is, the paste prepared from the powdery composition of the present embodiment has a role of silicon phosphate as the above-mentioned acidic component,
In combination with the above-mentioned role of barium ion which effectively derives the role of the acidic component, the role of aluminum hydroxide is given a synergistic effect, and the chemical phenomena occurring here are exerted in combination. By the synergistic effect of these three roles, a homogeneous and high-hardness solidified inorganic polymer is effectively produced and applied. As a result, since the aluminum hydroxide is mixed with the powdery composition to prepare the paste, an alkali component which is separated and unstable in an unstable state by the formation of a polysiloxane bond is present in the coexisting silica and water. Reacts with aluminum oxide to produce sodalite, a zeolite precursor. In this way, since the alkali component which is separated and separated can be fixed, the whitening phenomenon can be suppressed, and various physical properties such as water resistance can be effectively exhibited.

At this time, u in the composition formula needs to be 0.5 or more. When u is less than 0.5, the reactivity with alkali silicate or the like is poor, and the role as an alkali fixing component is low. Cannot be fully demonstrated. Also, u needs to be 5.0 or less, and when it is larger than 5.0, it becomes difficult to keep the aluminum oxide hydrate in a fluffy powder state. It is not preferable because it may cause troubles.

As the aluminum oxide hydrate, for example, reactive powdery aluminum hydroxide having a particle size of 200 μm or less and u = 3, which is generally commercially available as an industrial product because it is easily available and inexpensive, is used. It is suitable.

These reactive powdery aluminum oxide hydrates are used from the viewpoint of fixing alkali components released to the inorganic polymer and preventing troubles such as whitening.
It is necessary to mix only 10 to 50 parts by weight with respect to 100 parts by weight of the powdery alkali silicate of the skeletal component.
It is more preferable to mix in a range of parts by weight.

The reactive powdery aluminum oxide hydrate also functions to prevent the one-pack product from reacting during storage and to maintain stable shelf life. That is, in the present embodiment, the complicated in-situ mixing step is eliminated by previously filling the powdery four components of alkali silicate, barium salt, aluminum oxide hydrate, and silicon phosphate in a one-pack state. is there. Here, as described above, these four powdery components exhibiting a synergistic effect (a powdery alkali silicate soluble in water, a barium salt soluble in an alkaline solution, a phosphoric acid having a sustained release property of phosphoric acid) Silicon and reactive aluminum oxide hydrate) are used to form a powdery one-packed composition, in which an acidic component (in the present embodiment, silicon phosphate) coexists in an alkali component in a one-pack. Therefore, this one-pack product must ensure stable shelf life without reacting during storage. Here, when this aluminum hydroxide is added to the powdery composition, it functions to prevent direct contact between the acidic component and the alkaline component. While the sustained release of the phosphoric acid content of the silicon oxide is maintained, the workability of the paste prepared by adding water is also ensured, and the storage and management can be stably performed.

The alkali silicate composition according to the present embodiment comprises, in addition to the above four essential components,
Other components may be added as appropriate. Hereinafter, these other components will be described in order from (2) to (6).

(2) Sulfate Compound The alkali silicate composition according to the present embodiment can be used to complete the solidified product immediately after the paste having sufficient fluidity and working life is applied, if necessary. In order to develop the hardness at an early stage, a sulfate compound which is defined as "poorly soluble in an alkaline solution" and has a sulfate group elution of 50% or less is mixed as a hardening accelerator component. In this way, by blending the sparingly soluble sulfate compound in the alkaline solution, the sulfate group in the sulfate compound dissolves in the alkali during the time period after construction, reacts with the coexisting barium, and becomes insoluble. Barium sulfate can be formed and the behavior of barium ions can be stopped. As a result, the action of the barium salt formulated to ensure the fluidity of the paste and the pot life is stopped immediately after the completion of the construction, and the curing reaction speed is rapidly accelerated. Early expression can be promoted. The sulfate compound to be blended must be sparingly soluble in an alkaline solution since it is necessary to ensure a usable time due to fluidity in the initial stage of adding water (for example, within 2 hours). Is important. Therefore, in general, calcium sulfate (anhydrite) which is dehydrated in a baking step or the like and is hardly soluble in an alkaline solution is preferred because it is easily available and inexpensive. However, examples of the sulfate compound that is hardly soluble in other alkaline solutions include magnesium sulfate, sodium sulfate, potassium sulfate, zinc sulfate, and aluminum sulfate that are hardly soluble in a specific treatment. Also,
It is preferable that the mixing ratio of these sulfate compounds is homogeneously mixed so as to be in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the powdery alkali silicate of the present embodiment.
When the amount is less than 0.1 part by weight, the ability to fix coexisting barium ions is inferior, and when the amount is more than 10 parts by weight, the hydration reaction caused by the sulfate itself tends to adversely affect the solidified product. Is not preferred.

(3) Alkali Borate The alkali silicate composition according to the present embodiment may have a buffer band capable of coping with energy distortion generated in a siloxane bond formed from alkali silicate as a skeleton component, if necessary. For this purpose, a water-soluble alkali metal borate may be provided as a buffer zone component.

That is, the inorganic polymer in the present embodiment is basically composed of tetravalent silicon (Si) and divalent oxygen (O).
A siloxane-bonded polymer, wherein the resulting matrix is regularly structured. However, siloxane polymer formation from alkali silicates
Shrinkage occurs due to dehydration, and strain energy generated by the shrinkage tends to accumulate in the solidified body. on the other hand,
Since the matrix is regular, there is no place for the strain energy generated here to escape, and cracks or cracks may occur in the polymer in order to eliminate the strain energy, which is a cause of product trouble. In order to prevent this, a field that can absorb the strain energy generated in the polymer, a so-called “play field” is required, and it is effective to form the field as a buffer band. This idea is similar to the behavior of borosilicate glass in glass. Also in the inorganic polymer having a room temperature-solidified siloxane bond of the present embodiment, it is applied that a compound containing a trivalent boron element having a different valence is effective as a buffer zone component. That is, in the present embodiment,
Since alkali silicate is used as the skeletal component, water-soluble alkali borate, which is an alkali salt of boric acid, is selected and adopted as the buffer zone component. At this time, the water-soluble alkali metal borate is blended in an amount of 20 parts by weight or less, preferably 10 parts by weight or less, as needed, with respect to 100 parts by weight of the skeleton component of the alkali metal silicate. It is preferable to form a buffer band for eliminating strain energy in the inorganic polymer composed of siloxane bonds. As the water-soluble alkali borate to be selected, the alkali element is preferably potassium or sodium. For example, potassium borate or sodium borate can be selected. Further, since these alkali borates are in a powder form, it is preferable to select them from anhydrous salts, trihydrates, pentahydrates, heptahydrates, and hydrates.

(4) Alkali Fluorosilicate In addition, the alkali silicate composition according to the present embodiment secures the fluidity and pot life of the paste, controls the curing speed of the inorganic polymer, and improves the strength and strength of the solidified product. In order to improve physical properties such as water resistance, and also to improve adhesion to various substrates, a water-soluble alkali metal fluorosilicate may be selected and blended as necessary.

Examples of the water-soluble alkali metal fluorosilicate include powdery potassium fluorosilicate, sodium fluorosilicate, calcium fluorosilicate, magnesium fluorosilicate, and barium fluorosilicate which are generally commercially available as industrial raw materials. It can be selected and blended. These powdery alkali silicofluorides may be previously surface-treated with a coating agent known in the art in order to ensure stability during storage and a sustained release of phosphoric acid. Further, these water-soluble alkali metal silicates are blended in an amount of 10 parts by weight or less, preferably 8 parts by weight or less, as needed, with respect to 100 parts by weight of the skeleton component of the powdery alkali silicate. This is preferable in that the workability of the paste of the present embodiment and the curing speed of the inorganic polymer are controlled and the physical properties such as the strength and the water resistance of the inorganic polymer composed of siloxane bonds are improved.

(5) Filler The alkali silicate composition according to the present embodiment is in the form of a powder having a size of 200 μm or less depending on the physical properties, functionality, workability, purpose of use, etc. required for the produced inorganic polymer. Powder fillers such as pigments, functional agents, colorants, activators, fillers, and volume materials can be selectively compounded. These fillers may be appropriately blended within a range that does not impair the workability of the paste or various physical properties of the inorganic polymer. Specifically, the filler is added to 800 parts by weight of the powdery alkali silicate.
It can be added alone or in combination of two or more kinds in an amount ratio of not more than parts by weight after confirmation by preliminary experiments.

Examples of the filler adopted here are shown below in order. However, it goes without saying that the filler of the present embodiment is not limited to the filler exemplified here.

(A) Pigment As the pigment, various colored inorganic pigments, organic pigments and extender pigments generally known in the art can be suitably used for the powdery one-pack composition of the present embodiment. First, examples of inorganic pigments include inorganic colored pigments such as carbon black, zinc white, titanium dioxide, iron oxide, iron hydroxide, iron oxide, chrome oxide, graphite, ultramarine, various metal oxides, and so-called calcined pigments. The coloring of the inorganic polymer products of the present embodiment can be made possible as an inorganic substance. Further, as the organic pigment, for example, insoluble azo pigments generally used in red or yellow, soluble azo pigments, condensed polycyclic pigments, quinacridone pigments, isoindolinone pigments, and blue or green Cyanine blue, cyanine green, and the like that are used can be cited, but it is necessary to check the alkali resistance in advance and apply an appropriate coating if necessary before adopting. As the extender, metals, alloys, non-oxides, various colored powders composed of oxides and the like, furthermore various silicate-based powders, talc, white carbon, aluminum silicate, alumina, silica, Examples include fused alumina, zinc oxide, magnetic iron oxide, boron nitride, silicon carbide, and various clay powders. Among these extender pigments, silica, zinc white, montmorillonite, and the like, which are easily reactive to alkali metals, are effective in fixing the alkali component in combination with the alkali fixing component blended in the present embodiment,
It is preferable that the composition is actively adopted as the composition compound of the present embodiment. Further, among these extender pigments, metals such as silicon, aluminum, and zinc react with alkali of alkali silicate and generate hydrogen gas, so that caution is required when a dense inorganic polymer is expected to be produced. However, when the resulting inorganic polymer is expected to have a foam shape, it is effective to mix these metals.

(B) Functional Agent (Functional Material) As the functional material, generally known rust inhibitors, antioxidants, anti-slip agents, blocking materials, flame retardants, ultraviolet rays
Infrared absorbers, anti-fog agents, repellents, antibacterial agents, luminescent pigments,
Luminous body, photocatalyst, heat conductor, conductor, dielectric, insulating pigment, heating element, expanded body, elastic body, antistatic agent, piezoelectric element,
It can be appropriately obtained and selected from materials such as active materials and drugs. In particular, even when organic polymers are generally used as a photocatalyst carrier in the prior art, these organic polymers are not successfully compounded because they are destroyed and decomposed by the photocatalyst. However, since the inorganic polymer having a siloxane bond as a main component according to the present embodiment has resistance to destruction / decomposition by an active substance such as a photocatalyst, it can be suitably blended and effective.

(C) Colorant As the colorant, the above-mentioned inorganic pigments and organic pigments can also be used. An inorganic polymer having a desired hue can be obtained by selecting one or a combination of two or more.

(D) Activator As the activator, a powdery product such as a boric acid-containing compound, a lead-containing compound, a chromic acid-containing compound, and a phosphoric acid-containing compound can be selected. By premixing the activator in the powdery composition of the present embodiment, for example, when metals such as iron are adopted for the adhesive polymer product selected as the coating substrate, coating and coating with the paste are performed. It is suitable as a material for attachment, adhesion, etc., because it can improve the adhesion to the substrate and can be expected to have anticorrosion properties. Examples of the boric acid-containing compound at this time include known hydrous zinc borate as a flame retardant, and examples of the lead-containing compound include a lead compound for a glaze and lead silicate as a rust inhibitor. Examples of the chromic acid-containing compound include lead chromate and strontium chromate which are yellow pigments and are rust preventives. Specific examples of the phosphoric acid-containing compound adopted in the present embodiment include calcium phosphate [Ca ₃ (PO ₄ ) ₂ , Ca ₂ P ₂ O ₇ ], magnesium phosphate [Mg ₃ (PO ₄ ), Mg ₂ P ₂ O ₇ ], barium phosphate [Ba ₃ (PO ₄ ) ₂ , Ba ₂ P ₂ O ₇ ], zinc phosphate [Zn ₃ (PO ₄ ) ₃ ], aluminum phosphate [AlP
O ₄ , Al (H ₂ PO ₄ ) ₃ ], silicon phosphate [SiP
₂ O ₇ ], titanium phosphate [TiO ₂ · P ₂ O ₅ ], tin phosphate [Sn (H ₂ PO ₄ ) ₂ ] and the like.

(E) Filler and Volume Material The filler and the volume material may be flakes, pastes, powders of metals and alloys such as stainless steel, lead and iron.
Glass powder, ceramic powder, diamond powder, silicon oxide powder (silica sand, silica, silica, silica fume,
Fused silica), magnesium powder, calcium carbonate, zircon sand, various clays (purified products such as bentonite, smectite, gailome, kibushi clay), calcined clay (baked products such as bauxite, montmorillonite, kaolin), gypsum, aluminum fluoride , Calcium silicate, magnesium silicate, barium carbonate, aluminum silicate, various mica, asbestos, glaze of various composition contents, mica, fly ash, processed and processed products of various industrial wastes, incineration ash of household waste, etc. Powder having a particle size of 200 microns or less; furthermore, inorganic fibers such as glass fiber, rock wool, natural mineral fiber, and carbon fiber; and various particle size distributions and shapes of silica, silica sand, wax stone, feldspar, chamotte, mullite, alumina, Dolomite, Magnesia, Zirconia,
It can be appropriately selected from powders having a particle size of 200 μm or less, such as heat-resistant refractories such as calcium, zirconia, carbon, graphite, carbide, and nitride.

In many cases, the above-described filler generally has water, OH groups, and the like. It is generally preferred to use. In addition, in consideration of workability and purpose of use and storage stability and curing conditions after construction, etc., its particle size configuration, shape, pore volume, specific surface area,
Water absorption, oil absorption and other properties are thoroughly investigated, pulverized, classified,
It is effective to adopt a pretreatment such as mixing, sintering and purification, or to prepare a powder which has been surface-treated in advance with various coupling agents, surfactants, and the like, and then adopt it. Also, these fillers
It is preferable that the powdery composition is used alone or in combination in an amount of 800 parts by weight or less in the present powdery composition according to the purpose and the like.

(6) Additives The alkali silicate composition according to the present embodiment may be used, if necessary, as a modifying component of the formed inorganic polymer, such as gloss, leveling, dispersibility, impregnation, An additive capable of improving various properties such as defoaming property, fluidity, viscosity, coating property, adhesion, workability, and storage stability and physical properties can be added. These additives may be appropriately blended within a range that does not impair the performance, physical properties, workability, and the like of the powdery composition. Specifically, powdered alkali silicate 10
The additive may be added alone or in combination of two or more kinds thereof after confirmation by preliminary experiments so that the amount of the additive is 0.01 to 20 parts by weight with respect to 0 parts by weight.

The additives at this time are not particularly limited, but various surfactants, various organic compounds, resins, modifiers, etc., which are well known and widely used in the art and have been effective. Can be mentioned. It is preferable to select and use these additives as appropriate after confirming the quality and quantity through preliminary experiments.

The means for mixing and dispersing each of the powdery components described in the above (1) to (6) naturally differs depending on the content of the powdery components, the mixing ratio, the purpose of use, and the like. Appropriate among powder mixers and dispersers commonly used in the industry, cement industry, concrete industry, food industry, chemical manufacturing industry, etc., for example, stirrers, various mixers, various mixing / dispersion mills, etc. A method and means for selectively obtaining a homogeneous powder mixed state may be employed. In addition, when mixing and dispersing, in consideration of the season of mixing and dispersing and construction work, weather and environmental conditions, etc., each component material before mixing and dispersing is subjected to processing adjustment such as cooling or heating before mixing. It is also effective. Further, depending on the required state of the homogeneously mixed powdery composition, it is also effective to divide the pigment and a small amount of additives into multiple stages in order to increase the efficiency of the mixing and dispersion, particularly when mixing and dispersing.

(II) Paste-like alkali silicate-based solidifying agent The water-based one-pack alkali silicate composition of the first embodiment described in the above (I) is mixed with water to form a paste-like silicate. An alkali-based solidifying material is prepared and can be applied to various industrial waste treatments, inorganic polymer products, adhesive polymer products, composite products, and the like, as described below. Therefore, an embodiment of a paste-like alkali silicate-based solidifying material will be described as a second embodiment according to the present invention.

First, the paste was prepared in the range of 27 to 47 parts by weight of water with respect to 100 parts by weight of the powdery composition of the first embodiment (water mixing ratio by weight: 0.27 to 0.47). Add and mix. When the amount of water added is less than 27 parts by weight, the paste cannot maintain fluidity that allows workability, and when the amount of water added is more than 47 parts by weight, the paste is in a shrunken state, and the alkali silicate-based paste is formed. The purpose as a solidifying material cannot be achieved. At this time, as described above, the homogeneous mixing means may be a powder-liquid mixer or disperser known in the civil engineering industry, cement industry, concrete industry, paint / adhesion industry, food industry, chemical manufacturing industry, etc. Machines, for example, stirrer, various mixing and dispersing machines, mills, mortar mixer, homogenizer, roll, paint shaker, SG mill and the like may be appropriately selected from, powder-liquid homogeneous mixture paste, A method and means obtained in the form of mayonnaise, milk, paint, mortar, wax, etc. may be used.

Next, the paste homogeneously mixed and dispersed as described above is mixed with a method known per se, for example,
Spraying method, airless spray method, air spray method, brush coating, roller coating, iron coating, dipping method, lifting method, nozzle method, winding method, flow coating, pouring, plating method, patching method, various molding / processing methods, etc. By using the automatic or manual construction method generally adopted in this industry, it is applied to various treatments according to the purpose and application to finish the product base or processed product. At this time, the paste is opened to an atmosphere of 5 to 300 ° C., preferably room temperature to 250 ° C., and is exposed to drying and dehydration conditions to allow the curing reaction to proceed, thereby forming a solid state having a siloxane bond as a main chain. By forming the above inorganic polymer, various products exhibiting the functions and features of the inorganic polymer can be manufactured. As for the drying and dehydrating conditions at this time, a relatively low temperature of 5 ° C. is sufficient, but it is preferably room temperature or 300 ° C.
If the temperature is in the range of, preferably, 250 ° C. or less, it can be given under heating, under pressure, or under degassing conditions. If desired, the curing reaction can be started under reduced pressure in an atmosphere of an inert gas such as nitrogen gas or carbon dioxide gas.

The paste-like alkali silicate-based solidification material of the present embodiment thus formed is different from the hydrated cement-based solidification material in that it is composed of a polysiloxane-bonded main chain. Since it has heat resistance as well as heat resistance, it is effective as various non-combustible and heat resistant solidifying materials. It is also useful as a casting solidifying material for various molding dies and as a casting repair material for damaged parts such as refractory furnace materials, chimneys, boilers, and structures.

(III) Industrial Waste Treatment Method The paste-like alkali silicate-based solidifying material according to the second embodiment has the above-mentioned characteristics, and can be used for various industrial wastes (industrial waste, various incinerated ash, Level radioactive waste, fly ash, blast furnace slag, etc.)
It is effective as a solidifying agent for forming into granules such as granules. Therefore, next, an embodiment of a method for treating industrial waste in which various industrial wastes are solidified using the paste-like alkali silicate-based solidifying material will be described as a third embodiment.

In the solidification treatment according to the present embodiment, first, industrial waste of a specific shape (for example, low-level radioactive waste, fly ash, these primary treatment products, etc.) is stored in a predetermined container. Thereafter, the paste-like alkali silicate-based solidifying material of the second embodiment is poured into the container. Then, the polymer is opened in an atmosphere of 5 to 300 ° C., thereby forming a polymer having a polysiloxane bond as a main chain according to the principle described above. Thereby, the industrial waste can be fixed in the container.

Further, in particular, the paste of the second embodiment is
Because it has better fluidity than milk such as Portland cement, it is useful as a solidifying material for injection into the molded waste of garbage or special waste, such as radioactive waste from nuclear power plants It is.

(IV) Polymer product Further, each of the paste-like alkali silicate-based solidifying materials composed of the powdery composition of the second embodiment and having different amounts of water added thereto is:
It is appropriate to produce a construction product at the target object or construction site shown below, and is not particularly limited. Examples of the case where the invention is applied to a polymer product include the following.

(1) Inorganic polymer product As the inorganic polymer product, the prepared paste is
It is maintained in a lump, film, sheet, film, thin plate, fiber, string, square bar, bar, ball, powder, sand, foam, specific shape, etc., which have a predetermined shape by itself. Examples of products that form a molded solid and are provided for various uses can be given. That is, when these are produced, the powdered one-pack alkali silicate composition and water according to the first embodiment are mixed with water in an amount of 27 parts per 100 parts by weight of the powdered one-pack alkali silicate composition. A paste is formed by mixing to be in a range of not less than 47 parts by weight and not more than 47 parts by weight, and the paste is opened to an atmosphere of 5 to 300 ° C. to form a polymer having a polysiloxane bond as a main chain by itself. It should be done.

(2) Adhesive polymer product As an adhesive polymer product, the prepared paste is
A product that forms an inorganic polymer while adhering to the surface or inner surface of various base materials and performs its intended function as an adherent. Specifically, paints, base materials, sealers, coating materials, protective materials , Adhesive, sealing material, gasket, jointing agent, putty, hardening material, coking material, potting material,
Products such as cementing materials, anchor materials, binders, and cured products can be given. Further, the adhesive polymer product of the present embodiment is required for anchoring materials for structures and devices such as tanks, towers, buildings, etc., as well as for embedding and plastic patching materials and foaming embedding materials in the above-described fields. It can also be usefully used as various kinds of fixed cementing material at a given location. In particular, if the inorganic polymer according to the present embodiment is used, metal products such as iron, concrete products such as cement, ceramic / clay products,
By applying such as coating on the surface of various building materials such as enamel products, natural products such as wood, bamboo, paper, and synthetic processed products, etc., it is excellent in various effective large and small durability, It is possible to manufacture building materials and various structures having excellent stain resistance. Furthermore, the inorganic polymer according to the present embodiment can be usefully used as a material for repair, ground treatment, pre-treatment, filling material, finishing material, laying material, slip resistant material, and the like in each of the above-described locations. Furthermore, various ceramic materials, fibrous materials, abrasives, abrasion-resistant materials, various inorganic compounds, etc. are blended with this inorganic polymer and can be applied to materials that meet various needs such as water resistance, heat resistance, fire resistance, and acid resistance. , As solidification materials, processed materials, adhesives, binders, jointing materials, etc. of various materials similar to the above, chemical factories, food factories, plating factories, hot springs, cafeterias, kitchens such as hotels, flue, drains, Applicable to building materials.

When the adhesive polymer product as described above is produced, the powdered one-pack alkali silicate composition and water according to the first embodiment are mixed with the powdered one-pack alkali silicate composition. 100 parts by weight of water is mixed in a range of 27 parts by weight or more and 47 parts by weight or less to form a paste, and this paste is opened in an atmosphere of 5 to 300 ° C. By forming a polymer having a polysiloxane bond as a main chain on the surface, the surface of the substrate may be coated, painted, or bonded.

(3) Composite Product As a composite product, the prepared paste is made of various metals, concrete, ceramics, cement, rocks,
Shape maintaining material composed of clay, gypsum, slug, sand grains, aggregate, extender, glass, brick, enamel, wood / bamboo, paper, fiber / cloth, plastic, asphalt, reclaimed waste, etc. (Eg, lump, granule, powder,
Net, net, woven / non-woven fabric, plate, film, sheet, container, package, honeycomb, pipe, structure, etc.) and form an inorganic polymer in an integrated state for various applications. It is a composite product, specifically, various parts, various materials, structures, various devices, composite glass, film, sheets, floors, walls, building materials, blocks, flue, chimneys, furnaces and furnaces, furniture, horticulture , Soundproofing material, sound absorbing material, heat insulator,
Products such as heat insulating materials, containers, tools, devices / equipment, honeycombs, various molded bodies, and specific structures can be given.

When the above-described composite product is produced, the powdered one-pack alkali silicate composition and water according to the first embodiment are mixed with 100 wt. Of the powdered one-pack alkali silicate composition. More than 27 parts by weight of water per part
A paste having a polysiloxane bond as a main chain is formed by mixing the paste so as to be in a range of not more than part by weight to form a paste, integrating the paste with a target shape maintaining material, and releasing the paste into an atmosphere at 5 to 300 ° C. May be formed integrally with the shape maintaining material to form a composite.

As described above in (I) to (IV),
Each product manufactured according to each embodiment of the present invention is a heat-resistant, non-flammable, flame-retardant material that is resistant to heat and fire, a durable material that exhibits strong weather resistance to various light exposures, taking advantage of the characteristics of the polysiloxane bond, As a beautiful material that does not lose pollution, acid rain and chemicals, a resistant material that overcomes mold, and a material that is excellent in workability that enables normal temperature or baking work, it can be used in a wide range of application fields, such as social and lifestyle related, manufacturing and industrial industries, It can be used in the construction / civil engineering industry, service industry, etc., is environmentally friendly and is effective as a product useful for urban disaster prevention and crisis management.

[0098]

EXAMPLES Specific examples of the present invention will be described below.

(I) First Example First, as a first example of the present invention, examples of a powdery one-pack alkali silicate composition will be described with reference to Tables 1 to 7. However, in this example, each component of the powdery one-pack alkali silicate composition is indicated using the following abbreviations. -Skeleton component composed of water-soluble alkali metal silicate (A): A component-Immobilized component of alkaline component composed of aluminum oxide hydrate (B): B component-Soluble barium salt (C) Fluid stabilizing component of product paste consisting of: C component-Phosphoric acid compound having sustained release of phosphoric acid (D) Curing agent component consisting of D component-Water-soluble alkali borate (E) Buffer zone component: E component ・ Reaction assistant component consisting of alkali silicofluoride (F): F component ・ Functional component consisting of filler (G) capable of imparting various functions: G component ・ Workability, physical properties and performance Modifier composed of an additive (H) for improving the content: H component-Hardly soluble sulfate (J) for immobilizing Ba ²⁺ Curing accelerator component composed of J: J component-Prepared with A component and E component Modified alkali silicate (K): K component Raw materials employed in the examples are displayed in the following abbreviated. SS: sodium silicate PS: potassium silicate LS: lithium silicate SB: sodium borate PB: potassium borate HA: aluminum hydroxide HB: barium hydroxide SB: barium oxide EB: simple barium silicate SP: phosphoric acid Silicon ZP: Zinc phosphate SF: Alkali fluorosilicate CS: Calcium silicate PS: Orcanosiloxane (SR2402) SN: Antifoaming agent In this specification, “%” and “parts” are “weight” unless otherwise specified. ".

The components shown in Table 1 below were adopted as the basic components (the above components A to K) of the powdery one-pack alkali silicate composition of this example.

[0101]

[Table 1]

In Table 1, "Formulation Examples 1 to 6" indicates that the components were prepared according to typical composition examples (described later) of each component. Details of the adjustment method in these mixing examples will be sequentially described below.

(1) Formulation Example 1 This formula example is a powdery alkali silicate (A) used as a skeletal component of the present example, or this alkali silicate (A) and a water-soluble alkali borate salt. (E) is a typical example of a method for preparing the modified alkali silicate (K). That is, as the component A of the powdered alkali silicate, No. 2 powdered sodium silicate [representative composition (%) SiO ₂
55.5, Na ₂ O 23.0, SiO ₂ / Na ₂ O molar ratio 2.5; abbreviation 2SS], potassium silicate powder [typical composition (%) SiO ₂ 40.6, K ₂ O 20 0.0, Si
O ₂ / K ₂ O molar ratio 3.0; abbreviation 3PS] and lithium metasilicate powder [Li ₂ O · SiO ₂ ; abbreviation LS] are used. The water-soluble alkali borate E component used for the denaturation includes sodium borate powder [Na ₂ B ₄ O _7.
10H ₂ O; chose abbreviations PB]; abbreviations SB] and potassium borate powdery _{[K 2 B 4 O 7 ·} 8H 2 O.
Table 2 shows the contents and ratios of these raw materials and their sample numbers (the alkali silicate (A) sample number was also unified with the K series number).

[0104]

[Table 2]

(2) Formulation Example 2 This formulation example is a typical example of a method for preparing a simple barium silicate (EB) which is an example of a barium salt (C) as a stabilizing component used in the present example. It is an example.

That is, an acid-treated acid-treated product silphonite [typical composition (%) SiO ₂ 93.0;
Al ₂ O ₃ 1.5, Fe ₂ O ₃ 0.3, MgO 0.
3, CaO 0.2, Ig. Loss 3.7], and commercially available barium hydroxide for industrial use as a barium raw material, and both were homogeneously mixed so that the molar ratio of SiO ₂ / BaO becomes 1.0, and then 200 ° C. × 60 minutes After drying, the dried product is pulverized using a hammer impact type pulverizer so as to have a 200 mesh pass. The simple barium silicate prepared here was identified to have barium silicate as a main component by X-ray diffraction. This simple barium silicate is designated as sample number EB-1.

The soluble matter (Ba ²⁺ ) of the simple barium silicate in the alkaline solution in this formulation was measured by the following method, and the result was 800 mg / l. Measuring method of “soluble matter in alkaline solution”: 10 g of a powdery barium salt sample was added to 100 m of a 1 N caustic soda solution at 25 ° C.
After stirring and dispersing the sample solution in the sample solution for 10 minutes, barium ions in the solution collected by filtering the sample solution were quantitatively analyzed, and eluted in a 1 N caustic soda solution with the barium element amount in the collected sample as a standard (100). It was calculated based on the amount of barium ion (Ba ²⁺ ) (mg / l).

In addition, the soluble components of barium hydroxide [HB: Ba (OH) ₂ ] and barium oxide [SB: BaO], which were adopted in this formulation example, in the alkaline solution were measured in the same manner. Is 7300 mg / l,
SB was 15000 mg / l.

(3) Formulation Example 3 This Formulation Example is a typical example of a method for preparing silicon phosphate which is one of the phosphoric acid compounds (D) as a curing agent component used in this Example. .

That is, an acid-treated acid-treated product silphonite [typical composition (%) SiO ₂ 93.0;
Al ₂ O ₃ 1.5, Fe ₂ O ₃ 0.3, MgO 0.
3, CaO 0.2, Ig. Loss 3.7] was selected and the phosphoric acid raw material was a commercially available industrial phosphoric acid solution [H ₃ PO ₄
85.0%], and the two have a molar ratio of SiO ₂ / P ₂ O ₅
And 2.0 to 3.0 (however, a phosphoric acid which forms a normal salt with a basic component such as Al ₂ O _{3 in} the acid-treated clay is added separately). Then, 17
After drying at 0 to 200 ° C for 60 minutes, baking is performed at 800 to 1100 ° C for 30 minutes using a rotary kiln. After coarsely pulverizing each of the fired products, a 200 hammer impact type pulverizer is used.
The sample was pulverized so as to pass through a mesh sieve.
Each of the silicon phosphates prepared here was converted to S by X-ray diffraction.
It was identified that the main component was silicon phosphate of iP ₂ O ₇ . Further, the sustained release properties of each phosphoric acid (constants α and β in the above formula (*)) having different molar ratios and firing temperatures were measured, and the results are also shown in Table 3. In addition, powdered phosphoric acid compounds (DA) shown in Table 3 below were selected as curing aid components other than silicon phosphate employed in this example. For these powdery phosphoric acid compounds (DS), the sustained release of phosphoric acid (constants α and β) was measured, and the results are also shown in Table 3.

[0111]

[Table 3]

The sustained release of phosphoric acid in the phosphoric acid compound sample containing silicon phosphate in this formulation was measured by the following method. Measuring method of “slow release of phosphoric acid”: 1 g of a powdery sample was subjected to 25 ° C.
4 provisions caustic soda solution 100ml sample solution was allowed to stir dispersed in, respectively fractionated filtered elapsed time of 5 minutes and after 120 minutes, and quantified phosphoric acid content (P ₂ O ₅₎ in the filtrate obtained here of mg / 100 ml, the elapsed time (minutes) is plotted on the horizontal axis, and the integrated elution amount (m ₂ ) of phosphoric acid (P ₂ O ₅ ) is plotted on the vertical axis.
g / 100 ml), and plotted on a graph to obtain a straight line, and the elution amount β of the initial phosphoric acid content and the average hydrolysis rate constant α in the above-mentioned formula Y = αX + β (*) were calculated.

(4) Formulation Example 4 This Formulation Example shows a typical example when a filler (G), which is a functional component used in this Example, is used as a composite. Table 4 shows the composition (parts by weight).

[0114]

[Table 4]

These G components are selected from known commercially available powder materials (pigments, functional agents, coloring agents, fillers, etc.) or powders of various industrial wastes. The G component adopted in the powdery one-pack alkali silicate composition of the present example is not limited to the materials, industrial wastes, and composites thereof shown in the present formulation example.

(5) Formulation Example 5 This formulation example is a typical example of the sparingly soluble sulfate (J) component that fixes Ba ²⁺ adopted in this example. In this formulation example, a fine powder of calcium sulfate (CaSO ₄ : anhydrous gypsum) [Sample No. J-1] is selected as the J component.

(6) Formulation Example This formulation example is a typical example of the modifying additive (H) H component that improves workability, physical properties, and performance employed in this example. They are shown in Table 5.

[0118]

[Table 5]

After the basic components (components A to K) of the powdery one-pack alkali silicate composition were adopted as described above, the components were blended in the composition (parts by weight) shown in Table 6 below.
Mixing was performed by a dry mixing method with stirring to prepare 28 types of powdery compositions (sample numbers 1-1 to 1-28). At this time, in order to clarify the effect of this example, as a comparative example, 4
Various kinds of powdery compositions (sample numbers 1-29 to 1-32) were prepared.

[0120]

[Table 6]

[0121]

[0122]

To each of the powdery samples prepared as described above, water was added at a water mixing ratio (water / powder weight ratio) shown in Table 7 and stirred and mixed to prepare a fluid paste.

[0124]

[Table 7]

The paste was evaluated by conducting the following physical property evaluation tests. The contents are as follows. This evaluation result is also shown in Table 7.

[Physical Property Evaluation Test Method] Viscosity of fluid paste, ie, powdery sample kept at 30 ° C (powder composition)
The mixture is stirred and mixed at a predetermined water mixing ratio (water / powder weight ratio) using 35 ° C. water, and the fluid paste prepared here is cured in a 52 ° C. constant temperature bath. Paste viscosity was measured using C-type viscosity and expressed in centipoise (CP). In addition, the paste according to the present embodiment is used for workability,
In particular, the paste limit used in the injection solidification method and the like is set so that the paste viscosity after 10 minutes from the preparation of the paste does not exceed 8,000 CP, and the workable working time is 1 hour, during which the paste viscosity is 20,20. A range not exceeding 000 CP was regarded as a pass range as a paste having good workability.
As shown in Table 7, the samples I-1 and I-2 according to the present example were used.
All pastes according to 8 are in the above acceptable range,
It can be seen that the fluidity and pot life necessary for the construction work were secured. When the paste according to the present embodiment is used for solidifying radioactive waste as described below, it is preferable that the viscosity after 60 minutes of preparation of the paste does not exceed 10,000 CP. In addition, when the paste according to the present embodiment is used for laying, bonding, joints, and the like using a trowel or the like, even if the viscosity after 10 minutes of preparation of the paste exceeds 8000 CP, the workability of construction is not impaired.

[0127] 2. Uniaxial compressive strength That is, the paste prepared from the powdery sample is
The mixture was poured into a mold having a size of 90 mm, cured at 25 ° C. for a predetermined time and solidified to obtain a specimen for measuring uniaxial compressive strength. Each specimen was subjected to a uniaxial compressive fracture strength test by a compressive strength tester,
The strength was measured and expressed in kg / cm ² . The test piece of this example had a uniaxial compressive strength of 150 to
A case where the strength was 250 kg / cm ² or more after curing at 200 kg / cm ² and 28 days was judged as one standard and passed. As shown in Table 7, samples I-1 to 28 according to the present example were used.
All of the pastes according to the above are within the acceptable range, and it can be seen that sufficient strength can be secured by uniform solidified body formation. Needless to say, depending on the purpose of use of the solidified product, it is not restricted to the above-mentioned standard value.

3. Shelf life: That is, a powdery sample was subjected to a relative humidity of 8 at a temperature of 25 ± 5 ° C.
It is stored in a room maintained at 0 ± 10% for 6 months, and a state in which there is no abnormal change in the viscosity of the fluid paste of the powdery sample and the uniaxial compressive strength of the solidified body after 6 months is regarded as shelf life. Passed ". As shown in Table 7, the pastes of Samples I-1 to I-28 according to the present example all fall within the acceptable range, and it can be seen that stable shelf life can be secured without reacting during storage.

(II) Second Embodiment Next, as a second embodiment of the present invention, a low-level radioactive waste powder generated from a nuclear power plant is formed into a pellet and stored in a drum. In order to reduce the storage capacity, a low-level radioactive waste was prepared by using a flowable paste obtained by mixing water with the powdery one-pack alkali silicate composition of the first embodiment as an injection solidifying agent composed of an inorganic polymer. An embodiment of a waste disposal method for disposing of a waste as a storage body will be described.

First, as a powdered one-pack alkali silicate composition sample, sample numbers 1-4 in the first embodiment were used.
Was prepared, and water was added to the powdery sample so that the water mixing ratio was 0.32, and the mixture was mixed to prepare a fluid paste as a solidifying agent.

On the other hand, as low-level radioactive waste pellets generated from a nuclear power plant, about 25 × 25 dry powder of low-level radioactive waste mainly composed of sodium sulfate was used.
× 13 mm almond-shaped compression-molded pellets were selected, and 260 kg of the pellets were filled into a 200-liter drum can lined with special cement to obtain a solid.

Thereafter, 110 kg of the fluid paste of Sample No. 1-4 (specific gravity: about 1.7) was injected into the solidified body in 8 minutes, and the injection was completed. Here, when calculating the void volume in a state in which the 260 kg of pellets are filled in a 200-liter drum, it is approximately 65 liters, while calculating the volume of 110 kg of the poured fluid paste is approximately 64.7 liters. . As a result, the voids of the drum filled with the pellets were almost completely filled with the flowable paste, and it was found that the flowable paste according to the present example had good workability and fillability.

Thereafter, the pellet-containing drum can into which the fluid paste was injected was left at 25 ° C. for 2 days, after which the surface of the solidified body exhibited sufficient hardness (350 kg / cm ² or more) and the low-level radioactive waste was removed. It was confirmed that an integrated solidified body was formed without causing wet swelling of the pellet.

(III) Third Example Next, as a third example of the present invention, a fluid paste obtained by mixing water with the powdery one-pack alkali silicate composition of the first example was used. An example in which the present invention is applied to the preparation of a nonflammable exterior wall building material as an inorganic polymer product will be described with reference to Table 8.

First, as a powdery one-pack alkali silicate composition sample, sample numbers 1-3 in the first embodiment were used.
The powdery sample prepared by the method described in the above was selected, and water was added to the powdery sample at a water mixing ratio shown in Table 8 and mixed to prepare a fluid paste as a solidifying agent.

On the other hand, as an aggregate of an inorganic polymer product,
Composite aggregates as shown in Table 8 were selected.

[0137]

[Table 8]

Thereafter, the selected composite aggregate was kneaded into the prepared flowable paste solidifying agent, and then a plate-like molding form (5
0 × 30 × 2cm)
After leaving it to stand in an oven at 80 ° C. for 60 minutes to solidify, the board was taken out of the mold to prepare a non-combustible building material for an outer wall.

[0139] At this time, the compressive strength and the bending strength of the prepared building material for the outer wall were measured, and the nonflammability was confirmed by the following test method. The results are also shown in FIG. The confirmation test method is as follows. That is, the test piece was exposed to an electric furnace maintained at 650 ° C. for 15 minutes, then allowed to cool at room temperature, and the compressive strength of the test piece was measured. The case where the rate was 50% or less was regarded as "pass" in the nonflammability test. As shown in Table 8, all of the samples 2-1 to 4 according to the present example passed, and it can be seen that sufficient nonflammability was secured. The inventors of the present invention have confirmed that all of the hydrated solidified gypsum board and cement-based solidified board fail in the 650 ° C. confirmation test. As a result,
It was found that non-flammable and durable building materials for exterior walls could be manufactured.

(IV) Fourth Embodiment Next, as a fourth embodiment of the present invention, a fluid paste obtained by mixing water with the powdery one-pack alkali silicate composition of the first embodiment is used. An example of application as an adhesive which is an adhesive polymer product will be described with reference to Table 9.

First, as a material to be bonded, a brick base for interlocking (a cement secondary product: 197 × 97
× 60 mm) and a ceramic tile.

On the other hand, a powdery one-pack sample prepared by the method of Sample No. 1-3 in the first embodiment was selected as a sample to be used for the adhesive which is an adhesive polymer product, and a predetermined one Was added at a mixing ratio of water, and an extender was further kneaded as necessary to prepare a fluid paste-like inorganic binder (adhesive). Table 9 shows the water mixing ratio and extender pigment at this time.

[0143]

[Table 9]

The adhesive thus prepared was spread on the above-mentioned brick substrate so as to have a thickness of about 1 mm, and a porcelain tile was placed thereon, lightly pressed, and left standing at room temperature for 7 days to make up. Interlocking. Then, the adhesive strength at this time was measured by a strong-type adhesive strength test method. The results are also shown in Table 9.

As a result, it was found that the fluid paste based on the first embodiment can be an excellent nonflammable inorganic binder.

(V) Fifth Embodiment Next, as a fifth embodiment of the present invention, a fluid paste obtained by mixing water with the powdery one-pack alkali silicate composition of the first embodiment is used. A case where the present invention is applied to a composite product by utilizing the adhesive will be described. The present embodiment is an embodiment of a composite non-combustible soundproofing and heat insulating material in which lightweight beaded aggregates are combined in a millet-like plate.

First, as a lightweight bead-like aggregate, a glass bead was converted into a lightweight bead (apparent specific gravity: 0.4 g / c).
c) was prepared.

On the other hand, as a sample to be used for the adhesive as an adhesive polymer product, a powdery one-pack sample prepared by the method of Sample No. 1-3 in the first embodiment was selected. Water was added so that the mixing ratio became 0.32, to prepare a fluid paste-like inorganic binder.

Thereafter, the aforementioned lightweight beaded aggregate 30
To 0 parts by weight, 100 parts by weight of the fluid paste-like inorganic binder prepared as described above was added, and the inorganic binder was mixed into the bead-like aggregate so that the inorganic binder was evenly distributed over the whole, and then 900 × 900 × 50 mm And left standing at room temperature for 7 days to solidify. The solidified millet plate was taken out of the mold to obtain a composite non-combustible soundproofing and heat insulating material. Then, a product test of this composite non-combustible soundproofing and heat insulating material was performed. Table 10 shows the results.

[0150]

[Table 10]

As a result, it has been found that the fluid paste based on the first embodiment is an excellent non-combustible inorganic binder for a composite non-combustible soundproofing and heat insulating material.

[0152]

According to the present invention, it is possible to eliminate a complicated on-site mixing process, to have a uniform and sufficient hardness, to secure the fluidity and the pot life required for the construction work, to prevent the whitening phenomenon, and It is possible to provide an alkali silicate composition capable of improving water resistance, a paste-like alkali silicate-based solidifying material using the same, a method for treating industrial waste, and a polymer product. At this time, the formed inorganic polymer is friendly to the global environment and can be effectively used for urban disaster prevention and crisis management, and plays an important role in various fields such as industrial activities, urban planning, and living environment. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI (C04B 28/26 22:08 22:16 22:06) (71) Applicant 390002004 Hitachi New Clear Engineering Co., Ltd. Hitachi, Ibaraki 3-2-2, Sachimachi (72) Inventor Tatsuo Izumida 3-1-1, Sachimachi, Hitachi-shi, Ibaraki Prefecture Inside the Hitachi Works, Hitachi, Ltd. (72) Inventor Yasuo Hattori 3-chome, Sachimachi, Hitachi-shi, Ibaraki No. 2 Hitachi New Clear Engineering Co., Ltd. (72) Inventor Satoru Fujii 6276 Onoda, Oda-shi, Onoguchi, Yamaguchi Prefecture Chichibu Onoda Co., Ltd. Central Research Laboratory (72) Inventor Hiroyuki Naito 6-6 Minami Aoyama, Minato-ku, Tokyo No. 20 Inside Nato Research Laboratories

Claims (13)

[Claims] A powdered one-pack alkali silicate composition in which four powdery components of alkali silicate, barium salt, silicon phosphate and aluminum oxide hydrate are homogeneously mixed and packed in a one-pack state. Wherein (a) the alkali silicate is one of the alkali metal elements of Li, Na and K.
One of M, p the number of 1.2 to 3.2, the number of 0.5 to 1.5 as q, soluble powder in water represented by _{M 2 O · pSiO 2 · qH} 2 O The barium salt is composed of one or a combination of two or more alkali silicates, and (b) the barium salt is BaO.rSiO _2. , Where r is a number of 4.0 or less and s is a number of 9.0 or less. The barium ion represented by sH ₂ O is composed of a powdery barium salt having a soluble portion in an alkaline solution alone or in combination of two or more kinds. (c) The silicon phosphate is
Where t is a number from 1.0 to 8.0 and t is a powdery silicon phosphate having a sustained release property of phosphoric acid represented by tSiO ₂ · P ₂ O ₅ , which is composed of one or a combination of two or more. (D) the aluminum oxide hydrate is 0.5 to
5.0, where u is a reactive aluminum hydrate powder and represented by Al ₂ O ₃ .uH ₂ O, and these powder alkali silicate and powder barium salt , Powdered silicon phosphate, and powdered aluminum oxide hydrate,
Based on 100 parts by weight of the powdered alkali silicate, the powdered barium salt, the powdered silicon phosphate, and the powdered aluminum oxide hydrate were 0.1 to 10 parts by weight, 1 to 40 parts by weight, and 10 parts by weight, respectively. A powdered one-pack alkali silicate composition, which is mixed so as to be in a range of from 50 to 50 parts by weight. 2. The powdered one-pack alkali silicate composition according to claim 1, wherein the powdered alkali silicate, the powdered barium salt, the powdered silicon phosphate and the powdered aluminum oxide hydrate are added. A sulfate compound consisting of one or a combination of two or more selected from the group of powdery sulfates that are hardly soluble in an alkali solution,
And the sulfate compound is mixed in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the alkali silicate powder, wherein the one-pack silica silicate is mixed. Alkaline composition. 3. A powdered one-pack alkali silicate composition according to claim 1, wherein said powdered alkali silicate, powdered barium salt, powdered silicon phosphate, and powdered aluminum oxide hydrate are added. An alkali borate comprising one or a combination of two or more water-soluble powdery borates is further homogeneously mixed, and the alkali borate is added to 100 parts by weight of the powdery alkali silicate. 4
A powdery one-pack alkali silicate composition, which is mixed so as to be 0 part by weight or less. 4. The powdered one-pack alkali silicate composition according to claim 1, wherein the powdered alkali silicate, the powdered barium salt, the powdered silicon phosphate, and the powdered aluminum oxide hydrate are added. And an alkali silicofluoride comprising one or a combination of two or more water-soluble powdery silicofluorinated compounds is further homogeneously mixed, and the alkali silicofluoride is added to 100 parts by weight of the powdered alkali silicate. A powdered one-pack alkali silicate composition, which is mixed so as to be 10 parts by weight or less. 5. The powdered one-pack alkali silicate composition according to claim 1, wherein the powdered alkali silicate, the powdered barium salt, the powdered silicon phosphate, and the powdered aluminum oxide hydrate are added. , A filler consisting of one or two or more combinations selected from pigments, functionalities, activators, fillers, etc., is further homogeneously mixed, and this filler is
800 parts by weight per 100 parts by weight of the powdery alkali silicate
A powdery one-pack alkali silicate composition, which is mixed so as to be 0 part by weight or less. 6. The powdered one-pack alkali silicate composition according to claim 1, wherein the powdered alkali silicate, the powdered barium salt, the powdered silicon phosphate, and the powdered aluminum oxide hydrate are added. , A surfactant, an organic compound, a resin, an additive selected from a combination of two or more selected from a modifying agent, etc., and the filler is further homogeneously mixed. A powdery one-pack alkali silicate composition, which is mixed in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of alkali. 7. A powdered one-pack alkali silicate composition in which four powdery components of alkali silicate, barium salt, silicon phosphate and aluminum oxide hydrate are homogeneously mixed and packed in a one-pack state. Wherein (a) the alkali silicate is one of the alkali metal elements of Li, Na and K.
One of M, p the number of 1.2 to 3.2, the number of 0.5 to 1.5 as q, soluble powder in water represented by _{M 2 O · pSiO 2 · qH} 2 O The barium salt is composed of one or a combination of two or more alkali silicates, and (b) the barium salt is BaO.rSiO _2. , Where r is a number of 4.0 or less and s is a number of 9.0 or less. The barium ion represented by sH ₂ O is composed of a powdery barium salt having a soluble portion in an alkaline solution alone or in combination of two or more kinds. (c) The silicon phosphate is
Where t is a number from 1.0 to 8.0 and t is a powdery silicon phosphate having a sustained release property of phosphoric acid represented by tSiO ₂ · P ₂ O ₅ , which is composed of one or a combination of two or more. (D) the aluminum oxide hydrate is 0.5 to
5.0, where u is a reactive powdery aluminum oxide hydrate represented by Al ₂ O ₃ .uH ₂ O. These powdery alkali silicate, powdery barium salt, powdery The powdered silicon phosphate and the powdered aluminum oxide hydrate were prepared by adding powdered barium salt, powdered silicon phosphate, and powdered aluminum oxide hydrate to 100 parts by weight of the powdered alkali silicate, respectively. .1 to 10 parts by weight, 1 to 4
0 parts by weight and 10 to 50 parts by weight, and 2 parts by weight with respect to 100 parts by weight of the alkali silicate composition.
A powdery one-pack alkali silicate composition which is used for a polymer product by being mixed with 7 to 100 parts by weight of water to form a polymer having a polysiloxane bond as a main chain. 8. The powdery one-pack alkali silicate composition according to any one of claims 1 to 7, wherein the powdery one-pack alkali silicate composition and water are mixed. The water is 27 parts by weight or more with respect to 100 parts by weight of the product.
A paste-like alkali silicate-based solidifying material, which is mixed in a range of 7 parts by weight or less. 9. After injecting the paste-like alkali silicate-based solidifying material according to claim 8 into a container containing wastes,
A method for treating waste, wherein the waste is immobilized in the container by opening in a 300 ° C. atmosphere to form a polymer having a polysiloxane bond as a main chain. 10. The powdery one-pack alkali silicate composition and water according to any one of claims 1 to 7, based on 100 parts by weight of the powdered one-pack alkali silicate composition. Water is mixed in a range of 27 parts by weight or more and 47 parts by weight or less to form a paste.
A polymer product which is manufactured by forming a polymer having a polysiloxane bond as a main chain by opening to an atmosphere at ~ 300 ° C. 11. The polymer product according to claim 10, wherein the polymer having a polysiloxane bond as a main chain is formed alone. 12. The polymer product according to claim 10, wherein a polymer having the polysiloxane bond as a main chain is formed on the surface of the substrate to be adhered, whereby the surface of the substrate is coated, painted, Or a polymer product characterized by adhesion or the like. 13. The polymer product according to claim 10, wherein said paste is integrated with a target shape maintaining material and released into an atmosphere at 5 to 300 ° C. to remove said polymer having a polysiloxane bond as a main chain. A polymer product which is formed as a composite by being formed integrally with the shape maintaining material.