JPH101558A - Inorganic/organic composite foam and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inorganic/organic composite foam having improved flexibility, strengths and nonbrittleness and fireproofing performances by expanding and curing a water-based mixture comprising a phosphoric acid or sulfuric acid, a blowing agent and a resol phenol resin. SOLUTION: This foam is produced by method A comprising expanding and curing components comprising a phosphoric acid (a), a blowing agent (b) for the phosphoric acid, a resol phenol resin(c'), water and optionally an inorganic filler (d) under agitation or method B comprising expanding and curing components comprising sulfuric acid (a'), calcium or barium carbonate (b') and optionally calcium or barium oxide or hydroxide (b"), a resol phenol resin (c'), water and optionally an inorganic filler (d) under agitation. Blowing agent (b) is desirably a carbonate compound (e.g. desirably basic barium carbonate).

Description

DETAILED DESCRIPTION OF THE INVENTION

[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 has been remarkably improved by a curable organic material, having flexibility and resilience such as urethane foam and styrene foam. Inorganic-organic composite foam which can be compared with foam and also has fire protection performance; and inorganic-organic composite foam capable of forming a foam even under conditions of room temperature to 140 ° C A method for producing the same.

[0002]

2. Description of the Related Art Conventionally, among inorganic foams, phosphoric acid foams have been proposed as inorganic foams capable of forming foams even under normal temperature and normal pressure conditions.
No. 36145). The foam described in this publication is to obtain a foam by stirring and mixing a phosphoric acid such as a metal phosphate and a foaming agent such as a polyvalent metal carbonate and foaming and curing the following. Because of these characteristics, it can be positioned as an unprecedented superior material, for example, it can be applied not only to a fixed material such as a panel but also to an irregular filler for filling an opening. (1) The obtained foam is excellent in nonflammability and fire resistance. (2) In producing a foam, specific gravity control over a wide range can be easily performed. (3) Self-foaming.

[0003] However, the foam of phosphoric acid is fragile because it is a completely inorganic material, and has a drawback that the foam formed by even a small force is destroyed and cannot be restored. Particularly, a large panel having a low specific gravity is produced. In such a case, the surface layer is destroyed only by touching, and the panel strength is too weak to be carried around. As a means for improving the disadvantages of such a phosphoric acid foam, a method has been proposed in which a resin emulsion such as SBR is added into the system (for example, JP-A-6-24869). In this method, the strength of the foam is improved by adding a resin emulsion to such an extent that the excellent nonflammability and heat resistance characteristic of the foam of phosphoric acid are not impaired, and the foam is practically used even in a foam having a high expansion ratio. It is said that it is possible to obtain an excellent material.

[0004]

However, although the strength of the foam of phosphoric acid has been greatly improved by the addition of the resin emulsion, it is essentially a brittle material, and the brittleness of the foam having a high expansion ratio is not so high. However, it is difficult to obtain a foam having flexibility and resilience of plastic foams such as urethane foam and styrene foam.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve these problems of the conventional foams of phosphoric acids, and as a result, unlike the above resin emulsion, a resole type phenol having a crosslinking reactivity. A foam using resin curing was obtained. Further, as a result of the study of the present inventors, when this resol-type phenol resin is used, when a foam having a high expansion ratio is used, a foam having flexibility and strength despite being an organic-inorganic composite is used. The expansion ratio could be adjusted from semi-soft to hard, and the brittleness was found to be significantly improved in both cases of semi-soft and hard.

That is, the present invention comprises the following inorganic-organic composite foams <1>, <2>, <3> and methods <4>, <5> for producing inorganic-organic composite foams. <1> An inorganic-organic composite foam having a foam structure of a phosphoric acid (a) and a foaming agent for a phosphoric acid (b), and having improved brittleness by a cured product (c) of a resol-type phenol resin. <2> A foam structure made of sulfuric acid (a ′), calcium or magnesium carbonate (b ′), and, if necessary, calcium and barium, oxidation and hydroxide (b ″), and a resol type phenol An inorganic-organic composite foam whose brittleness is improved by the cured resin (c) <3> The foam according to the above <1> or <2>, further containing an inorganic filler (d). An inorganic-organic composite foam which is foam-cured by mixing a component comprising an acid (a), a foaming agent of phosphoric acid (b), a resol type phenol resin (c '), water and, if necessary, an inorganic filler (d). <5> Sulfuric acid (a '), calcium or barium carbonate (b') and, if necessary, calcium or barium oxide or hydroxide (b "), and resole pheno And Le resin (c '), water and, preparation of inorganic-organic composite foam of foaming cure by mixing the components consisting of the inorganic filler (d) if necessary.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The foam <1> of the present invention has an inorganic foam structure formed by reacting a phosphoric acid (a) with a foaming agent (b) of a phosphoric acid to form a foam. <2> Is a foam structure from sulfates (a ′), calcium or barium carbonates (b ′), and optionally calcium or barium oxides or hydroxides (b ″). The foams <1> and <2> have an inorganic-organic composite foam structure in which the brittleness is improved by the cured product (c) of the resol-type phenolic resin. Since the crosslinking reaction occurs at 140 ° C., the foams <1> and <2> of the present invention have improved brittleness.The foam <1> of the present invention includes, for example, phosphoric acids (a), Consisting of agent (b) and the resole type phenol resin (c ′) (A) and (b) and the cross-linking of the phenolic resin (c ′) by foaming and curing. The reaction proceeds to obtain the foam <1> of the present invention.
That is, by using this aqueous mixture, (a) and (b)
And the curing and crosslinking reaction of the phenolic resin of (c ′) proceed to obtain the foam <1> of the present invention. In the same manner as described above, the foam <2> of the present invention comprises, for example, sulfuric acid (a ′), calcium or barium carbonate (b ′), and, if necessary, calcium or barium oxide or hydroxide ( It is obtained by foaming and curing by forming an aqueous mixture of b '') and a component comprising the resole type phenol resin (c ').

In the present invention, the phosphoric acids (a) include, for example, phosphoric acid, phosphorous acid, phosphoric anhydride, condensed phosphoric acid, polyvalent metal salts thereof, and mixtures of two or more thereof. Among these, as the polyvalent metal salt of phosphoric acid,
There are polyvalent metal salts of primary phosphoric acid, polyvalent metal salts of secondary phosphoric acid, and polyvalent metal salts of tertiary phosphate. Examples of the metal constituting the polyvalent metal salt include barium, calcium, aluminum, zinc, barium, and iron. These polyvalent metal components may be added in the form of a polyvalent metal salt of phosphoric acid, a polyvalent metal salt of phosphite, or a metal compound chemically active with phosphoric acid or phosphorous acid, for example, oxidation. Polyvalent metal oxides such as barium and calcium oxide, aluminum hydroxide gel,
It is also possible to employ a method in which a polyvalent metal hydroxide such as barium hydroxide or calcium hydroxide is added to the system separately from phosphoric acid, phosphorous acid or the like, and the reaction is performed in the system. (A) is an aqueous solution exhibiting acidity and is usually an aqueous solution having a pH of 4 or less, preferably 3 or less, and particularly preferably 2 or less. Among the phosphoric acids (a), preferred are phosphoric acid, barium monophosphate, aluminum monophosphate, zinc monophosphate and a mixture of two or more thereof, and particularly preferred are Phosphoric acid, barium monophosphate, aluminum monophosphate and a mixture of two or more thereof.

The content of the phosphoric acid (a) is usually 3 to 50% by weight based on all components constituting the foam of the present invention.
When converted to the content of phosphorus atoms in the foam of the present invention,
In a preferred range, 3 to 20% by weight, especially 4 to 18% by weight.
% By weight. When the content of phosphorus atoms is less than 3% by weight, the fire prevention performance of the obtained foam is reduced. If the phosphorus atom content exceeds 20% by weight, the dispersibility of the phenolic resin (c ') may decrease, and a uniform foamed structure may not be obtained. Examples of the sulfuric acid (a ′) include industrial sulfuric acid whose concentration is adjusted by various water dilutions.

In the present invention, examples of the foaming agent (b) include the following (b1) and (b2). (B1) Carbonate compound (b2) Specific examples of the light metal carbonate compound (b1) which reacts with an acid or alkali to generate gas include sodium carbonate, sodium hydrogen carbonate, potassium carbonate, ammonium carbonate, calcium carbonate, carbonate Barium, basic barium carbonate, basic zinc carbonate and the like, and the above light metals (b
Specific examples of 2) include barium, aluminum, and zinc. Other foaming agents that can be used in combination with the foaming agent (b) of the present invention include organic foaming agents (dinitrosopentamethylenetetramine and NN'dimethylNN'dinitroso Nitroso-based blowing agents such as terephthalamide; sulfohydrazide-based blowing agents such as benzenesulfonyl hydrazide azodicarbonamide, p-toluenesulfonyl hydrazide, and p, p'-oxybis (benzenesulfonyl hydrazide 3-3'disulfohydrazide diphenyl sulfone) , Azobisisobutyronitrile, azobisformamide, azo-based foaming agent such as diethylazodicarboxylate, etc.) are mixed in advance to form the foam of the present invention, and the added foaming agent is further heated by heating. A secondary foaming method can be used. ) Illustrated preferred among those with as is the basic barium carbonate. The amount of foaming agent (b) may be determined depending on the desired expansion ratio of the wide range of semi-soft to hard.
The amount of (b) is not particularly limited as long as (a) and (b) are well mixed in an aqueous mixture, but usually 0.1 to 200 parts by weight based on 100 parts by weight of phosphoric acid (a). Parts by weight, preferably 1 to 100 parts by weight. Examples of the calcium or barium carbonate (b ′) include calcium carbonate and barium carbonate. Examples of the calcium or barium oxide or hydroxide (b ″) used as needed include, for example, quicklime and slaked lime. , Barium oxide and barium hydroxide (b ').
And the sum of (b ″) and (a ′) is 100 parts by weight,
Usually, it is 1 to 200 parts by weight, preferably 5 to 100 parts by weight.

The resole-type phenolic resin (c ') is an uncured (precondensation step) corresponding to resole (bakelite A) or resitol (bakelite B) which has been further condensed, and is obtained by a known method. Manufactured products can be used. Resol-type phenolic resins (c ') include mono- or di-alkylphenols such as phenol, cresol, xylenol, butylphenol, octylphenol, and nonylphenol; halogenated phenols such as chlorophenol; phenols such as styrenated phenol; It is obtained by precondensing aldehydes such as paraformaldehyde and acetaldehyde with an alkali catalyst such as sodium hydroxide, barium hydroxide, and a tertiary amine such as triethylenediamine and trisdimethylaminophenol. In the above production method, the molar ratio of phenols to aldehydes is usually in the range of 1: 1 to 1: 3. Also,
As (c '), the content of unreacted phenols having a solid content of 75% by weight or more is reduced as much as possible. If the degree of condensation is 2 to 10, and the liquid has a low to high viscosity at room temperature, Good.

Further, it is also possible to use (c ') to which a lower alcohol is added for the purpose of stabilizing storage.

The amount of the resol-type phenol resin (c ') used is preferably 5 to 30% by weight of the total solids constituting the foam from the viewpoint of nonflammability and strength. If it is less than 5%, the resulting foam is very brittle, and if it exceeds 30%, the nonflammability is reduced and the foam becomes flammable.

Among these resole type phenolic resins (c '), preferred are phenol and / or cresol and formalin in a ratio of 1: (1.5 to 2.0).
300-20,000c obtained by condensation at a molar ratio of
P / 25 ° C., non-volatile content 70-100%.

In order to make the foam flexible,
As the phenols in (c ′), phenol and alkylphenols may be used in combination.

Further, a resole type phenol resin (c ')
Is preferably 30 to 5% by weight based on the total solid content of the foam. If it is more than 30%, the fire protection performance is greatly reduced, and if it is less than 5%, the foam is brittle and cannot exert a reinforcing effect, making it unsuitable for practical use.

The foam of the present invention may optionally contain an inorganic filler (d) in consideration of physical properties and cost.
Examples of the inorganic filler (d) include the following (d1) to (d)
5). (D1) Cement: Portland cement, silica cement, alumina cement, blast furnace cement, fly ash cement, white cement, etc. (d2) Clay mineral: morillonite, bentonite, mica, sericite, kaolin, talc, philite, zeolite, etc. (d3) ) Inorganic lightweight aggregate: perlite, shirasu balloon, etc. (d4) Inorganic fiber: carbon fiber, asbestos, rock wool, glass fiber, ceramic fiber, potassium titanate fiber, steel fiber, etc. (d5) Other water-insoluble Inorganic powder materials: fly ash, silica fume, silica powder, ceramic powder, aluminum hydroxide, alumina, calcium carbonate, calcium sulfate, etc.

There is no particular limitation on the selection of those exemplified as (d) above, and they may be added singly or in any combination in accordance with the requirements such as physical properties and cost of the foam.
For example, the hardness of the foam is improved by adding the cement (d1). Among the cements (d1), alumina cement is preferable in that it has low reactivity with the phosphoric acids (a) because it has low alkalinity even in cement. The addition of the inorganic fiber (d4) improves the tensile strength and the bending strength of the foam and the shape retention after the organic substances in the foam are temporarily burned. In addition, aluminum hydroxide and calcium carbonate in (d5) improve the fire prevention performance by being added. Others exemplified as (d) can be used mainly as an increasing material for cost reduction. The amount of (d) added 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 phosphoric acid (a). Organic fibers can be used instead of or in combination with the inorganic fibers (d4), and organic fibers also have an effect of improving the tensile strength, bending strength, and the like of the foam. Examples of the organic fiber include vinylon fiber, polyamide fiber, acrylic fiber, polyester fiber, polypropylene fiber, and cellulose fiber. However, the amount of the organic fibers used must be within a range that does not cause any problem in consideration of the required level of the fire protection performance of the foam.

The foam of the present invention has a considerably high fire resistance if the content of (c) is within the above-mentioned preferred range. However, in order to impart even higher fire resistance, a flame retardant is added to the components. Can be foamed and cured. Examples of the flame retardant include non-halogen phosphates (triphenyl phosphate, cresyl diphenyl phosphate, ammonium polyphosphate, etc.), and halogen-containing phosphates (trischloroethyl phosphate, tris dichloropropyl phosphate, tris ( Tribromophenyl) phosphate, trisdibromopropylphosphate, etc., active hydrogen-containing flame retardants (di (isopropyl) N, Nbis (2hydroxyethyl) aminomethylphosphate, alkylene oxide adduct of brominated bisphenol A, etc. ), Antimony trioxide, antimony pentoxide, zinc oxide, and the like. One or more of the above examples may be used. The amount of the flame retardant to be used is generally 40 parts by weight or less, preferably 0.1 to 30 parts by weight, per 100 parts by weight of (c ′).

According to the method of the present invention, phosphoric acids (a),
When the foaming agent (b), the resol-type phenol resin (c '), water and, if necessary, a component comprising an inorganic filler (d) are mixed to form an aqueous mixture and foamed and cured, the foam of the present invention is obtained. Is obtained. As long as the amount of water in the aqueous mixture is within a range that can be made into a mixed water slurry, it is not necessary to add more water than necessary. As the amount of water increases, the foamed and hardened product takes more time and labor to dry. The amount of water is not particularly limited, but usually the concentration of the aqueous mixture is 50 to 90% by weight.
It is an amount that will be about.

In the method of the present invention, in order to control the reaction curing rate of the resol-type phenolic resin (c '), it can be carried out by further heating at the time of foaming curing and after foaming curing. It is usually at room temperature to 140 ° C, preferably at 60 to 120 ° C. Further, in the resol-type phenolic resin (c ′), phosphoric acid (a) acts as a curing catalyst at the time of foaming and curing. However, in order to further control the speed of the crosslinking reaction, another catalyst can be added and used. Examples of the catalyst include inorganic acids and organic acids such as hydrochloric acid, sulfuric acid, phenolsulfonic acid, toluenesulfonic acid, xylenesulfonic acid, nonyl and octylphenolsulfonic acid.

The amount of the other catalyst to be used is usually 0.1 to 100 parts per 100 parts of the resole type phenol resin (c ').
5 parts.

In the method of the present invention, a foam stabilizer may be added to control the cell structure of the foam. Examples of the foam stabilizer include conventionally known silicone-based activators. For example, SH-192 and SH-19 manufactured by Tore Silicone Co., Ltd.
3, SH-194, etc. ・ TFA-4200 made by Toshiba Silicone Co., Ltd. ・ L-5320, L-5340, L made by Nippon Unicar Co., Ltd.
-5350, etc. ・ Shin-Etsu Silicon F-121, F-122 and the like. The addition amount of the foam stabilizer is usually 3 parts or less, preferably 0.001 to 1 part based on 100 parts by weight of the resol-type phenol resin (c ').

In order to obtain the foam of the present invention,
Each component of (a), (b) and (c ′) is previously diluted and mixed with water such as tap water, natural water, deionized water, river water, well water, or mixed with water to form an aqueous mixture. There is a need to. In the method of the present invention, there are various methods as exemplified in the following [1] to [4] as a method of foaming and curing by mixing respective components. [1] The phosphoric acids (a), the foaming agent (b), the resole type phenolic resin (c '), water and, if necessary, the inorganic filler (d) are added and mixed at a time, and foam hardening is performed at room temperature to 90 ° C. Method to make. [2] After mixing the phosphoric acid (a), the resole type phenol resin (c ') and water, the blowing agent (b) and, if necessary, the inorganic filler (d) are also added and mixed, and mixed at room temperature to 90 ° C. A method of foaming and curing at ℃. [3] After mixing the phosphoric acid (a) and the resole type phenol resin (c '), the foaming agent (b),
A method in which water and, if necessary, an inorganic filler (d) are mixed and slurried, and then mixed and foam-hardened at room temperature to 90 ° C. [4] After mixing the phosphoric acid (a), the resole type phenol resin (c ′) and a part of water, the blowing agent (b), and if necessary, the inorganic filler (d) and the remaining water are mixed. The mixture is slurried and mixed.
A method of foaming and hardening at 0 ° C. Of these, the methods [1], [2] and [4] are preferable, and the method [2] is particularly preferable. The same applies to the cases (a ′), (b ′) and (c).

The foam of the present invention is mixed and foam-cured by the method of the present invention at room temperature to 90.degree.
To complete the curing.

According to the method of the present invention, the mixture is poured into a mold and formed into a foam. In the case of a molded body, a foam may be formed by a method exemplified above using a mold having an arbitrary shape (eg, a mold of a large panel).

The specific gravity of the foam of the present invention can be adjusted over a wide range by adjusting the amount of the foaming agent (b). Further, even when the obtained foam has a low specific gravity of 0.1 or less, the foam surface has no brittleness, and from the adjustment of composition and composition, foams of a wide range of materials from hard to semi-soft are obtained. be able to. In addition, the thermal insulation performance of the foam is controlled by the specific gravity, for example, 0.03 kcal / m.
・ It is possible to provide a low thermal conductivity of hr · ° C or less, and the fire resistance is also at a level equivalent to non-combustible material from non-combustible material. , And is regarded as a material with excellent properties. Therefore, the foam of the present invention can be used as a heat insulating material, a soundproofing material, a fireproofing material, a fireproofing covering material, a lightweight aggregate, a heatproofing material for a fireproof safe, etc. of a large outer wall panel or an inner wall panel.

[0028]

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 <Production of the resole-type phenol resin (c ′)> A phenol and an alkaline catalyst (caustic soda) were charged into a reaction vessel, and formalin was added dropwise at 20 to 30 ° C. with stirring and cooling. The reaction was performed at 2.5 ° C. for 2.5 hours. Caustic soda was added successively to maintain the pH at 8.5 to 9.5 during the reaction. Thereafter, the pH was adjusted to 7 to 8 with an acid of p-toluenesulfonic acid, and then the mixture was cooled and the unreacted raw material and a part of the condensed water were removed out of the system under reduced pressure. 1 to c-3 were obtained. c-1; reacted with phenol: formalin = 1: 1.9 (molar ratio). (76% solids, 18500 viscosity
cps) c-2; reacted with phenol: formalin = 1: 1.5 (molar ratio). (81% solids, 1200c viscosity
ps) c-3; phenol: cresol: formalin = 0.
Those reacted at a ratio of 8: 0.2: 1.5 (molar ratio). (Solid content 83%, viscosity 760 cps)

Production Example 2 <Examples 1-4, Comparative Examples 1-4
Production of Foam of Example> Each of Examples 1 to 4 was based on the composition shown in Table 1 below, and the phosphoric acid (a) and the resole type phenol resin (c ′) were uniformly stirred with a homomixer, and then the foaming agent ( b), water and the inorganic filler (d) were added, and the mixture was similarly stirred and mixed. Thereafter, the mixture was poured into a mold (50 × 30 × 3 cm) and allowed to freely foam to obtain a molded product. Then, the foam was dried at 75 ° C. for 3 hours, and further post-cured at 120 ° C. for 2 hours to form a foam. Similarly, each of Comparative Examples 1 to 4 is based on the composition of Table 1 below,
(A) and (c ') were mixed, (b), water and (d) were further added, and the mixture was stirred and mixed. Thereafter, it was similarly poured into a mold and foamed to obtain a molded product. However, in Comparative Example 3, the flame retardant noted in Table 1 was added, and in the case where the flame retardant was uniformly stirred in advance in (c ′), the mixture was stirred and mixed with (d) and then poured into the mold. The molded product was obtained by free foaming.

[0031]

[Table 1]

Note 1) The compounds indicated by the abbreviations are as follows. (A) Phosphoric acids a-1: Aluminum phosphate monobasic a-2: Phosphoric acid a-3: Barium phosphate monobasic (b) Blowing agent b-1: Basic barium carbonate (c ') The resole phenol Resin c-1; reacted with phenol: formalin = 1: 1.9 (molar ratio). (76% solids, 18500 viscosity
cps) c-2; reacted with phenol: formalin = 1: 1.5 (molar ratio). (81% solids, 1200c viscosity
ps) c-3; phenol: cresol: formalin = 0.
Those reacted at a ratio of 8: 0.2: 1.5 (molar ratio). (Solid content 83%, viscosity 760 cps) (d) inorganic filler d-1: aluminum hydroxide d-2: alumina cement d-3: silas balloon [Sanki Kogyo Co., Ltd., trade name:
Sankilite Yo.2] 2) In Comparative Example 2, Nippon Oil & Fats Co., Ltd.
And a halogen-containing phosphoric acid ester (trade name: Aranfuram 70) were added, and this flame retardant was previously used by uniformly stirring the resol-type phenolic resin (c ′).

Test Example 1 [Examples 1-4, Comparative Examples 1-4]
Evaluation of Foam of Example] The foams of Examples 1 to 4 and Comparative Examples 1 to 4 obtained in Production Example 2 were left in a well-ventilated room for one month, and then subjected to a test according to the following test method. [Test Method for Physical Properties of Foam] (1) Compressive strength: JIS K-7220 (Compression test method for hard foamed plastic) (2) Thermal conductivity: JIS A-1412 (Method of measuring thermal conductivity of heat insulation plate) (3) Flexibility of foam: conforms to the flexibility test specified in JIS Z1536 (buffer for packaging polystyrene foam). Judgment was made by observing the state when the test piece was wound around the circumference of a 40 mm cylinder. (4) Fire protection performance level (non-flammable / quasi-flammable / flame-retardant): 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 method for non-combustible materials) The measurement was carried out in accordance with the surface test method specified in the above.

[Test Results] Table 2 summarizes the results of the physical property test and appearance observation of each foam.

[0035]

[Table 2] Note) Unit: Density is kg / m ³ , thermal conductivity is kcal / mhr ° C, and compressive strength is kPa.

[Supplementary Explanation of Test Results] Of the foams of the present invention of Examples 1 to 4, Examples 1 to 3 were used.
Was a resilient and flexible semi-rigid foam, and the foam of Example 4 was a hard foam having low resilience and flexibility. The surface state of the foams of Examples 1 to 4 was such that the powder and the like did not peel off even when rubbed by hand, and the molded articles that had been removed had sufficient strength performance to operate as large panels. . The level of fire protection was also quite high, from non-combustible to quasi-noncombustible. Of the foams of Comparative Examples 1 to 4, Comparative Example 2 had a low level of fire resistance equivalent to a flame retardant, and Comparative Example 3 contained a flame retardant, but had the same difficulty as Comparative Example 2. It was equivalent to fuel material. In Comparative Examples 1 and 4, although the fire protection level was considerably high, which was equivalent to a noncombustible material, the foam was very brittle, the surface was peeled off, and the like. It could not be said that the molded article had strength performance enough to be used as a panel, for example, cracks occurred in the molded article.

[0037]

The inorganic-organic composite 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 brittleness, which has been a problem of conventional foams of phosphoric acids. When the foam has a high expansion ratio, it is an organic-inorganic composite. Nevertheless, it is a foam having flexibility and resilience enough to be mistaken for a soft urethane foam. The expansion ratio can be adjusted from soft to hard, and the brittleness is improved in both soft and hard cases. I have. (2) Even a foam having a low specific gravity and a high foaming ratio has a strength that does not cause any problem in operation, 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 made porous in a mold having a desired shape and can be cured. It is also possible to perform troweling, spraying, and the like on the wall surface to cure the wall. (5) In terms of appearance and performance, existing urethane foam,
Although it is almost at the same level as styrene foam, the fire resistance of the material is at a level equivalent to nonflammable materials to quasi-nonflammable materials that are higher than these existing organic insulation materials. Can supply to market.

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. In applications where fire protection performance is required, such as trains, automobiles, houses, buildings, etc., alternatives to those in which inorganic foams such as ALC, calcium silicate boards, inorganic fiber boards, etc. are conventionally used; for example, steel frame covering materials, fire bricks, kitchens Interior wall panels, including kitchens and kitchens, exterior panels with fire protection, heat shield materials for combustion machines such as boilers, seat cushion materials for automobiles and the like, heat shield materials for exhaust lines, interior panels and gap filling materials for ships, etc.
Filler for fireproof safe. For applications requiring insulation performance such as houses, buildings, trains, aircrafts, ships, etc., alternatives to those in which organic foams such as urethane foam and styrene foam have been used conventionally; for example, ceilings, walls, floors, roofs, etc. Interior / exterior insulation boards and panels for houses and buildings, tatami core materials, void filling materials for doors, etc., thermal insulation backings for roof tiles and roofing materials, roof lining materials for cars, trains, aircraft, ships, etc., interior materials around engines 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, refrigeration Insulation packing material for transporting goods. Applications where low density is required; for example, synthetic wood and its core, lightweight aggregate, packing material for packaging. Applications that require a larger surface area than foams that are open cells; for example, replacement for sand for sand drain method, carrier for exhaust gas combustion catalyst, carrier for deodorant and fragrance. Applications requiring sound absorption: sound absorbing panels for houses, soundproof inner wall materials in tunnels, soundproof railings for train tracks, soundproof lining materials for engines and machinery, and housing lining materials. Applications that are required due to their low biodegradability and low environmental pollution compared to organic materials, which are not foamed in organic materials; alternatives to lightweight embankments, backfilling materials for tunnels, blocks for vegetation, sword mountains for ikebana, horticulture For vermiculite, etc.

Claims (9)

[Claims] 1. A foam structure composed of phosphoric acid (a) and a foaming agent of phosphoric acid (b), and brittleness is improved by a cured product (c) of a resol-type phenol resin formed in situ. Inorganic-organic composite foam. 2. The foam according to claim 1, wherein the aqueous mixture comprising (a) and (b) and the resol-type phenol resin (c ′) is foamed and cured. 3. A foam structure from sulfuric acid (a ′), calcium or barium carbonate (b ′), and optionally calcium or barium oxide or hydroxide (b ″), An inorganic-organic composite foam whose brittleness is improved by curing (c) of a resol-type phenol resin formed in situ. 4. The foam according to claim 3, wherein an aqueous mixture comprising (a ′), (b ′) and, if necessary, (b ″), and a resol-type phenolic resin (c ′) is foamed and cured. . 5. The foam according to claim 2, wherein the content of (c) in the aqueous mixture in terms of solid content is 5 to 30% by weight. 6. The foam according to claim 1, wherein the foaming agent (b) is a carbonate compound. 7. The foam according to claim 1, further comprising an inorganic filler (d). 8. Foaming and curing by mixing a component comprising phosphoric acid (a), phosphoric acid foaming agent (b), resol type phenol resin (c '), water and, if necessary, inorganic filler (d). A method for producing an inorganic-organic composite foam. 9. An oxide or hydroxide of sulfuric acid (a ′) and calcium or barium (b ′) and optionally calcium or barium (b ″)
And a resol-type phenol resin (c '), water and, if necessary, a component comprising an inorganic filler (d).