JP2001278677A - Method for producing inorganic foam molded article - Google Patents

Abstract

(57) [Problem] To provide a method for producing an inorganic foam molded article having excellent heat insulating properties, mechanical properties, water resistance, etc., and having a uniform and highly accurate shape and dimensions. (A) An aqueous solution or aqueous dispersion of a phosphoric acid,
(B) Mixing the oxides or hydroxides of Groups 2, 13, 14 or transition metals of the Periodic Table and the components of (c) metal carbonates and bringing the temperature immediately after mixing to -15 to + 10 ° C. The slurry-like mixture thus adjusted is made into a precursor shape of a foam molded article to be produced, and then foaming and curing are advanced to form a foam.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a molded article of an inorganic foam, and more particularly, to a method for producing a uniform and highly accurate shape and size having excellent heat insulating properties, mechanical properties and water resistance. The present invention relates to a method for producing an inorganic foam molded article having the same.

[0002]

2. Description of the Related Art Conventionally, polyurethane, polyurethane, etc. have been used as building materials and various heat insulating materials having excellent heat insulating properties and light weight.
Organic foams such as polystyrene and polyethylene are widely used. However, in recent years, the flammability and damage caused by toxic gases during a fire have become a major problem, and there has been an increasing demand for non-combustible insulation materials to ensure safety. Because of its flammability, the use as a non-combustible material is limited.

[0003] On the other hand, lightweight foam concrete, glass foam, and the like are known as foam materials having excellent non-combustibility, but all of these materials require a large amount of energy and special equipment in the manufacturing process. Therefore, there is a problem that the manufacturing cost is increased. On the other hand, an inorganic foam of a metal phosphate has been proposed as a non-combustible foam that can be produced under normal temperature and normal pressure. For example, in Japanese Patent Publication No. 55-4709, pH
A method for producing an inorganic heat insulating material has been proposed in which an aqueous solution of an acidic phosphate of 1.5 or less, an anhydrous alkali silicate, a metal-based foaming agent and a foaming stabilizer are mixed in a paste form. A similar method of manufacturing a heat insulating material has also been proposed in Japanese Patent Publication No. 56-14623 and Japanese Patent Publication No. 56-14624. In Japanese Patent Publication No. 56-36145, the ratio of the total number of metal atoms constituting the metal phosphate to the total number of phosphorus atoms is 2/3 to 2/1.
It contains at least one polyvalent metal, has an equivalent ratio of the total valence of the metal to the total valence of the phosphate ion of 0.65 to 0.95, and has a closed cell structure with an average cell diameter of 3 mm or less. An inorganic foam made of a metal salt of phosphoric acid having a specific gravity of 0.15 or less has been proposed.

In Japanese Patent Application Laid-Open No. Hei 4-83771,
A metal salt of phosphoric acid, a metal salt of boric acid and / or a metal salt of aluminate, and if necessary, an inorganic porous material derived from a polyvalent metal hydroxide and / or a polyvalent metal carbonate (b) are proposed. Have been. Japanese Patent Application Laid-Open No. Hei 6-24869 proposes a porous body comprising phosphoric acid, polyvalent metal oxide, resin emulsion, water and a foaming agent.

Further, Japanese Patent Application Laid-Open No. 9-157061 proposes an inorganic-organic composite foam in which the brittleness of the foam structure from phosphoric acid and a foaming agent of phosphoric acid is improved by a urethane prepolymer having an NCO group. I have. The inorganic foams of these metal phosphates are subjected to a neutralization and solidification reaction with a powder of a basic metal oxide or a hydrate thereof in a phosphoric acid aqueous solution, and at the same time, a metal carbonate or a foaming agent is used. It is believed that the metal powder is oxidized to generate fine gas bubbles by generating carbon dioxide gas and hydrogen gas.

On the other hand, when continuously producing an organic foam such as polyurethane slab foam, a reaction solution is discharged onto a traveling conveyor, and a jig called a fork, a nip roll, a blade, or the like is used for smoothing. A method in which the undiluted solution is uniformly cast on the top and then moved on a conveyor while foaming, or the undiluted solution is collected in a reaction undiluted solution reservoir called a trough, and the undiluted solution is raised by pulling up a bottom sheet passing through the trough outlet. And uniformly cast on a conveyor.

[0007]

However, unlike the above-mentioned organic foam, when an inorganic foam is produced, foaming of a metal carbonate or metal powder with phosphoric acid, which is a raw material of the foam, is performed. The oxidation reaction of the agent is extremely fast. Therefore, since the raw material mixture forming the foam has already begun foaming immediately after mixing, for example, when molded into a sheet or board, the flowability of the mixture is poor, and the above-described organic foam is manufactured. It is difficult to adjust the liquid level of the slurry-like mixture using a smoothing jig as described above. Thus, in the case of the inorganic foam, it has been difficult to obtain a sheet-like molded product or a board-shaped molded product having a uniform thickness and density.

Also, in the case of an inorganic foam, when the mixture of the foaming material is injected into a panel or a deformed mold and molded, similarly, the start and rise time of foaming are fast, so that the foam is uniformly and sufficiently contained in the mold. Since it is difficult to fill the mixture, the inorganic foam molded product is less likely to have a predetermined high-precision shape and size, and the dispersed state and density of the bubbles in the obtained foam molded product become non-uniform, There has been a problem that the mechanical properties and the heat insulating properties become insufficient.

[0009] The present invention solves the above problems,
An object of the present invention is to provide a method for producing an inorganic foam molded article having excellent heat insulation properties, mechanical properties, water resistance, etc., and having a uniform and highly accurate shape and dimensions.

[0010]

The present invention achieves the above object, and comprises mixing the following components (a) to (c) and adjusting the temperature immediately after mixing to -15 to + 10 ° C. A method for producing an inorganic foam molded article, characterized in that after obtaining a slurry-like mixture, the foamed article is formed into a precursor shape of a foam molded article to be produced, and then foaming and curing are advanced to form a foam. (A) phosphoric acid aqueous solution or aqueous dispersion, (b) periodic table second
An oxide (b1) or a hydroxide (b2) of a metal selected from the group consisting of group metals, groups 13 and 14, and transition metals;
(C) Metal carbonate.

[0011] In the method for producing an inorganic foam molded article of the present invention, by controlling a slurry-like mixture containing phosphoric acid, which is a raw material of the inorganic foam, to a low temperature within a specific range, the mixture is partially formed. Although foaming occurs, it is possible to delay the rise time of foaming as a whole and to maintain the fluidity of the mixture. In this way, while the slurry-like mixture retains fluidity, a precursor shape adapted to the shape of the foam to be produced is formed from the slurry-like mixture, and then foaming of the mixture,
The curing is advanced to form the foam into a desired shape.

[0012]

In the present invention, the temperature of the slurry mixture containing the components (a) to (c) is adjusted so that the temperature immediately after mixing becomes -15 to + 10 ° C. While maintaining the temperature, it is necessary to reduce the precursor shape of the foam molded article to be produced.

When the temperature of the slurry-like mixture exceeds 10 ° C., the foaming rate of the mixture increases, the foaming proceeds excessively, and the fluidity decreases. A molded product having a uniform pod density cannot be obtained, and it is difficult to fill the mixture into the inside and the details of the mold even when the mixture is injected into a mold or the like. On the other hand, when the temperature is lower than −15 ° C., the reactivity of the aqueous solution or aqueous dispersion of phosphoric acids becomes extremely poor, so that the time until curing becomes long and the foamed bubbles gradually become hardened before being hardened. And cause sedimentation of the foam. It is appropriate that the temperature of the slurry mixture is, in particular, -5 to + 10 ° C.

When the temperature of the slurry-like mixture is adjusted, each component may be controlled at the aforementioned temperature in advance and mixed, or during or immediately after mixing each component, the temperature may be controlled within the aforementioned temperature range. Is also good. However, from the viewpoint of the easiness of the means and the obtained effects, it is preferable to control the temperature of the aqueous solution or aqueous dispersion of phosphoric acids. Thus, the temperature of the aqueous solution or aqueous dispersion (a) of phosphoric acid is preferably -20 to + 5 ° C, particularly preferably -10 to
+ 5 ° C., and mixing the above-mentioned components (b) and (c), which are other components, with the aqueous solution or aqueous dispersion (a) of phosphoric acid maintained at such a temperature, thereby obtaining the above-mentioned temperature. A range of slurry-like mixtures is obtained.

The method for measuring the temperature of the slurry mixture and the aqueous solution or aqueous dispersion (a) of phosphoric acid is not particularly limited, and a mercury thermometer, an alcohol thermometer, a thermocouple, and a thermocouple utilizing thermal expansion may be used. A non-contact type thermometer such as a contact thermometer using a platinum resistor or a thermistor, or a radiation thermometer using an infrared ray may be used. In particular, when measuring the slurry-like mixture, the reaction and foaming of the mixture have started little by little, so that it is necessary to measure the mixture quickly. It is preferable to use a radiation thermometer when measuring the mixture.

Examples of the phosphoric acid forming the aqueous solution or the aqueous dispersion (a) of the phosphoric acid of the present invention include acidic phosphoric acid such as orthophosphoric acid, phosphorous acid, phosphoric anhydride, condensed phosphoric acid, and the like. Or a mixture of two or more thereof. The metal salt compound of phosphoric acid herein includes a metal salt compound of acidic phosphoric acid, and the metal salt compound of acidic phosphoric acid is a metal salt compound of phosphoric acid having at least one hydroxyl group bonded to a phosphorus atom. Say. Examples of the metal salt compound of the acidic phosphoric acid include a metal phosphate monobasic, a metal phosphate dibasic, and a metal phosphate monobasic. In addition to the metal salt compound of phosphoric acid, phosphate esters such as phosphoric acid monoesters and phosphoric acid diesters can be exemplified. As the phosphoric acids, at least one kind selected from the above may be used, but two or more kinds may be used in combination.

The metal constituting each of the above-mentioned metal phosphates, metal phosphates and metal phosphites includes, for example, magnesium, calcium, aluminum, zinc, barium, iron and the like. Can be mentioned.

Examples of the phosphate monoesters include monomethyl phosphate, monoethyl phosphate, monobutoxyethyl phosphate and the like. Examples of the phosphate diesters include dimethyl phosphate, diethyl phosphate, and diphosphate phosphate. Butoxyethyl and the like can be mentioned. Above all, in consideration of fire resistance and nonflammability of the obtained foam, those having a relatively small number of carbon atoms in the carbon skeleton are preferable. The above-mentioned phosphoric acid monoesters or phosphoric acid diesters have the effect of lowering the surface tension of the slurry before foaming and improving the function of a foam stabilizer (surfactant) during foaming. Then, since unfavorable effects on the fire resistance and flame retardancy of the foam, when using the phosphoric acid monoesters or phosphoric diesters, the orthophosphoric acid, the metal phosphate monobasic, and the phosphorous secondary phosphate. It is preferable to use an acid metal salt or a metal phosphite in combination.

Preferred among the above-mentioned phosphoric acids are:
One or a mixture of two or more selected from orthophosphoric acid, magnesium monophosphate, aluminum monophosphate, and zinc monophosphate. Since these are inorganic substances, the fire resistance of the obtained foam is It does not adversely affect heat resistance and flame retardancy, and has high reactivity with metal oxides, metal hydroxides or metal carbonates (c) described later. Among these, orthophosphoric acid, aluminum monophosphate, magnesium monophosphate or a mixture thereof is particularly preferable because of its good solubility in water.

The acidic phosphoric acid compound is used in the form of an aqueous solution or an aqueous dispersion. The concentration of the aqueous solution or the aqueous dispersion is 30 to 80% by mass in order to be able to mix uniformly with other components described later, to facilitate the operation at the time of foaming, and to shorten the drying and curing time as much as possible. And more preferably 50 to 70% by mass.

When the concentration of the aqueous solution or aqueous dispersion of the acidic phosphoric acid compound is less than 30% by mass, the amount of water contained in the slurry before foaming increases, and the drying and curing time increases,
Productivity may decrease. On the other hand, the concentration is 80% by mass.
If it exceeds 3, the viscosity of the aqueous solution will increase, and it may be difficult to mix it uniformly with other components described below.

The content of phosphoric acid in the foam of the present invention is preferably 3 to 20% by mass, particularly preferably 4 to 20% by mass in terms of the content of phosphorus atoms in the foam produced by the present invention. 18% by weight is suitable. If the content is less than 3% by mass, the flame retardancy of the obtained foam may decrease. On the other hand, if the content exceeds 20% by mass, a uniform foamed structure may not be obtained. The aqueous solution of phosphoric acid referred to here is a solution in which a water-soluble phosphoric acid such as a metal phosphate primary salt, orthophosphoric acid, phosphorous acid, or the like is dissolved in water as a solvent, and adjusted to 30 to 80% by mass. It is preferable to use a phosphoric acid aqueous solution or a metal phosphate aqueous solution that has been prepared since storage stability and handleability are improved. In addition, the aqueous dispersion of phosphoric acids refers to a dispersion in which a relatively low solubility in water such as a metal phosphate is used. This aqueous solution of phosphoric acid and the aqueous dispersion of phosphoric acid are used. The liquid may be used alone, or may be used in combination with adjusting the water content if necessary.

As the aqueous solution or aqueous dispersion of phosphoric acids (a), an aqueous solution or aqueous dispersion of an acidic metal phosphate, particularly a polyvalent metal salt thereof, is used in combination with a water-soluble amine. It can be preferably used. Examples of the water-soluble amines include secondary or tertiary alkylamines such as diethylamine, diisopropylamine, diallylamine, triethylamine and triallylamine; pyridine,
Heterocyclic amines such as piperidine, N-methylpiperidine, morpholine, N-methylmorpholine, N-ethylmorpholine, lutidine; amino acids such as monoethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine Water-soluble amines having a boiling point at room temperature to about 200 ° C. of alcohols are preferred. These are against water
Those that dissolve at 1% by mass or more are preferably employed.

The component (b) used in the present invention includes metals belonging to Group 2 of the periodic table (Be, Mg, Ca, Sr, Ba, Ra),
Group 13 metals (Al, Ga, In, Tl), 14
Group metals (Ge, Sn, Pb) and transition metals (3rd Periodic Table)
Group 12 to Group 12 metals, Ti, Cr, Mn, Fe,
Co, Ni, Zn, etc.) are metal oxides (b1) or hydroxides (b2) of metals selected from the group consisting of: These metals react with the phosphoric acids to form a skeleton of the inorganic foam, and a part thereof also functions as a filler. In the case of the metal hydroxide of the component (b), the foam is preferably employed because it also functions as a heat absorbing substance that releases water and absorbs heat when the foam is exposed to a high temperature to absorb a temperature rise. You. Further, the oxides and hydroxides of Group 2 metals of the periodic table are highly reactive with the aqueous solutions or aqueous dispersions of the phosphoric acids, so that self-heating is likely to be promoted, and the oxides and hydroxides are kept at a low temperature of -15 to + 10 ° C. It is preferable to facilitate the curing of the mixture more effectively, and to prevent collapse of the foam cells. Therefore, even when an oxide or hydroxide of another metal is used in combination as the component (b), it is preferable that the oxide or hydroxide of all metals contains 5% by mass or more. More preferably, it is contained by mass% or more.

Preferred examples of the oxide (b1) of the metal belonging to Group 2 of the periodic table include magnesium oxide, calcium oxide, barium oxide and the like. Examples of the hydroxide (b2) of the metal belonging to Group 2 of the periodic table include: And preferably, magnesium hydroxide, calcium hydroxide, barium hydroxide and the like. These may be used alone or in combination.

As preferred examples of the component (b) used in the present invention, oxides or hydroxides of metals other than Group 2 metals of the periodic table are widely used, are easily available, and are relatively inexpensive. Therefore, aluminum oxide, aluminum hydroxide, zinc oxide, zinc hydroxide, or the like is preferable.

In the present invention, in order to reduce the cost of the obtained inorganic foam molded article, the above-mentioned (b) may be used.
As a component, a mineral-based material can also be used. These minerals include gypsite minerals, diaspor,
Aluminum oxide hydrates such as boehmite; natural zeolites or artificial zeolites such as calcite, soda zeolite, mordenite, clinoptilolite, hulandite, mordenite, and zeolite; Minerals such as kaolinite, halloysite, deckite, nacranite, kibushi clay, frog-eye clay, kaolin, kaolin clay, calcined clay, ziglite, etc .; talc, talc, stone brush Minerals containing hydrated magnesium silicate as a main component, such as stone, soapstone, and kamitark; mica minerals, such as phlogopite, biotite, muscovite, sericite, illite, and siegrite; brucite, attapulgite, etc. Magnesia minerals; wollastonite, calcium minerals such as Rarunaito; can corundum, diaspore, boehmite, bauxite, 礬土 shale, mullite, sillimanite, kyanite, and the like of aluminum minerals such as non-foamed vermiculite.

The mineral-based material is selected from the group consisting of (b1) and (b)
2) Some components contain the component (b1) or (b)
2) It can also be used as a component. Note that the mineral containing a metal oxide can also function as an inorganic aggregate or an inorganic thickener. In the present invention, (b)
In the slurry-like mixture, the component (a)
It is suitable that the amount is preferably 10 to 150 parts by mass, particularly preferably 20 to 100 parts by mass with respect to 100 parts by mass of the phosphoric acid constituting the component.

The metal carbonate as the component (c) used in the present invention is a component that generates carbon dioxide gas by reacting with the phosphoric acid to generate bubbles, that is, functions as a foaming agent. The remainder (mainly metal oxide) after the generation of carbon dioxide gas performs the same function as that of the metal oxide. As such a metal carbonate (c), it is preferable to use ammonium carbonate in addition to carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, basic magnesium carbonate, calcium carbonate, and basic zinc carbonate. Can be. Metal carbonate (c)
Minerals containing, for example, dolomite, calcite and the like can also be used. Among them, they are easily available and relatively inexpensive because they are widely used, and have high reactivity with the phosphoric acids, and thus contain at least one of basic magnesium carbonate and calcium carbonate, or both. It is preferred to use minerals.

The metal carbonate (c) may be used by selecting one kind alone, or two or more kinds may be used in combination. The metal carbonate (c) is preferably contained in the slurry mixture in an amount of 10 to 100 parts by mass with respect to 100 parts by mass of the phosphoric acid. If the amount of the metal carbonate (c) is less than 10 parts by mass, the foaming becomes insufficient, and an inorganic foam having a desired density cannot be obtained. On the other hand, when the use amount of the metal carbonate (c) exceeds 100 parts by mass, lumps of bubbles are formed in the inorganic foam, and the distribution of the bubbles becomes uneven, which is not preferable for the strength and the heat insulating performance of the inorganic foam. affect. Since the density of the inorganic foam varies depending on the amount and type of the metal carbonate (c),
The amount and type of the metal carbonate (c) are appropriately set so as to have a density required according to the use of the inorganic foam and the like, and according to the type of phosphoric acid used. Above all,
The amount of the metal carbonate (c) used is 2 parts per 100 parts by mass of phosphoric acid since the degree of foaming is easily controlled.
Suitably it is from 0 to 70 parts by weight.

In the present invention, the amounts of the components (b) and (c) used to obtain the slurry mixture are as follows:
With respect to 100 parts by mass of an aqueous solution or aqueous dispersion of a phosphoric acid as a component, the two components are preferably combined in a total amount of 40 parts by mass.
It is preferable that the amount be 100 parts by mass. When the amount is smaller than the above range, the effect of using the components (b) and (c) is not sufficient, while when the amount is larger than the range, the components (a) to (c) are not used. Of the slurry obtained from the mixture of the above is insufficient. Among them, the total amount of the components (b) and (c) is particularly preferably 40 to 80 parts by mass.

In the present invention, it is preferable that the mixture contains a resin (d) in order to improve the brittleness of the foam to be produced. As the resin (d), in particular,
One or more of an aldehyde-based condensation resin, an isocyanate, an epoxy resin or a precursor thereof and, if necessary, a curing agent thereof are included, and the curing of the inorganic foam and the curing of the resin proceed simultaneously. Is preferred. The resin (d) is preferably contained in an amount of 3 to 30% by mass, and more preferably 5 to 25% by mass, based on the total solid content in the obtained foam. For this reason,
When mixing the components (a) to (c), it is preferable to use 10 to 50 parts by mass based on 100 parts by mass of the phosphoric acid.

The aldehyde-based condensed resin (d1) used in the present invention preferably crosslinks by condensing a methylol group in the molecule by heating in the presence of an acid catalyst.
It is a compound that cures. When a highly acidic catalyst is used, this aldehyde-based condensable resin becomes a gel in a few seconds to a few minutes after the resin starts to thicken even at room temperature.
The aldehyde-based condensable resin is thickened by the action of the phosphoric acid as a catalyst, gradually increasing the viscosity of a slurry obtained by mixing the components used in the present invention,
Function of retaining generated foam (foam control function)
Also fulfills.

Examples of such aldehyde-based condensable resins include urea, thiourea, melamine, acetoguanamine, benzoguanamine, guanidine, dicyandiamide, and the like.
It is preferable to use a precondensate obtained by a condensation reaction of a phenol such as phenol, cresol, xylenol, resorcin and an aldehyde such as formaldehyde. Among them, urea resins, melamine resins, and phenol resins are preferable, and melamine resins are particularly preferable in that the cured resin itself does not burn easily and has excellent water resistance, so that the performance of the inorganic foam can be improved.

The aldehyde-based condensable resin can be used in the form of a liquid, a solid, or an aqueous solution. However, it is preferable to use the aldehyde-based condensable resin in the form of an aqueous solution in advance because it is easily mixed with other components. The concentration of the aldehyde-based condensable resin in the case of an aqueous solution is preferably 40 to 80% by mass. When the concentration of the aldehyde-based condensable resin is less than 40% by mass, the amount of water contained in the slurry before foaming increases, and the effect of the foam regulating function becomes insufficient.
The drying and curing time of the inorganic foam may be prolonged, and the productivity may decrease. On the other hand, when the concentration of the aldehyde-based condensable resin exceeds 80% by mass, the viscosity of the aqueous solution increases, and it may be difficult to uniformly mix the aqueous solution with other components.

Further, in order to adjust the rate at which the aldehyde-based condensable resin thickens, another acid catalyst may be used in addition to the phosphoric acids. Such acid catalysts include, for example, formic acid, acetic acid, citric acid, oxalic acid, phthalic acid, salicylic acid, organic carboxylic acid esters, sulfonic acid esters, taurine, triethanolamine hydrochloride, urea phthalate, nitrourea, guanyl Examples thereof include urea organic salts, sodium salts of ethyl sulfate, and formate esters, and among them, those which are water-soluble are preferable. In addition, when using the said acid catalyst, it is preferable to use it in 0.1-5 mass parts with respect to 100 mass parts of said aldehyde-type condensable resins.

The aldehyde-based condensable resin may be used by selecting one kind alone, or two or more kinds may be used in combination. The aldehyde-based condensable resin is used in an amount of preferably 10 to 50 parts by mass based on 100 parts by mass of the phosphoric acid. When the amount of the aldehyde-based condensable resin is less than 10 parts by mass, the effect of improving brittleness is hardly obtained. On the other hand, when the amount exceeds 50 parts by mass, the aldehyde-based condensable resin is a resin that is difficult to burn, but unfavorably affects the fire resistance and thermal shock resistance of the obtained inorganic foam.

The isocyanates (d2) used in the present invention are composed of an organic polyisocyanate or a reaction between an organic polyisocyanate compound and an active hydrogen-containing compound, and particularly, a urethane having an NCO group in the molecule. Preferably, a prepolymer is included.
When the organic polyisocyanate compound is used alone, an active hydrogen-containing compound may be separately added to the slurry mixture. Preferred examples of the organic polyisocyanate compound include hexamethylene diisocyanate (HDI),
Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MD
I), methylcyclohexane-2,4-diisocyanate (hydrogenated TDI), 2,4- or 2,6-toluene diisocyanate (TDI), or 4,4′-diphenylmethane diisocyanate (MDI).

Examples of the active hydrogen-containing compound include polyols. The polyol has substantially O 2 in the molecule.
There is no particular limitation as long as the compound has two or more H groups.
Polyether polyol, high molecular weight polyol forming the main chain of polyurethane such as polyester polyol,
Crosslinking agents and low molecular weight polyols as reactive flame retardants are exemplified.

Preferred examples of the polyether polyol include an ethylene oxide-added polyether polyol and polytetramethylene ether glycol obtained by polymerization of tetrahydrofuran. Also,
Preferred examples of the polyester polyol include polyester obtained from natural products, polyester obtained by polycondensation of carboxylic acid / polyol, polycaprolactone polyol, aromatic polyester polyol, polycarbonate polyol, acrylic polyol, castor oil polyol, and polymer polyol. And the like. Other examples include polyetherester polyols and modified polyether polyols. Examples of the modified polyether polyols include graft polyols, polyurea-dispersed polyols, bisphenol A-modified polyols, and amine-modified polyols. Preferred examples of the low molecular weight polyol include aliphatic dihydric alcohols, low molecular diols having a cyclic group, trihydric alcohols, polyhydric alcohols having four or more functional groups, alkanolamines, and ethylene of these compounds. Oxides and / or low molar adducts of propylene oxide are mentioned.

Particularly preferred as the active hydrogen-containing compound are ethylene oxide adducts of polyoxyalkylene polyols and polytetramethylene ether glycol obtained by polymerization of tetrahydrofuran, and the above ethylene oxide adducts and polytetramethylene It is preferable to use ether glycol alone or partially. Further, the low-molecular-weight polyol and the high-molecular-weight polyol may be used alone or in combination, and the usage ratio of the low-molecular-weight polyol and the high-molecular-weight polyol is not particularly limited, and the improvement of the brittleness of the foam,
It is preferable to appropriately set the mass ratio in order to impart flexibility.

The isocyanate (d2) is preferably used in an amount of 10 parts by mass of the phosphoric acid constituting the component (a) in the slurry mixture.
５０50 parts by mass. If it is smaller than this range, it is difficult to obtain the effect of improving the brittleness of the foam, while if it is larger than the above range, the fire resistance and thermal shock resistance of the foam are inferior, which is not preferable.

The epoxy resin (d3) used in the present invention is not particularly limited, and is a compound having one or more epoxy groups in a molecule. For example, phenolic di- or polyglycidyl ether type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, resorcin diglycidyl ether, phenol novolak polyglycidyl ether, cresol novolak polyglycidyl ether; glycidyl ester of hexahydrophthalic acid, dimer Di- or polyglycidyl ester type epoxy resins such as acid glycidyl ester; cycloaliphatic epoxy resins such as 3,4-epoxy-6-methylcyclohexyl carboxylate and 3,4-epoxycyclohexylmethyl carboxylate can be used.

These epoxy resins may be in the form of an oligomer.
A type may be selected or two or more types may be used in combination. Furthermore, the epoxy resin and the low-viscosity monoepoxy-based reactive diluent may be used in combination in consideration of the workability and the strength improving effect.

In order to mix the epoxy resin with the slurry mixture according to the present invention, it is necessary to dissolve or disperse the epoxy resin in the slurry mixture at the time of mixing. A method of emulsifying using an activator may be mentioned. As the surfactant used here, a nonionic surfactant having an HLB of 15 or more, such as an ethylene oxide adduct of an alkyl phenol such as octyl phenol or nonyl phenol, or a pluronic surfactant of ethylene oxide propylene oxide is preferably used.

As the curing agent for the epoxy resin, aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, hexamethylenediamine, isophorodiamine, polymercaptan and polysulfide are used. can do. Among them, it is more preferable to use triethylenetetramine, hexamethylenediamine, xylenediamine, or the like, which is easily dissolved or dispersed in the slurry mixture.

As another method of dissolving or dispersing in the slurry mixture, a slurry mixture of the epoxy resin and a modified aliphatic polyamine in which amino groups are partially neutralized with an acid can be used. The ratio of the epoxy resin and the curing agent used is from 0.8 to 0.8 in the amino group in the aliphatic polyamine curing agent for one epoxy group.
It is preferable to mix them so as to obtain 1.2 active hydrogens. Further, the epoxy resin and the curing agent are preferably mixed at a predetermined time before mixing the slurry-like mixture depending on the curing time, and the timing of the progress of the curing of the epoxy resin and the curing of the foam are adjusted. This is very important.

In the present invention, the epoxy resin (d
3) In the slurry-like mixture, the (a)
It is preferably contained in an amount of 10 to 50 parts by mass based on 100 parts by mass of the phosphoric acid constituting the component. If it is smaller than this range, it is difficult to obtain the effect of improving the brittleness of the foam, while if it is larger than the above range, the fire resistance and thermal shock resistance of the foam are inferior, which is not preferable.

Further, the slurry mixture of the present invention preferably contains urea (e). The urea (e) is preferably contained in the slurry-like mixture in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the phosphoric acid constituting the component (a). The urea (e) suppresses the reaction between the components (a) and (c). When the urea is smaller than the above range, the effect is hardly obtained. Is undesirably long. The urea (e) is mixed even if the temperature of the aqueous solution or aqueous dispersion of the phosphoric acid component (a) and the temperature of the slurry-like mixture are set relatively high within the above-mentioned range. This makes it possible to improve the fluidity of the slurry mixture.

Further, in the present invention, in order to improve the physical properties of the foam and the cost of raw materials, inorganic fibers, cement, lightweight aggregates and the like can be mixed with the above-mentioned slurry-like mixture and used. Examples of the inorganic fibers include glass fibers and rock wool.
Examples of the glass composition of the glass fiber include A glass, E glass, and S glass. In order to maintain the fluidity of the slurry and uniformly disperse it in the inorganic foam, the inorganic fibers are cut in a length of 1.5 mm to 10 cm, or in a length of 1.5 mm or less. It is preferred to use it in a crushed form.

The inorganic fiber functions as a reinforcing material that prevents cracks and warpage due to shrinkage when the inorganic foam is dried and cured, and improves the dimensional stability of the inorganic foam. In order to make this function sufficient, it is preferable to use inorganic fibers having an aspect ratio of 10 or more on average. The aspect ratio is a ratio obtained by dividing the length of the fiber by the diameter of the fiber. In order to uniformly disperse the inorganic fibers in the inorganic foam, it is particularly preferable to use milled fiber of E glass or ground pulverized glass wool which is apparently powdery.

The inorganic fiber is preferably contained in the slurry mixture in an amount of preferably 5 to 100 parts by mass with respect to 100 parts by mass of the phosphoric acid. If the amount of the inorganic fiber used is less than 5 parts by mass, cracks and warpage may occur due to shrinkage during drying and curing of the inorganic foam. If the amount used exceeds 100 parts by mass, the fluidity of the slurry-like mixture becomes poor, and the reaction between phosphoric acids and the oxide (b1) and / or hydroxide (b2) of the component (b) component metal occurs. The amount of inorganic fibers relative to the skeleton portion of the formed inorganic foam is relatively too large,
Instead, the strength of the inorganic foam is reduced. Since the resulting inorganic foam has both lightness and good strength, and can completely prevent the occurrence of cracks, the inorganic fiber is 1
It is preferably contained in an amount of 0 to 80 parts by mass.

In the present invention, it is also possible to mix a surfactant with the slurry mixture. This surfactant functions as a foam stabilizer. Examples of such surfactants include, for example, anionic surfactants such as sodium oleate, sodium stearate, and alkyl sulfate, and nonionic surfactants such as an ethylene oxide adduct of octylphenol and an ethylene oxide adduct of a higher alcohol. And the like.

The surfactant is preferably contained in the slurry mixture in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the phosphoric acid. When the amount of the surfactant is less than 0.01 parts by mass, the foam-regulating effect is not sufficient. In addition, even if the amount exceeds 10 parts by mass, the foam-regulating effect is not improved for the amount used, and adversely affects water resistance such as water absorption of the inorganic foam.

Examples of the cement material usable in the present invention include natural cement, Portland cement,
White portland cement, alumina cement, lime mixed cement, ettringite mixed cement, high sulfate slag cement and the like can be mentioned. These hydraulic cements perform the same functions as the metal oxides and metal hydroxides. In addition, air-hardening cement such as gypsum or magnesia cement can be appropriately added to the hydraulic cement for use.

The hydraulic cement is preferably contained in the slurry-like mixture in an amount of preferably 20 parts by mass or less based on 100 parts by mass of the phosphoric acid. If the amount of the hydraulic cement exceeds 20 parts by mass, the water resistance and thermal shock resistance of the obtained foam may decrease.

Examples of the inorganic lightweight aggregate that can be used in the present invention include expanded vermiculite, pearlite, expanded shale, pumice, shirasu balloon, etc., which are natural mineral expanded or expanded substances, as well as gypsum or silica gel. Artificial inorganic and lightweight materials such as granulated and foamed steel slag, granulated and foamed glass waste, and granulated and foamed clay powder Aggregate is also included.

In the present invention, the above-mentioned components are mixed to form a slurry-like mixture. The amount of water contained therein can be adjusted by uniformly mixing the components to form a slurry. It is preferable that the amount is within a range that allows sufficient fluidity to be obtained. However, the more water contained in the slurry, the more time and labor it takes to dry and harden the foam. Therefore, water should not be added more than necessary. The amount of water contained in the slurry is not particularly limited,
In consideration of fluidity and ease of drying, it is preferable to adjust the water content so that the solid content is 40 to 90% by mass of the entire slurry.

In the present invention, there is no limitation on the method of mixing the above components to form a slurry-like mixture, and foaming, curing and drying the mixture to obtain an inorganic foam having a desired shape.
For example, the following method can be adopted.

First, a slurry mixture of the above components is obtained by any of the following procedures (1) to (3).

(1) Phosphoric acid aqueous solution or aqueous dispersion (a), metal oxide (b1) or hydroxide (b2),
The metal carbonate (c) and, if necessary, the resin (d) and / or other inorganic fillers, and a surfactant are mixed together to form a slurry mixture.

(2) An aqueous solution or aqueous dispersion of a phosphoric acid (a), preferably a resin (d), is mixed to prepare a premix 1
And then the metal oxide (b1) or hydroxide (b
2) A preliminary mixture 2 of the metal carbonate (c) and, if necessary, the inorganic filler is charged and mixed to form a slurry mixture.

(3) An aqueous solution or aqueous dispersion of phosphoric acid (a), preferably resin (d), is mixed with
And then the metal oxide (b1) or hydroxide (b
2) A slurry-like preliminary mixture 2 in which a metal carbonate (c), water and, if necessary, an inorganic filler are mixed is charged and mixed to form a slurry mixture.

Of the above procedures, it is preferable to employ the procedure (1) or (2) because the components can be uniformly mixed. In the case where the inorganic foam is continuously formed into a plate shape or another shape, a static mixer or a continuous stirring mixer capable of efficiently and continuously mixing the liquid raw material and the powder raw material, for example, It is preferable to use a spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.) or the like.

In the present invention, the temperature of the slurry-like mixture is lowered to -15 to 10 by lowering the temperature of the aqueous solution or dispersion of the phosphoric acid component (a) as described above.
C., but the temperature of the slurry mixture can also be controlled by controlling the temperature of the mixer described above. The temperature of the slurry mixture can be obtained by measuring the temperature of the slurry mixture when discharged from the mixer (in a batch system, the temperature of the slurry mixture in the batch after stirring).

Next, the obtained slurry-like mixture is formed into a precursor shape of a foamed product produced by, for example, the following method (a) or (b), and then, foaming and curing are advanced to form the mixture. And drying to obtain an inorganic foam molded article.

(A) The slurry-like mixture is flowed on a molding conveyor such as a resin belt conveyor, a steel conveyor, a slat conveyor or the like in synchronization with the conveyor, a film for a carrier or a skin material, a nonwoven fabric, a paper, a mat, etc. On top, continuously poured the slurry-like mixture, then, while smoothly casting the mixture on a flat surface, continuously foaming, after proceeding the curing, cut to a desired length and width, Heat to dry and completely cure.

After filling the slurry-like mixture into a mold or a frame having a desired shape and advancing the foaming hardening in the mold or the frame, the mold is removed or the frame is removed or dried by heating as it is. Let it cure completely.

When it is desired to obtain a plate-like inorganic foam molded product with high productivity from the above foaming-curing methods, it is preferable to employ the method (a). On the other hand, inorganic foams of various shapes are preferred. When it is desired to obtain a molded product, the method (b) is preferably employed.

In the above method, foaming and curing can proceed at room temperature, but may be carried out by heating to a temperature of 50 to 80 ° C. in consideration of productivity. Further, in the above-mentioned method, drying can be performed by a general hot-air oven or the like, and it is preferable to perform drying at a temperature in the range of 60 to 200 ° C., depending on the drying time. When the drying temperature is lower than 60 ° C., it takes time to remove moisture contained in the inorganic foam and complete the curing, and the productivity is deteriorated, and the curing of the phosphoric acid cured product and various resins is insufficient. In some cases, the physical properties of the foam are inferior. On the other hand, if the drying temperature exceeds 200 ° C., cracks in the foam due to rapid evaporation of water and deterioration of some of the resins used may occur. Therefore, the drying temperature is 80
It is particularly preferable that the temperature is in the range of from 150 to 150 ° C.

The inorganic foam molded article obtained by the production method of the present invention can be used for the same applications as conventional inorganic foams. For example, after being cut into a predetermined shape,
Core materials for doors and sandwich panels using fire-resistant coating materials for structural members such as steel, insulation and sound-absorbing materials used for buildings such as houses, equipment used for heating and cooling, warehouses, etc., or surface materials such as steel plates. And so on.

[0072]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but it is needless to say that the interpretation of the present invention is not limited by the examples. Example 1 50 mg of monobasic magnesium phosphate was added to tank A for supplying liquid raw material.
Mass% aqueous solution (a-1) and 50% of aluminum monophosphate
A mixture of a mass% aqueous solution (a-2) was prepared, and the liquid temperature was set at 0 ° C.
Held.

In the powder material supply tank B, magnesium oxide (b-1), aluminum hydroxide (b-2), wollastonite (b-3), basic magnesium carbonate (c-
A mixture of 1) and calcium carbonate (c-2) was prepared. The mixing ratio of each raw material is as shown in Table 1.

The two tanks A and B were simultaneously supplied to a spiral pin mixer (manufactured by Taiyo Kiko Co., Ltd.), which is a continuous stirring and mixing machine for powder and liquid, and stirred and mixed to obtain a slurry mixture. Next, the outlet of the spiral pin mixer (40mm
From (φ), the slurry mixture is discharged onto an inclined plate held at an angle of 45 ° from the horizontal plane,
cm, and discharged onto a PET (polyethylene terephthalate) nonwoven fabric placed on a belt conveyor moving at 1 m / min. The discharge rate from the spiral pin mixer was 4 kg / min, and the temperature of the slurry mixture at the discharge port was 6 ° C. At this time, the slurry-like mixture can be uniformly cast on the nonwoven fabric by controlling the temperature of the aqueous solution of phosphoric acid mixture as described above, so that the rising speed of foaming is reduced and the fluidity is improved. This is possible (see foam flow width in Table 1). The manufactured plate-shaped foam molded article had uniform and uniform foam cells. Thereafter, by heating and drying at 90 ° C. for 2 hours, the remaining purified water was volatilized.

Example 2 50 mg of monobasic magnesium phosphate was added to tank A for supplying a liquid raw material.
Mass% aqueous solution (a-1) and monobasic aluminum phosphate 50
A mixture of a mass% aqueous solution (a-2) was prepared, and the liquid temperature was set to -2.
C. was maintained.

In the liquid material supply tank B, the melamine resin
A 60% by mass aqueous solution (d-1) was prepared. Magnesium oxide (b-1), aluminum hydroxide (b-2), wollastonite (b-3), basic magnesium carbonate (c-1) and calcium carbonate (c)
-The mixture of 2) was prepared. Table 1 shows the mixing ratio of each raw material.
It is as follows.

A slurry mixture was obtained from the three tanks A, B, and C by simultaneously supplying the mixture to the spiral pin mixer and stirring and mixing in the same manner as in Example 1.
Next, the slurry mixture was discharged onto the inclined plate from the discharge port of the spiral pin mixer, and the mixture was similarly discharged for about 30 c.
m and then discharged onto a PET non-woven fabric on a belt conveyor moving at 1 m / min.

The discharge rate from the spiral pin mixer was 4 kg / min, and the temperature of the slurry mixture at the discharge port was 5 ° C. At this time, the slurry mixture is uniformly cast on the nonwoven fabric because the rising speed of foaming is reduced and the fluidity is improved by controlling the temperature of the phosphoric acid mixed aqueous solution in the same manner as in Example 1. (See foam flow width in Table 1).

The produced plate-like foam molded product had uniform and uniform foam cells. Thereafter, by heating and drying at 90 ° C. for 2 hours, the remaining purified water was volatilized. In addition,
The melamine resin (d-1) used in this example is a melamine and a 37% formalin aqueous solution in the presence of a basic catalyst, wherein the ratio of melamine to formaldehyde is 1 mol: 2.
The reaction is carried out so as to be 2 moles, and the colorless transparent liquid
% Aqueous solution.

Example 3 50 mg of monobasic magnesium phosphate was added to tank A for supplying a liquid raw material.
A mixture of a mass% aqueous solution (a-1) and an orthophosphoric acid 85 mass% aqueous solution (a-3) was prepared, and the liquid temperature was maintained at -3 ° C.

A urethane resin prepolymer (d-2) was prepared in the liquid material supply tank B. A mixture of magnesium oxide (b-1), aluminum hydroxide (b-2), basic magnesium carbonate (c-1) and calcium carbonate (c-2) was prepared in a powder material supply tank C. The mixing ratio of each raw material is as shown in Table 1.

In the same manner as in Example 1, the three tanks A, B, and C were simultaneously supplied to a spiral pin mixer and mixed by stirring to obtain a slurry mixture. Next, the slurry-like mixture is discharged from the discharge port of the spiral pin mixer onto the inclined plate, and is similarly allowed to flow down by about 30 cm, and further, a PET non-woven fabric on a belt conveyer moving at a moving speed of 1 m / min. Discharged upward.

The discharge rate from the spiral pin mixer was 4 kg / min, and the temperature of the slurry mixture at the discharge port was 5 ° C. At this time, the slurry mixture is uniformly cast on the nonwoven fabric because the rising speed of foaming is reduced and the fluidity is improved by controlling the temperature of the phosphoric acid mixed aqueous solution in the same manner as in Example 1. (See foam flow width in Table 1).

Thereafter, by heating and drying at 90 ° C. for 2 hours, the remaining purified water was volatilized, and the produced plate-like foam molded product had uniform and uniform foam cells. In comparison with the above, it was less brittle and flexible.

The urethane resin prepolymer (d-2) used in this example is as follows. [TDI
-80; manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate T-80] 100 parts by mass of polyoxyethylene polyoxypropylene glycol [molecular weight 2188,
A prepolymer obtained by reacting 420 parts by mass of a block copolymer of 80% by mass of ethylene oxide and 20% by mass of propylene oxide. Prepolymer NCO
A resin solution having a content of 6.2% by mass and a number average molecular weight of 1355, which is viscous at room temperature.

Example 4 50 mg of monobasic magnesium phosphate was added to tank A for supplying a liquid raw material.
Mass% aqueous solution (a-1) and monobasic aluminum phosphate 50
Prepare a mixture with the aqueous solution (a-2) by weight, and adjust the liquid temperature to −
It was kept at 3 ° C.

A 67% by weight mixed aqueous solution (d-3) of an epoxy resin and a curing agent was prepared in a liquid material supply tank B. Incidentally, this epoxy resin mixed aqueous solution was mixed and adjusted immediately before mixing all the raw materials.

In the powder material supply tank C, magnesium oxide (b-1), aluminum hydroxide (b-2), basic magnesium carbonate (c-1) and calcium carbonate (c-
The mixture of 2) was prepared. The mixing ratio of each raw material is as shown in Table 1.

In the same manner as in Example 1, the three tanks A, B, and C were simultaneously supplied to the spiral pin mixer and mixed by stirring to obtain a slurry mixture. Next, the slurry-like mixture is discharged from the discharge port of the spiral pin mixer onto the inclined plate, and is also allowed to flow down by about 30 cm, and further on the PET non-woven fabric on a belt conveyor that is moved at a moving speed of 1 m / min. Was discharged.

The discharge rate from the spiral pin mixer was 4 kg / min, and the temperature of the slurry mixture at the discharge port was 5 ° C. At this time, the slurry mixture is uniformly cast on the nonwoven fabric because the rising speed of foaming is reduced and the fluidity is improved by controlling the temperature of the phosphoric acid mixed aqueous solution in the same manner as in Example 1. (See foam flow width in Table 1).

After that, by heating and drying at 90 ° C. for 2 hours, the remaining purified water was volatilized, and the produced plate-like foam molded article had uniform and uniform foam cells. It was superior in bending strength and compressive strength as compared with.

The epoxy resin (d-3) used in this example was prepared by adding polyoxyethylene polyoxypropylene glycol to a bisphenol A type epoxy resin and then emulsifying with water at an epoxy equivalent of 250% by mass. Concentration emulsion. The curing agent is triethylenetetramine, and the epoxy resin mixed aqueous solution contains the epoxy resin emulsion and the curing agent in 10:
2 mixed.

Comparative Example 1 A slurry-like mixture was discharged from the discharge port of a spiral pin mixer onto the inclined plate in the same manner as in Example 1 except that the temperature of the aqueous phosphoric acid mixed solution was maintained at 20 ° C. Similarly, it was allowed to flow down by about 30 cm, and then discharged onto a PET non-woven fabric on a belt conveyor moving at a moving speed of 1 m / min.

The discharge rate from the spiral pin mixer was 4 kg / min, and the temperature of the slurry mixture at the discharge port was 27 ° C. At this time, the slurry-like mixture had already begun to foam at the discharge port of the spiral pin mixer, had poor fluidity, and could not be uniformly cast on the inclined plate and the nonwoven fabric ( Table: Foaming liquid flow width).

Thereafter, the resultant was dried by heating at 90 ° C. for 2 hours to evaporate the residual water. Since the produced foam molded product did not have sufficient fluidity at the time of slurry, the foam cells were non-uniform and had a bulky shape with non-uniform thickness. Further, compared to the foam of Example 1, uniform physical properties could not be obtained.

Example 5 In Example 3, the solution temperature of the phosphoric acid mixed aqueous solution was changed to −3 ° C.
And the slurry mixture was placed on the inclined plate from the outlet of the spiral pin mixer in the same manner as in Example 1 except that zinc oxide (b-4) was used instead of magnesium oxide (b-1). In the same manner, the mixture was allowed to flow down by about 30 cm, and further discharged onto a PET non-woven fabric on a belt conveyor moving at a moving speed of 1 m / min.

The discharge rate from the spiral pin mixer was 4 kg / min, and the temperature of the slurry mixture at the discharge port was 5 ° C. At this time, the slurry mixture is uniformly coated on the nonwoven fabric by controlling the temperature of the aqueous solution of phosphoric acid mixture in the same manner as in Example 1, so that the rising speed of foaming is reduced and the fluidity is improved. (Refer to the flow width of the foaming liquid in Table 1). Then 90 ° C
By heating and drying for 2 hours, the remaining purified water was volatilized. In the manufactured plate-like foam molded article, the foam cells were slightly inferior in uniformity.

Example 6 The same procedure as in Example 3 was carried out except that urea was added, and the temperature of the aqueous solution of phosphoric acid mixture was kept at 3 ° C., and the slurry mixture was discharged from the outlet of the spiral pin mixer.
Discharge on the inclined plate, and let it flow down about 30 cm in the same way,
Further, PET (polyethylene terephthalate) on a belt conveyor that moves at a moving speed of 1 m / min installed under it
It was discharged on a nonwoven fabric.

The discharge rate from the spiral pin mixer was 4 kg / min, and the temperature of the slurry mixture at the discharge port was 8 ° C. At this time, the slurry mixture is uniformly coated on the nonwoven fabric by controlling the temperature of the aqueous solution of phosphoric acid mixture in the same manner as in Example 1, so that the rising speed of foaming is reduced and the fluidity is improved. (Refer to the flow width of the foaming liquid in Table 1). Then 90 ° C
By heating and drying for 2 hours, the remaining water is volatilized,
The manufactured plate-like foam molded article had uniform and uniform foam cells.

Example 7 In exactly the same manner as in Example 3, a spiral pin mixer (manufactured by Taiyo Kiko Co., Ltd.) as a continuous stirring mixer for powder and liquid was used.
A slurry-like mixture was obtained. Next, the slurry-like mixture was dropped by about 30 cm at a discharge rate of 1 kg / min from the discharge port (40 mmφ) of the spiral pin mixer, and a rectangular parallelepiped metal of 30 × 20 cm × 10 cm in height with the upper surface opened. The slurry mixture having a temperature of 6 ° C. was discharged into a mold, and after foaming and curing, the metal mold was removed to produce a block-shaped foam molded article.

Since the slurry-like mixture had good fluidity, it was uniformly filled on the bottom surface of the metal mold, foaming proceeded after filling, and the foam was filled up to the corners of the metal mold. The manufactured foam molded article had a high-precision shape, and its foam cells were uniform and ordered.

Comparative Example 2 The same procedure as in Example 8 was carried out except that the temperature of the slurry mixture was changed to 25 ° C. by changing the aqueous solution of phosphoric acid mixture to 18 ° C.
Was performed in the same manner as described above. Further, the slurry mixture was discharged into the same metal mold as in Example 8 to produce a foam molded product. Such a slurry-like mixture was inferior in fluidity, and was not uniformly filled on the bottom surface of the metal mold, and foaming proceeded, so that the foam was not filled up to the corner of the metal mold. The manufactured foam molded product has low shape accuracy,
And the foam cells were not uniform.

Regarding the foam molded products obtained in the above Examples and Comparative Examples, (1) foaming end time, (2) curing end time, (3) fluidity, (4) filling uniformity, (5) heat insulation sex,
(6) The falling off property of the foam was evaluated. Table 1 shows the results.
Shown in In addition, the evaluation method of the said item is as follows. (1) Time until foaming of the slurry-like mixture was completed The time from when the slurry-like mixture was discharged from the spiral pin mixer until it gradually rose and reached the upper limit in the thickness direction was visually measured. (2) Time Until Hardening of Slurry Mixture Completed The time from the discharge of the slurry mixture from the spiral pin mixer until the foam surface became tack-free was measured by touch. (3) Fluidity of the slurry mixture The slurry mixture discharged from the spiral pin mixer flowed down the inclined plate, and the width of the liquid surface diffused on the conveyor was measured. (4) Density of foam molded article Measured according to JIS A1412. (5) Appearance of foam molded article The uniformity, cracks, cracks, etc. of foam cells were visually evaluated. (6) Thermal conductivity of foam molded article Measured according to JIS A1412.

[0104]

[Table 1]

According to the present invention, an inorganic foam molded article having excellent heat insulating properties, mechanical properties, water resistance, etc., and having a uniform and high-precision shape and dimensions can be produced. More specifically, when a sheet-shaped or board-shaped inorganic foam molded article having a uniform thickness and density is used, and even when an irregular-shaped inorganic foam molded article is manufactured using a mold, a predetermined high precision is also required. A foam molded article having the shape and dimensions of above is obtained, and the produced foam molded article has a non-uniform distribution state and density of bubbles in the foam, heat insulation properties, mechanical properties and water resistance. Excellent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08K 3/22 C08K 3/22 3/26 3/26 3/32 3/32 3/34 3/34 5 / 21 5/21 7/04 7/04 C08L 61/00 C08L 61/00 63/00 63/00 C 75/04 75/04 101/00 101/00 (72) Inventor Koichi Shigeno Kanda, Chiyoda-ku, Tokyo 3-6, Kajicho 3 Asahi Fiberglass Co., Ltd. F-term (reference) 4F074 AA58 AA63 AA64 AA78 AA80 AA97 AC17 AC19 AC20 AC24 AC26 AC27 AC31 AC34 AC36 AD13 AE04 AG01 AG10 AH04 BA02 BA03 BA04 BC11 CA22 CA23 CC23X 4G012 PA07 PA10 PA14 PA15 4G052 FA01 FA07 FA08 FB01 FB31 4G056 AA06 AA13 CA04 CD51 4J002 AA021 CC041 CC051 CC061 CC161 CC171 CC181 CC191 CD051 CD061 CD081 CD101 CK031 CK041 CK051 DE047 DE067 DE077 DE087 DE147 DE157DE157 DE117DE157 DE117 DE117 DE117 DE117 DE117 DE157 DE117 DE117 DE117 DE157 DE117 DE117 DE157 DE117 DE157 DE157 DE157 DE117 DE157 DE157 DE157 DE117 DE157 DE157 DE117 DE157 DE157 DE157 DE157 DE157 DE157 DE157 DE157 DE157 DE157 DE117 DE157 DE157 DE157 DE157 DE117 DE157 DE157 DE117 DE157 9 ET019 EW046 FA049 FD138 FD140 FD150 FD310 GL00 HA06

Claims (12)

[Claims] 1. A foam molded article produced by mixing the following components (a) to (c) to obtain a slurry-like mixture adjusted so that the temperature immediately after mixing is -15 to + 10 ° C. A method for producing a molded article of inorganic foam, characterized in that the foamed article is formed by forming the foam into a precursor shape and then proceeding with foaming and curing. (A) an aqueous solution or aqueous dispersion of phosphoric acids; (b) an oxide (b1) or hydroxide (b2) of a metal selected from Group 2 of the periodic table, Group 13 of the periodic table, Group 14 of the periodic table, and a transition metal , (C)
Metal carbonates. 2. The composition according to claim 1, further comprising (d)
The production method according to claim 1, wherein the slurry-like mixture is produced by mixing a thermosetting resin and, if necessary, a curing agent component of the thermosetting resin. 3. When the slurry mixture is obtained, the components (b) and (c) are used in a total amount of 40 to 100 parts by mass with respect to 100 parts by mass of the component (a). Or the production method according to 2. 4. The slurry-like mixture is produced by adjusting the temperature of the component (a) to a temperature of -20 to + 5 ° C. and mixing the components with the components (b) and (c). The production method described in 1. 5. The phosphoric acid constituting the component (a) is at least one selected from orthophosphoric acid, magnesium monophosphate, aluminum monophosphate and zinc monophosphate.
The production method according to any one of claims 1 to 4, which is a seed. 6. The component (b) is an oxide (b1) or a hydroxide (b2) of a metal belonging to Group 2 of the periodic table.
The production method according to any one of the above. 7. The production method according to claim 6, wherein the oxide (b1) or the hydroxide (b2) of a metal belonging to Group 2 of the periodic table is contained in at least 5% by mass of all the components (b). 8. The method according to claim 1, wherein the component (c) is a carbonate selected from at least one selected from magnesium and calcium. 9. The method according to claim 1, wherein the component (d) is any one of an isocyanate, an aldehyde-based condensation resin and an epoxy resin.
The method according to any one of claims 2 to 8, which is one. 10. The slurry according to claim 1, wherein the slurry-like mixture contains 0.1 to 10 parts by mass of urea based on 100 parts by mass of phosphoric acid constituting component (a). Manufacturing method according to any one of the above. 11. The method according to claim 1, wherein the slurry-like mixture contains inorganic fibers, cement, or lightweight aggregate. 12. The process according to claim 1, wherein the slurry-like mixture is cast into a flat form or filled in a mold to form a precursor of the foam. Method.