JPH11181137A - Inorganic/organic composite foam and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a foam which does not disintegrate even on exposure to a flame and has flexibility and resiliency by improving the inherent brittleness of a foamed structure comprising a phosphoric acid and a metal carbonate with the aid of a cured product of an NCO-containing urethane prepolymer and incorporating a water-soluble inorganic metal salt compound having a specified or higher water solubility in the structure. SOLUTION: This foam is prepared by improving the inherent brittleness of a foamed structure comprising a phosphoric acid (salt) (e.g. aluminum primary phosphate), desirably, at least one member selected among (anhydrous) phosphoric acid, phosphorous acid, condensed phosphoric acid, and a polyvalent metal salt thereof and a metal carbonate (e.g. basic magnesium carbonate) with the aid of a cured product of an NCO-containing urethane prepolymer (e.g. a prepolymer obtained from toluene diisocyanate, polyoxyethylene polyoxypropylene glycol) and incorporating a water-soluble inorganic metal salt compound, desirably, a metal borate, having a water solubility of 3.0 g/100 g or above at 20 deg.C and, optionally another inorganic filler in the structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an inorganic-organic composite foam and a method for producing the same. More specifically, it is an inorganic-organic composite foam having an inorganic foam structure, and whose brittleness is remarkably improved by a reactive elastic polymer, and having flexibility and resilience such as urethane foam and styrene foam. The present invention relates to an inorganic-organic composite foam which can be made comparable to a certain foam and also has fire prevention performance, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, foams of phosphoric acids have been proposed as inorganic foams capable of forming foams under normal temperature and normal pressure conditions (for example, Japanese Patent Publication No. 56-36145). The foam described in this publication is obtained by stirring and mixing a phosphoric acid such as a metal phosphate and a blowing agent such as a polyvalent metal carbonate, and foaming and curing the foam. Because it has, not only fixed materials such as panels,
It can be positioned as an unprecedented superior material, for example, it can be applied to an irregular-shaped filler for filling an opening. (1) The obtained foam is excellent in nonflammability and fire resistance. (2) In the production of foam, specific gravity can be easily controlled in a wide range.

[0003] However, the phosphoric acid foam is fragile because it is a completely inorganic material, and has a drawback that the foam is destroyed even with a small force and cannot be restored. In this case, there are problems such as the surface layer collapsing just by touching, and the panel strength is too weak to carry.
The material was not practical.

As a means for improving the disadvantages of such foams of phosphoric acids, a method of adding a urethane prepolymer to the system has been proposed (for example, Japanese Patent Application Laid-Open No. 9-1570).
No. 61). In this method, the strength of the foam is improved by adding a urethane prepolymer that does not impair the excellent incombustibility and heat resistance that are characteristic of the foam of phosphoric acid, and the foam is practically used even in a low-density foam. A material excellent in the above can be obtained.

[0005]

However, although the strength of the foam of phosphoric acid has been greatly improved by the addition of the urethane prepolymer, the strength of the foam when exposed to a flame is weak, and the strength of the foam during exposure to the flame is low. There was a problem that the foam collapsed.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems of the conventional foams of phosphoric acids, and as a result, have found that the foams of phosphoric acids reinforced by the urethane prepolymer have been developed. Thus, a foam to which a specific inorganic metal salt was added was obtained. Further, as a result of the study by the present inventors, it has been found that when these inorganic metal salts are used, the obtained foam does not collapse even when exposed to a flame.

That is, the present invention relates to a phosphoric acid foam structure comprising phosphoric acid (a) and metal carbonate (b),
A water-soluble inorganic metal salt compound (d) whose brittleness is improved by a cured product of the urethane prepolymer (c) having a CO group and which has a solubility in water at 20 ° C. of 3.0 g / 100 g or more, and An inorganic-organic composite foam containing another inorganic filler (e) as required.
The present invention also relates to phosphoric acids (a), metal carbonates (b),
Urethane prepolymer (c) having NCO group, 20 ° C
Is a water-soluble inorganic metal salt compound (d) having a water solubility of 3.0 g / 100 g or more, and an inorganic-organic composite foam which is foamed and cured by mixing water.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The inorganic-organic composite foam of the present invention (hereinafter referred to as "foam of the present invention") is an inorganic foam formed by reacting phosphoric acid (a) with metal carbonate (b). The urethane prepolymer (c) having a body structure and having an NCO group has improved brittleness, and has a water-soluble inorganic metal salt compound (d) having a solubility in water at 20 ° C. of 3.0 g / 100 g or more. The foam strength when exposed is improved. The above metal carbonate (b)
Reacts with the phosphoric acids (a) to form an inorganic skeleton and, at the same time, generates carbon dioxide. This carbon dioxide causes foaming. The urethane prepolymer (c) is a reactive elastic polymer and has an NCO group reactive with a compound having active hydrogen such as water.

In the method for producing a foam of the present invention, the brittleness of the foam is improved by an elastic polymer formed by the reaction and curing of the urethane prepolymer (c). The water-soluble inorganic metal salt compound (d) improves the strength of the foam when exposed to a flame.

In the present invention, the above-mentioned phosphoric acids (a) are not particularly restricted but include, for example, phosphoric acid, phosphorous acid, phosphoric anhydride, condensed phosphoric acid, polyvalent metal salts thereof, and two or more of these. Mixtures and the like can be mentioned. Examples of the polyvalent metal salts of phosphoric acid include polyvalent metal salts of primary phosphoric acid, polyvalent metal salts of dibasic phosphate, and polyvalent metal salts of tertiary phosphate. Examples of the metal constituting the polyvalent metal salt include magnesium, calcium, aluminum, zinc, barium, iron and the like. These polyvalent metal components may be added in the form of a polyvalent metal salt of phosphoric acid, a polyvalent metal salt of phosphite, etc.
Phosphorous acid and chemically active metal compounds, for example, magnesium oxide, polyvalent metal oxides such as calcium oxide, aluminum hydroxide gel, magnesium hydroxide, polyhydric metal hydroxides such as calcium hydroxide, etc. , Phosphoric acid, phosphorous acid, etc. may be separately added to the system and reacted in the system.

Among the above-mentioned phosphoric acids (a), preferred are phosphoric acid, magnesium monophosphate, aluminum monophosphate, zinc monophosphate and a mixture of two or more of these. Preferred are phosphoric acid, magnesium monophosphate, aluminum monophosphate and mixtures of two or more thereof.

The content of the above-mentioned phosphoric acid (a) is usually 3 to 50% by weight based on all components constituting the foam of the present invention, and the content of phosphorus atom in the foam of the present invention Speaking of a preferable range converted to 3 to 20% by weight, especially 4 to 1%
8% by weight. When the content of the phosphorus atom is less than 3% by weight, the fire prevention performance of the obtained foam decreases. When the content of the phosphorus atom exceeds 20% by weight, the dispersibility of the urethane prepolymer (c) is reduced, and a uniform foamed structure may not be obtained.

As the above metal carbonate (b), for example,
Examples include calcium carbonate, basic magnesium carbonate, basic zinc carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate and the like. The amount of the metal carbonate (b) may be determined according to a desired expansion ratio in a wide range from soft to hard. The amount of the metal carbonate (b) is not particularly limited as long as the phosphoric acid (a) and the metal carbonate (b) are mixed well when mixed with the phosphoric acid (a).
For 100 parts by weight, usually 0.1 to 200 parts by weight,
Preferably it is 1 to 100 parts by weight.

Further, other foaming agents may be used in combination with the metal carbonate (b). As another foaming agent, the urethane prepolymer (c) may generate carbon dioxide gas by water in the system to be a part of foaming. Organic foaming agents (for example, nitroso foaming such as dinitrosopentamethylenetetramine and N, N'-dimethyl-N, N'-dinitrosoterephthalamide) which decompose by heating in the urethane prepolymer (c). Agents: Sulfohydrazide foaming agents such as benzenesulfonylhydrazide azodicarbonamide, p-toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide-3-3'-disulfohydrazide diphenyl sulfone; azobisisobutyronitrile Azo foaming agents such as azobisformamide, diethyl azodicarboxylate, etc.), and secondary foaming by heating. Alternatively, a carbonate compound such as ammonium carbonate may be used in combination. Good.

In the present invention, examples of the urethane prepolymer (c) include those derived from an organic polyisocyanate compound (n) and an active hydrogen-containing compound (h) and having NCO in the molecule. No. Examples of the organic polyisocyanate compound (n) include the following (n1) to (n5).
However, the carbon number in (n1) to (n5) is a value excluding the carbon number in the NCO group. (N1): an aliphatic polyisocyanate having 2 to 12 carbon atoms (n2): an alicyclic polyisocyanate having 4 to 15 carbon atoms (n3): an araliphatic polyisocyanate having 8 to 12 carbon atoms (n4): a carbon number 6 to 20 aromatic polyisocyanate (n5): Modified polyisocyanate of (n1) to (n4)

Specific examples of the above aliphatic polyisocyanate (n1) include: ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexa. Methylene diisocyanate, • lysine diisocyanate, • 1,3,6-hexamethylene triisocyanate.

Specific examples of the alicyclic polyisocyanate (n2) include:-isophorone diisocyanate (IPDI),-dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), and 1,4-cyclohexane diisocyanate. • Methylcyclohexane-2,4-diisocyanate (hydrogenated TDI), • 1,4-bis (2-isocyanatoethyl) cyclohexane and the like.

The araliphatic polyisocyanate (n)
Specific examples of 3) include: p-xylylene diisocyanate, tetramethyl xylene diisocyanate, and the like. Specific examples of the aromatic polyisocyanate (n4) include: 1,4-phenylenediisocyanate, 2,4- or 2,6-toluene diisocyanate (T
DI), diphenylmethane-2,4 'or 4,4'-diisocyanate (MDI), naphthalene-1,5-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, crude TDI, Polyphenylmethane polyisocyanate (commonly called crude MDI. Condensate of aromatic amine such as aniline or a mixture thereof with formaldehyde (diaminodiphenylmethane and a small amount, for example, 1 to 20% by weight of a polyamine having three or more amino groups And phosgenated compounds).

Specific examples of the modified polyisocyanate (n5) of the above (n1) to (n4) include, for example, (n
Modified products in which a carbonamide group, uretdione group, uretoimine group, urea group, buret group, isocyanurate group, urethane group, etc. are introduced instead of the isocyanate group of the polyisocyanate exemplified above as 1) to (n4). And the like.

The selection of the organic polyisocyanate compound (n) is not particularly limited, and is used alone or in any combination as a component for deriving the urethane prepolymer (c) according to the physical properties and cost of the foam. be able to.

As the active hydrogen-containing compound (h),
For example, a low molecular weight polyol (h1) and a high molecular weight polyol (h2) can be mentioned. Here, when the ranges of the molecular weights of the above (h1) and the above (h2) are represented by hydroxyl values, the hydroxyl value of (h1) is usually 300 to
It is 1000 or more, preferably 350-800. The hydroxyl value of (h2) is usually less than 300, preferably 20-250, especially 50-200. Further, the number of functional groups of the active hydrogen-containing compound (h) is usually 2 to 8 or more in any of the above (h1) and (h2).

Examples of the low molecular weight polyol (h1) include the following (h1-1) to (h1-6). (H1-1): Aliphatic dihydric alcohols (h1-2): Low molecular weight diols having a cyclic group (h1-3): Trihydric alcohols (h1-4): Polyhydric alcohols having four or more functional groups (H1-5): Alkanolamines (h1-6): Low molar addition product of the above compounds (h1-1) to (h1-5) with ethylene oxide and / or propylene oxide

Examples of the high molecular weight polyol (h2) include the following (h2-1) to (h2-6). (H2-1): Polyoxyalkylene polyol (h2-2): Polyester polyol (h2-3): Polyolefin polyol (h2-4): Acrylic polyol (h2-5): Castor oil-based polyol (h2-6): Polymer polyol

Of the low molecular weight polyol (h1),
Specific examples of the aliphatic dihydric alcohols (h1-1) include, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol,
1,4-butanediol, neopentyl glycol,
Examples include 1,6-hexanediol and 1,8-octamethylenediol. Specific examples of the low molecular weight diols (h1-2) having a cyclic group include, for example, 1,4
-Bis (2-hydroxyethoxyphenyl) propane and the like. Specific examples of the trihydric alcohols (h1-3) include, for example, glycerin, trimethylolpropane, hexanetriol and the like.

The above-mentioned tetrafunctional or higher polyhydric alcohols (h1
Specific examples of -4) include sorbitol and shoe rose. Specific examples of the alkanolamines (h1-5) include, for example, triethanolamine, methyldiethanolamine and the like.
Specific examples of the low molar adduct (h1-6) include, for example, those exemplified as (h1-1) to (h1-5), and ethylene oxide and / or propylene oxide, And those having a low molarity in the range of 300 or more.

Of the above high molecular weight polyols (h2),
Examples of the polyoxyalkylene polyol (h2-1) include the compounds (h1-1) to (h1-5) described in the section of the low molecular weight polyol (h1), low molecular amines, and polyhydric phenols. And the like, to which an alkylene oxide has been added. Examples of the low molecular amines include low molecular polyamines such as ethylenediamine, tetramethylenediamine, and hexamethylenediamine, and low molecular monoamines such as nbutylamine and stearylamine. Examples of the polyhydric phenols include hydroquinone, bisphenol A, bisphenol F, bisphenol S and the like. As the alkylene oxide added to these, for example,
Examples thereof include alkylene oxides having 2 to 4 carbon atoms, for example, ethylene oxide, propylene oxide, butylene oxide, and a combination thereof (in the case of a combination, block or random addition may be used).

The above polyoxyalkylene polyol (h
Specific examples of 2-1) include, for example, polyoxypropylene glycol, polyoxypropylene triol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene triol, polyoxypropylene tetraol, polyoxytetramethylene glycol, and the like. Is mentioned.

The above polyester polyol (h2-2)
For example, the following (h2-21) to (h2-2)
3) and the like. (H2-21): Condensed polyester polyol obtained by reacting difunctional or higher polyhydric alcohol with dicarboxylic acid (h2-22): Polylactone polyol obtained by ring-opening polymerization of lactone (h2-23): Polycarbonate polyol obtained by reacting ethylene carbonate with 1,6-hexanediol

The above condensed polyester polyol (h2-
Examples of the dicarboxylic acids constituting 21) include:-aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.);-aromatic dicarboxylic acids (terephthalic acid, Isophthalic acid, etc.), anhydrides of these dicarboxylic acids, lower alkyl (1 to 4 carbon atoms) esters or acid halides (acid chlorides, etc.), and mixtures of two or more of these. The above polylactone polyol (h2-
Examples of the lactone used in 22) include ε-caprolactone.

The above polyester polyol (h2-2)
Specific examples of, for example, polyethylene adipate,
Polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene polypropylene adipate, polyethylene butylene adipate, polybutylene hexamethylene adipate, polydiethylene adipate, poly (polytetramethylene ether) adipate, polyethylene azelate, polyethylene sebacate, poly Butylene azelate, polybutylene sebacate, polyethylene terephthalate, polycaprolactone diol, polycarbonate diol and the like.

The above polyolefin polyol (h2-
Specific examples of 3) include, for example, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, and the like. Specific examples of the acrylic polyol (h2-4) include, for example, a copolymer of hydroxyethyl acrylate and ethyl acrylate,
Examples include a copolymer of hydroxyethyl acrylate, ethyl acrylate and styrene.

Examples of the castor oil-based polyol (h2-5) include: (h2-51): castor oil (h2-52): polyester polyol of castor oil fatty acid with polyhydric alcohol or polyoxyalkylene polyol, and And a mixture of two or more of the above. Specific examples of the above (h2-52) include, for example, mono, di or triester of castor oil fatty acid and trimethylolpropane; mono or diester of castor oil fatty acid and polyoxypropylene glycol.

Examples of the polymer polyol (h2-6) include, among the high molecular weight polyols exemplified as (h2-1) to (h2-5), ethylenically unsaturated monomers such as acrylonitrile and styrene. And the like obtained by polymerizing (US Pat. No. 3,383,351). The content of the ethylenically unsaturated monomer unit constituting the polymer polyol (h2-6) is usually
It is 0.1 to 90% by weight, preferably 5.0 to 80% by weight. Examples of the method for producing the polymer polyol (h2-6) include a method of polymerizing an ethylenically unsaturated monomer in a polyol in the presence of a polymerization initiator (such as a radical generator) (for example, US Pat. No. 3,383,351). The method described in Japanese Patent Application Laid-Open (JP-A) no.

Among the compounds exemplified above in detail as the active hydrogen-containing compound (h), particularly preferred are the ethylene oxide adducts of the polyoxyalkylene polyol (h2-1). It is preferably used as a part of the active hydrogen-containing compound (h). In this case, the active hydrogen-containing compound (h)
In terms of the content of oxyethylene units,
% By weight, especially 50 to 90% by weight. By using the ethylene oxide adduct, the dispersibility of the urethane prepolymer (c) in the aqueous mixture is improved.

The low molecular weight polyol (h1) and the high molecular weight polyol (h2) may be used alone or in combination. The use ratio of the above (h1) and the above (h2) is not particularly limited. For example, in order to make the effect of improving the brittleness of the foam higher, or to make the effect of imparting flexibility higher, (H1) :( h2) by weight ratio
= (0-50): (50-100) so that (h
It is better to increase the use ratio of 2). On the other hand, in order to further increase the rigidity of the foam, the weight ratio is (h1) :( h
2) = (50-100): (0-50)
It is preferable to increase the usage ratio of (h1).

In order to adjust the molecular weight and viscosity of the urethane prepolymer (c), a monool (h3) may be used as a component (h), if necessary. Examples of the monol (h3) include:-aliphatic monohydric alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, 2-ethylhexanol and dodecanol;-alkylenes of alkylphenols (octylphenol, nonylphenol, dodecylphenol and the like). Oxide (ethylene oxide, propylene oxide, etc.)
Adducts and the like. The molecular weight of the monol (h3) is usually in the same range as (h1) or (h2).
The proportion of the monol (h3) in the active hydrogen compound (h) is such that the average number of functional groups in the active hydrogen compound (h) is usually
It is in the range of 2 or more, preferably 2.5 or more.

NC in the urethane prepolymer (c)
The O content is preferably between 0.5 and 30% by weight. The properties of the urethane prepolymer (c) are not particularly limited, but are preferably liquid at room temperature and have a certain molecular weight and molecular composition. The molecular weight of the urethane prepolymer (c) is preferably 1,000-5
It is 0000. As an example of the method for producing the urethane prepolymer (c), for example, an organic polyisocyanate (n) and an active hydrogen-containing compound (h) are charged into a reaction vessel,
It can be produced by reacting at a reaction temperature of 50 to 120 ° C. The content of the urethane prepolymer (c) unit in the foam of the present invention, that is, the content of the urethane prepolymer (c) based on the total solid content during the production of the foam is 5 to 30.
% By weight, especially 10 to 25% by weight.

As the water-soluble inorganic metal salt compound (d), for example, sodium metaborate, sodium tetraborate,
Sodium borate compounds such as sodium pentaborate, sodium hexaborate, sodium octaborate, and sodium borate; and potassium borate compounds such as potassium metaborate, potassium borate, potassium pentaborate, potassium hexaborate, and potassium octaborate. Among these, a sodium borate compound is preferable, and sodium octaborate is more preferable.

The amount of the water-soluble inorganic metal salt compound (d) to be used is generally 1 to 50% by weight, preferably 5 to 40% by weight, based on all components constituting the foam.

The foam of the present invention may optionally contain an inorganic filler (e) in consideration of physical properties and cost. As the inorganic filler (e), for example, the following (e)
1) to (e4). (E1) Cement: Portland cement, silica cement, alumina cement, blast furnace cement, fly ash cement, white cement, etc. (e2) Clay minerals: montmorillonite, bentonite,
Mica, sericite, kaolin, talc, philite, zeolite, etc. (e3) Inorganic lightweight aggregate: perlite, shirasu balloon, etc. (e4) Other water-insoluble inorganic powder materials: fly ash, silica fume, silica stone powder, ceramic powder, Aluminum hydroxide, alumina, calcium sulfate, etc.

The selection of the inorganic filler (e) exemplified above in detail is not particularly limited, and the physical properties of the foam,
It may be added alone or in any combination according to the requirements such as cost. The addition amount of the inorganic filler (e) is not particularly limited, and is usually 1800 parts by weight or less, preferably 500 parts by weight or less based on 100 parts by weight of the phosphoric acid (a).

In the present invention, the amount of water is determined by mixing a component consisting of phosphoric acid (a), metal carbonate (b), urethane prepolymer (c), water-soluble inorganic metal salt compound (d) and water. At this time, it is not necessary to add more water than necessary, as long as the slurry can be made into a water slurry. The more water there is, the more time and effort it takes to dry the foam-cured one. The amount of water is not particularly limited, but usually the concentration of the mixture is 50 to
The amount is about 90% by weight.

In the production method of the present invention, in order to control the curing rate of the urethane prepolymer (c), for example, a catalyst may be added. Examples of the above catalyst include: dibutyltin dilaurate, alkyl titanate, organosilicon titanate, stannas octoate, lead octylate, zinc octylate, bismuth octylate, dibutyltin diorthophenylphenoxite, tin oxide A metal-based catalyst such as a reaction product of a compound with an ester compound (such as dioctyl phthalate); monoamines (such as triethylamine), diamines (such as N, N, N ', N'-tetramethylethylenediamine), and triamines (such as N , N, N ', N ", N"-
Amine-based catalysts such as pentamethyldiethylenetriamine and cyclic amines (such as triethylenediamine). The catalyst may be used alone or in combination of a metal or an amine, or a combination of a metal and an amine. The amount of the catalyst is usually 10 parts by weight or less, preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the urethane prepolymer (c).

In the production method of the present invention, in order to control the cell structure of the foam, a foam stabilizer may be added. Examples of the foam stabilizer include conventionally known silicone-based activators. Examples thereof include: SH-192 and SH-19 manufactured by Toray Silicone Co., Ltd.
3, SH-194, etc .; TFA-4200, manufactured by Toshiba Silicone Co., Ltd .; L-5320, L-5340, L, manufactured by Nippon Unicar Co., Ltd.
-5350 and the like;-F-121 and F-122 manufactured by Shin-Etsu Chemical Co., Ltd. and the like. The amount of the foam stabilizer to be added is usually 3 parts by weight or less, preferably 0.001 to 1 part by weight, based on 100 parts by weight of the urethane prepolymer (c).

In the production method of the present invention, there are various methods as exemplified in the following [1] to [6] as a method of foaming and curing by mixing each component. [1] A method in which phosphoric acid (a), metal carbonate (b), urethane prepolymer (c), water-soluble inorganic metal salt (d) and water are added at once, mixed, and foam-cured. [2] A method of mixing phosphoric acid (a), the urethane prepolymer (c) and water, then adding the metal carbonate (b) and the water-soluble inorganic metal salt (d) together, mixing, and foaming and curing. . [3] Phosphoric acid (a) mixed with the urethane prepolymer (c), and then slurried by previously mixing the metal carbonate (b), the water-soluble inorganic metal salt (d) and water. And mixing and foaming and curing. [4] After mixing the phosphoric acid (a), the urethane prepolymer (c) and a part of water, the metal carbonate (b) and the water-soluble inorganic metal salt (d) are previously mixed with the rest of the water. A method in which a slurry is formed, mixed, and foamed and hardened. [5] A method of mixing phosphoric acid (a), the above-mentioned water-soluble inorganic metal salt (d), and water, then putting in a metal carbonate (b) and the above-mentioned urethane prepolymer (c), mixing and foam-curing. [6] A method in which phosphoric acid (a), the urethane prepolymer (c), the water-soluble inorganic metal salt (d), and water are mixed, and then the metal carbonate (b) is mixed and foamed and cured. Of these, [1], [2],
[4] and [6].

According to the production method of the present invention,
The foam of the present invention is obtained by mixing and resting the components according to the above method. The mixed solution (slurry)
After standing, it foams within a few minutes to several tens of minutes, and then the curing is completed to form a foam. However, in winter, when the temperature is low, or when it is desired to shorten the foam hardening time in the process, heating may be performed to about 50 ° C. during the standing.

According to the production method of the present invention, the foam of the present invention can be formed by pouring the mixture into a mold and molding.
The foam of the present invention can be applied to an arbitrary substrate such as a wall surface or filled in an arbitrary space. In the case of a molded body, a foam may be formed by a method exemplified above using a mold having an arbitrary shape (for example, a mold of a large panel). In the case of application, the mixture obtained by the above method may be applied by spraying or trowel application to form a foam.

In the production method of the present invention, the specific gravity of the foam obtained can be adjusted over a wide range by adjusting the amount of the metal carbonate (b) used. In addition, even when the specific foam has a low specific gravity of 0.1 or less, the obtained foam has no brittleness on the foam surface, and can be obtained from a wide range of materials from hard to soft by adjusting the composition and composition. Can be.
In addition, the thermal insulation performance of the foam can be given a low thermal conductivity of, for example, 0.03 kcal / m · hr · ° C. or less by controlling the specific gravity. A considerable level can be secured, and it is positioned as a material having excellent properties even when compared with existing heat insulating materials such as glass wool and rigid urethane foam.
Therefore, the foam of the present invention can be used as a heat insulating material for large outer wall panels and inner wall panels, a soundproofing material, a fireproofing material, a fireproof covering material, a lightweight aggregate, a heat insulating material for a fireproof safe, and the like.

[0049]

The present invention will be further described with reference to the following examples.
The present invention is not limited to this. Parts in Production Examples, Examples and Comparative Examples are parts by weight.

Production Example 1 Preparation of urethane prepolymer (c)
Preparation of raw materials necessary for 4-port separable kolben,
According to the method of reacting at 90 ° C. for 5 hours, the following NCO
Urethane prepolymers c-1 to c-2 having groups were obtained. c-1: 100 parts by weight of TDI (manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate T-80), and polyoxyethylene polyoxypropylene glycol (molecular weight: 21)
88, a prepolymer obtained by reacting 420 parts by weight of a block copolymer of ethylene oxide 20% by weight and propylene oxide 80% by weight (Newport PE-62, manufactured by Sanyo Chemical Industry Co., Ltd.). The NCO content of the prepolymer is 6.2%, the number average molecular weight is 1355,
A viscous resin solution at room temperature. c-2: relative to 100 parts by weight of crude MDI (manufactured by Nippon Polyurethane Co., Ltd., trade name: Millionate MR-100)
Polyoxyethylene polyoxypropylene triol (molecular weight 3000, glycerin propylene oxide adduct to which ethylene oxide is added. Sanyox GL-3000 manufactured by Sanyo Chemical Industries, Ltd.) 15
A prepolymer obtained by reacting 0 parts by weight. The prepolymer has an NCO content of 10.0% and a number average molecular weight of 127.
6. A viscous resin solution at normal temperature.

Examples 1 to 4 and Comparative Examples 1 and 2 For Examples 1 to 4 and Comparative Examples 1 and 2,
Based on the composition of No. 2, the phosphoric acids (a), the urethane prepolymer (c) and tap water were uniformly stirred with a homomixer. Examples 1 and 3 further include a metal carbonate (b) and a water-soluble inorganic metal compound (d), and Examples 2 and 4 respectively include a metal carbonate (b) and a water-soluble inorganic metal compound in the obtained stirred mixture. (D) and an inorganic filler (e) were added, respectively, Comparative Example 1 added a metal carbonate (b), and Comparative Example 2 added a metal carbonate (b) and an inorganic filler (e), respectively. After stirring and mixing, the mixture was poured into a mold (50 × 30 × 3 cm) and free-foamed to obtain molded foams of Examples 1-4 and Comparative Examples 1-2.

[0052]

[Table 1]

[0053]

[Table 2]

In the table, the compounds indicated by abbreviations are as follows. (A) Phosphoric acids a-1: Aluminum monophosphate a-2: Phosphoric acid a-3: Magnesium monophosphate (b) Metal carbonate b-1: Basic magnesium carbonate (c) Urethane prepolymer c -1, c-2: urethane prepolymer obtained in Production Example 1 (d) water-soluble inorganic metal salt compound d-1: sodium 8-borate d-2: sodium metaborate d-3: potassium 8-borate d-4 : Potassium metaborate (e) Inorganic filler e-1: Aluminum hydroxide

Test Example 1 Examples 1-4 and Comparative Examples 1-2
Evaluation of foams The foams of Examples 1 to 4 and Comparative Examples 1 and 2 were left in a well-ventilated room for one month, and then dried in a dryer at 40 ° C. for 120 minutes.
After being dried for a period of time, one left in a desiccator for 24 hours was subjected to a test according to the following test method. [Test Methods for Physical Properties of Foam] (1) Thermal Conductivity In accordance with JIS A-1412 (Method of measuring thermal conductivity of heat insulating plate). (2) Flexibility of the foam conforms to the flexibility test specified in JIS Z1536 (buffer for packaging polystyrene foam). The test piece is 40 mm
Judgment was made by observing the condition when the film was wound along the circumference of the cylinder. (3) Non-combustible / quasi-incombustible / flame retardant (hereinafter collectively referred to as fire protection) Ministry of Construction Public Notice No. 1231 (test method for semi-combustible materials and flame retardant materials), Ministry of Construction Public Notice No. 1828 (test of noncombustible materials) Method), the measurement was carried out in accordance with the surface test method specified respectively. (4) Compressive strength The foam after the combustion test was cut into a 30 mm square,
The compressive strength was measured in accordance with JIS K-7220 (compression test method for hard foamed plastic).

[Test Results] Table 3 summarizes the results of the physical property test and appearance observation of each foam.

[0057]

[Table 3]

[0058]

The foam of the present invention and the method for producing the same have the following effects. (1) The foam of the present invention significantly improves the brittleness and the strength of the foam when exposed to a flame, which are the problems of the conventional phosphoric acid foam, and provides a low-density foam. In the case of, despite being an organic-inorganic composite, it is a foam having the same degree of flexibility and resilience as soft urethane foam, this foam can be adjusted from soft to hard, and soft Any of the hard cases is brittle, and the strength of the foam when exposed to a flame is improved. (2) Even a low-density foam has a strength that does not cause any problem in use, so that a lightweight panel or the like having excellent heat insulating properties can be manufactured. (3) Since it can be produced even under conditions of normal temperature and normal pressure, a special reaction device such as autoclave curing is not required. (4) It can be easily foamed and cured in a mold having a desired shape. It is also possible to perform troweling, spraying, and the like on the wall surface to cure the wall. (5) Although the appearance and performance are almost at the same level as the existing urethane foam and styrene foam, the fire resistance of the material is a nonflammable material which is higher than these existing organic insulation materials.
This is a level equivalent to a quasi-noncombustible material, and can supply a highly safe material to the market in disaster prevention.

Due to the above-mentioned effects, the foam of the present invention has its fireproofing properties, heat insulating properties, elasticity, flexibility, strength,
It is suitable for use in, for example, the following applications by taking advantage of the property of having both low density and the like. For applications requiring fire protection such as trains, cars, houses, buildings, etc.
Alternative applications to those in which inorganic foams such as LC, calcium silicate plate, inorganic fiber plate, etc. were used; for example, steel frame covering materials, firebricks, inner wall panels including kitchens and kitchens, fireproof exterior panels, boilers, etc. Heat shield material for combustion machinery of automobiles, seat cushion material for automobiles and the like, heat shield material for exhaust lines, interior panels and void fillers for ships, etc., and fillers for fireproof safes. For applications requiring insulation performance such as houses, buildings, trains, aircraft, ships, etc., alternative applications to those in which organic foams such as urethane foam and styrene foam have been used; for example, ceilings, walls, floors, roofs, etc. Interior and exterior insulation boards and panels for houses and buildings, tatami core materials, void filling materials such as doors, insulation lining materials for roof tiles and roofing materials, roof lining materials for cars, trains, aircraft, ships, etc., and interiors around engines Timber,
Replacement material for honeycomb-used parts, insulation for refrigerators, air conditioners, freezers, air conditioning equipment and air conditioning lines, insulation for natural gas tanks and pipelines such as LNG, insulation for utility lines in factories, frozen products Insulation packing material for transportation such as.

Applications requiring low density; for example, synthetic wood and its core material, lightweight aggregate, packing material for packaging. Applications that require a larger surface area than foams that are open cells; for example, alternatives to sand for the sand drain method, carriers for exhaust gas combustion catalysts, carriers for deodorants and fragrances. Applications requiring sound absorption: sound absorbing panels for houses, soundproof inner wall materials in tunnels, soundproof railing coverings for train tracks, soundproof lining materials for engines and machinery, and housing lining materials. Foam applications requiring low biodegradability and low environmental pollution compared to organic materials; alternative applications for lightweight embankments, backfill materials for tunnels, blocks for vegetation, kenzan for ikebana, vermiculite for horticulture, etc.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masanori Monobe 1531-7 Wadahama Takasuka, Toyohama-cho, Mitoyo-gun, Kagawa Prefecture Unicharm Corporation Development Division (72) Inventor Naoki Yazawa 5-6 Shinba, Kakegawa City, Shizuoka Prefecture Unicharm Co., Ltd. (72) Inventor Misao Okamoto 1-1-88 Oyodonaka, Kita-ku, Osaka City Sekisui House Co., Ltd. (72) Inventor Shinzo Kaida 11th, Hitotsubashi Nohonmachi, Higashiyama-ku, Kyoto-shi 1 Sanyo Chemical Industries Co., Ltd. (72) Inventor Tadaaki Yamazaki 1 Sanyo Chemical Industries Co., Ltd.

Claims (7)

[Claims] 1. A phosphoric acid foam structure comprising phosphoric acid (a) and a metal carbonate (b), wherein brittleness is improved by a cured product of a urethane prepolymer (c) having an NCO group, And an inorganic-organic composite comprising a water-soluble inorganic metal salt compound (d) having a solubility in water at 20 ° C. of 3.0 g / 100 g or more and, if necessary, another inorganic filler (e). Foam. 2. The phosphoric acid (a) according to claim 1, wherein the phosphoric acid (a) is at least one compound selected from the group consisting of (anhydrous) phosphoric acid, phosphorous acid, condensed phosphoric acid, and polyvalent metal salts thereof. Inorganic-organic composite foam. 3. The inorganic-organic composite foam according to claim 1, wherein the content of the water-soluble inorganic metal salt compound (d) is 1 to 50% by weight. 4. The inorganic-organic composite foam according to claim 1, wherein the water-soluble inorganic metal salt compound (d) is a metal borate. 5. The inorganic-organic composite foam according to claim 4, wherein the metal borate is a sodium borate compound. 6. The inorganic-organic composite foam according to claim 5, wherein the sodium borate compound is sodium 8-borate. 7. Phosphoric acid (a), metal carbonate (b), N
It comprises a urethane prepolymer (c) having a CO group, a water-soluble inorganic metal salt compound (d) having a solubility in water at 20 ° C. of 3.0 g / 100 g or more, water, and if necessary, other inorganic filler (e). A method for producing an inorganic-organic composite foam, comprising foaming and curing by mixing components.