JPH1129648A - Inorganic and organic composite foamed product and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject foamed product that is improved in its fragility, maintains its low combustion heat and reduced smoke quantity on burning and is excellent in fire prevention with increased foam strength after burning by using a phosphoric acid foamed product, an NCO group-bearing urethane polymer cured product, a polyvalent metal borate and, when necessary, an inorganic filler. SOLUTION: This foamed product contains (A) phosphoric acid, (B) a foaming agent as basic magnesium carbonate, (C) a urethane polymer bearing NCO groups (a reaction product of ethylene diisocyanate with ethylene oxide adduct), (D) a powdery polyvalent metal borate as zinc borate and, when necessary, (E) an inorganic filler. In a preferred embodiment, the amount of the component A is 3-50 wt.%, the component C is 5-30 wt.%, the component D is 1-50 wt.% and the components B and E are 0.1-200 pts.wt. and <=1,800 pts.wt. per 100 pts.wt. of the component A, respectively.

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 remarkably improved brittleness by an elastic polymer, compared to a foam having flexibility and resilience such as urethane foam or styrene foam. The present invention relates to an inorganic-organic composite foam which can be made comparable to the above, and also has a fire prevention performance; and a method for producing an inorganic-organic composite foam capable of forming a foam even under normal temperature and normal pressure conditions.

[0002]

2. Description of the Related Art Hitherto, a foam of phosphoric acid has been proposed as an inorganic foam capable of forming a foam under normal temperature and normal pressure conditions (eg, Japanese Patent Publication No. 56-36145).
The foam described in this publication is to obtain a foam by mixing and stirring a phosphoric acid such as a metal phosphate and a foaming agent such as a polyvalent metal carbonate, and foaming and curing the foam.
Since it has the following features, it can be positioned as a superior material that has not been seen in the past, for example, it can be applied to not only a fixed material such as a panel but also 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 is broken even by a small force and cannot be restored. In particular, a large panel having a low specific gravity has been produced. In this case, there are problems such as the surface layer being collapsed just by touching, and the panel strength being too weak to be portable, and thus it cannot be said to be a material suitable for practical use. As a means for remedying such a drawback of the phosphoric acid foam, a method of adding a urethane prepolymer to the system has been proposed (for example, JP-A-9-157061). In this method, when a foam having a high expansion ratio is used by using a urethane prepolymer, a foam having flexibility and resilience enough to be mistaken for a soft urethane foam despite being an organic-inorganic composite. Can be adjusted from soft to hard by the composition of the urethane prepolymer to be used, and brittleness can be remarkably improved in both cases of soft and hard.

[0004]

However, by using a urethane prepolymer, the brittleness of a foam having a high expansion ratio is improved, and a foam having flexibility and resilience such as urethane foam or styrene foam is obtained. Although the heat of combustion and the amount of smoke generated during combustion of the foam can be significantly reduced compared to those of the organic foams, the strength of the foam after combustion is weak, and when the foam is exposed to a flame for a long time. May cause the foam to collapse.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve these problems, and as a result, have found that powdered polyvalent polyphosphoric acid foams having improved brittleness by a cured urethane prepolymer have been obtained. By adding metal borate, while maintaining the same foam physical properties as before and low combustion heat and low smoke generation during combustion, the foam strength after combustion is further improved, and fire spread in the event of fire It was found that it can be delayed and can be positioned as a very good material for disaster prevention.

That is, the present invention relates to a phosphoric acid foam structure comprising phosphoric acid (a) and a foaming agent (b),
Inorganic organic material having improved brittleness by a cured product of a urethane prepolymer (c) having a group, and containing a powdery polyvalent metal borate (d) and optionally another inorganic filler (e). Composite foam; phosphoric acid (a), foaming agent (b), urethane prepolymer having NCO group (c), powdered polyvalent metal borate (d), water and, if necessary, inorganic filler (e) This is a method for producing an inorganic-organic composite foam which is foamed and cured by mixing components consisting of:

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The foam of the present invention comprises, for example, a phosphoric acid (a), a metal carbonate (b), the prepolymer (c), a powdered polyvalent metal borate (d), and if necessary. It is obtained by foaming and hardening by using an aqueous mixture as the component comprising the inorganic filler (e). That is, by using this aqueous mixture, the foaming and curing reaction of (a) and (b) and the curing reaction of (c) with water proceed, and the foam of the present invention is obtained.

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 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 or a polyvalent metal salt of phosphorous acid, or a metal compound chemically active with phosphoric acid or phosphorous acid, for example, magnesium oxide. , Polyhydric metal oxides such as calcium oxide, polyhydric metal hydroxides such as aluminum hydroxide gel, magnesium hydroxide, calcium hydroxide, etc. are separately added to the system separately from phosphoric acid, phosphorous acid, etc. Alternatively, the reaction may be carried out in a system. Preferred examples of the phosphoric acids (a) include:
Phosphoric acid, magnesium monophosphate, aluminum monophosphate, zinc monophosphate and a mixture of two or more thereof, particularly preferred are phosphoric acid, magnesium monophosphate, aluminum monophosphate And mixtures of two or more of these.

The content of the phosphoric acid (a) is usually 3 to 50% by weight based on all components constituting the foam, from the viewpoint of the fire protection performance of the foam and the uniformity of the foam structure. In a preferred range converted to the content of phosphorus atom of
-20% by weight, especially 4-18% by weight.

In the present invention, as the foaming agent (b),
For example, (b1) a carbonate compound, and (b2) a light metal which reacts with an acid or alkali to generate a gas, and the like can be mentioned.
Specific examples of the carbonate compound (b1) include sodium carbonate, sodium hydrogencarbonate, potassium carbonate, ammonium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, basic zinc carbonate and the like, and the light metal (b2) Specific examples include magnesium, aluminum, zinc and the like. Preferred among those exemplified as the blowing agent (b) are basic magnesium carbonate. The amount of the blowing agent (b) may be determined according to a desired expansion ratio in a wide range from 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.

In the present invention, examples of the urethane prepolymer having an NCO group (c) include those derived from an organic polyisocyanate compound (n) and an active hydrogen-containing compound (h) and having NCO in the molecule. Can be
Examples of the organic polyisocyanate compound (n) include the following (n1) to (n5). However, (n
The carbon number in 1) 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) having 6 to 20 carbon atoms Aromatic polyisocyanate (n5) Modified products of these polyisocyanates

Specific examples of the aliphatic polyisocyanate (n1) include: ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene 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), 1,4-cyclohexane diisocyanate, methyl Cyclohexane-2,4-diisocyanate (hydrogenated TDI); and 1,4-bis (2-isocyanatoethyl) cyclohexane.

Specific examples of the araliphatic polyisocyanate (n3) include: p-xylylene diisocyanate, and tetramethyl xylene diisocyanate.

Specific examples of the aromatic polyisocyanate (n4) include: 1,4-phenylene diisocyanate, 2,4- or 2,6-toluene diisocyanate (TDI), diphenylmethane-2,4'- or 4 , 4′-diisocyanate (MDI) ・ naphthalene-1,5-diisocyanate ・ 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate ・ crude TDI ・ polyphenylmethane polyisocyanate (crude MD
I) and the like.

Specific examples of the modified polyisocyanate (n5) include a carbonamide group, a uretdione group,
Modified products into which a uretoimine group, a urea group, a burette group, an isocyanurate group, a urethane group or the like are introduced.

The selection of the organic polyisocyanate compound (n) is not particularly limited, and may be used alone or in any combination as a component for deriving a urethane prepolymer in accordance with the physical properties and cost of the foam. it can.

Examples of the active hydrogen-containing compound (h) include the following (h1) to (h7). (H1) Alcohols (h2) Polyoxyalkylene polyol (h3) Polyester polyol (h4) Polyolefin polyol (h5) Acrylic polyol (h6) Castor oil-based polyol (h7) Polymer polyol

Specific examples of the alcohols (h1) include:
Aliphatic dihydric alcohols (ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4 butanediol, neopentyl glycol, 1,6 hexanediol, 1,8 octamethylenediol, etc.), having a cyclic group Low molecular weight diols (1,4 bis (2hydroxyethoxyphenyl) propane, etc.), trihydric alcohols (glycerin, trimethylolpropane, hexanetriol, etc.), tetrafunctional or higher polyhydric alcohols (sorbitol, sucrose, etc.) , Alkanolamines (triethanolamine,
Methyldiethanolamine, etc.). Also,
Some of these include aliphatic monohydric alcohols (ethanol,
Methanol, pentanol, dodecanol, etc.).

Polyoxyalkylene polyol (h2)
Examples thereof include alcohols (h1), low molecular weight amines, phenols, and the like, to which 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 phenols include alkylphenol, hydroquinone, bisphenol A and the like. Examples of the alkylene oxide to be added 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). Polyoxyalkylene polyol (h2)
Examples of the polyoxypropylene glycol,
Examples thereof include polyoxypropylene triol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene triol, polyoxypropylene tetraol, and polyoxytetramethylene glycol.

Examples of the polyester polyol (h3) include the following (h31) to (h33). (H31) Condensed polyester polyol obtained by reacting a difunctional or higher polyhydric alcohol with dicarboxylic acids. (H32) Polylactone polyol obtained by ring-opening polymerization of lactone. (H33) Ethylene carbonate and 1,6-hexanediol Polycarbonate polyol obtained by reaction

The dicarboxylic acids constituting the condensed polyester polyol (h31) include, for example, aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.); Group dicarboxylic acids (such as terephthalic acid and isophthalic acid); anhydrides of these dicarboxylic acids, lower alkyl (1 to 4 carbon atoms) esters or acid halides (such as acid chloride), and mixtures of two or more of these. Examples of the lactone used for the polylactone polyol (h32) include ε-caprolactone.

These polyester polyols (h3)
Specific examples of polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene polypropylene adipate, polyethylene butylene adipate, polybutylene hexamethylene adipate, polydiethylene adipate, poly (polytetramethylenetel) adipate , Polyethylene azelate, polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polyethylene terephthalate, polycaprolactone diol, polycarbonate diol and the like.

Specific examples of the polyolefin polyol (h4) include polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol and the like. Specific examples of the acrylic polyol (h5) include a copolymer of hydroxyethyl acrylate and ethyl acrylate, and a copolymer of hydroxyethyl acrylate, ethyl acrylate and styrene. Examples of the castor oil-based polyol (h6) include (h61) castor oil; (h62) polyester polyol of a castor oil fatty acid with a polyhydric alcohol or a polyoxyalkylene polyol, and a mixture of two or more thereof.
Specific examples of (h62) include mono, di or triester of castor oil fatty acid and trimethylolpropane; and mono or diester of castor oil fatty acid and polyoxypropylene glycol.

The polymer polyol (h7) includes (h
JP-A-4-2926 in polyols such as 2) to (h6)
No. 83 can be obtained by polymerizing the ethylenically unsaturated monomer. The content of the ethylenically unsaturated monomer units constituting the polymer polyol is usually 0.1
-90% by weight, preferably 5.0-80% by weight.
As a method for producing the polymer polyol (h7), for example,
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, a method described in US Pat. No. 3,383,351)
Is mentioned.

Among the compounds exemplified above as the active hydrogen-containing compound (h), particularly preferred are the ethylene oxide adducts of the polyoxyalkylene polyol (h2). It is preferably used as a part of (h). By using the ethylene oxide adduct, the dispersibility of the prepolymer (c) in forming an aqueous mixture is improved.

The NCO content in the prepolymer (c) is
Preferably it is 0.5 to 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, and the molecular weight of (c) is preferably 1,000. ~ 50,000. As an example of a method for producing the prepolymer (c), the prepolymer (c) can be produced by charging an organic polyisocyanate (n) and an active hydrogen-containing compound (h) in a reaction vessel and 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 (c) with respect to the total solid content during the production of the foam, depends on the brittleness improving effect of the foam and the fireproof performance. In light of this, it is usually 5 to 30% by weight, and preferably 10 to 25% by weight.

As the polyvalent metal borate (d) in powder form,
Examples include zinc borate, aluminum borate, lead borate, barium borate, manganese borate, magnesium borate, nickel borate, cadmium borate, bismuth borate, copper borate, silver borate, and the like. The powder may be of any particle size, including granules and lumps. These polyvalent metal borates may be added in the form of a polyvalent metal borate, or a metal compound chemically active with boric acid, for example, a polyvalent metal oxide such as magnesium oxide or calcium oxide, or water. Add a polyvalent metal hydroxide such as aluminum oxide gel, magnesium hydroxide, calcium hydroxide, etc., or a polyvalent metal carbonate such as magnesium carbonate, calcium carbonate, zinc carbonate, etc., separately from boric acid into the system. The reaction can be carried out by Preferred examples of the powdered polyvalent metal borate (d) include zinc borate, magnesium borate,
Calcium borate, aluminum borate, iron borate and mixtures of two or more of these.

The content of the powdery borate (d) unit in the foam of the present invention, that is, the content of (d) with respect to the total solid content in the production of the foam, is determined by the strength of the foam obtained by combustion and carbonization. From the viewpoint of the expansion ratio of the foam, the amount is usually 1 to 50% by weight, preferably 5 to 40% by weight.

The foam of the present invention may contain an inorganic filler (e) if necessary in consideration of physical properties and cost.
Examples of the inorganic filler (e) include the following (e1) to (e)
5). (E1) Cement: Portland cement, silica cement, alumina cement blast furnace cement, fly ash cement, white cement, etc. (e2) Clay mineral: morillonite, bentonite, mica, sericite, kaolin talc, philite, zeolite, etc. (e3) Inorganic Light aggregate: perlite, shirasu balloon, etc. (e4) Inorganic fiber: carbon fiber, asbestos, rock wool, glass fiber, ceramic fiber, potassium titanate fiber, steel fiber, etc. (e5) Other water-insoluble inorganic powder materials: Fly ash, silica fume, silica powder, ceramic powder, aluminum hydroxide, alumina, calcium sulfate, etc.

There is no particular limitation on the selection of those exemplified as (e) above, and they may be added alone or in any combination according to the requirements of the physical properties and cost of the foam.
For example, the hardness of the foam is improved by adding the cement (e1). Among the cements (e1), alumina cement is preferable because it has low alkalinity even in the cement, and thus has low reactivity with the phosphoric acids (a). By the addition of the inorganic fiber (e4), the tensile strength and the bending strength of the foam are improved, and the shape retention after the organic matter in the foam is temporarily burned is improved. Further, the aluminum hydroxide of (e5) improves the fire prevention performance by being added. Others exemplified as (e) can be mainly used as an expanding material for cost reduction. (E)
There is no particular limitation on the addition amount of the phosphoric acid (a) 10
1800 parts by weight or less, preferably 5 parts by weight with respect to 0 parts by weight
Not more than 00 parts by weight. Organic fibers can be used instead of or in combination with the inorganic fibers (e4). Organic fibers also have an effect of improving the tensile strength, bending strength, etc. 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.

If the content of (c) is within the above-mentioned preferred range, the foam of the present invention has a considerably high fire protection. However, in order to provide a higher fire protection, a flame retardant is added to the component. Can be foamed and cured. Non-halogen phosphates (triphenyl phosphate,
Cresyl diphenyl phosphate, ammonium polyphosphate, etc.), halogen-containing phosphates (trischloroethylphosphonate, trisdichloropropylphosphate, tris (tribromophenyl)
Phosphate, trisdibromopropyl phosphate, etc.), active hydrogen-containing flame retardant (di (isopropyl)
N, N bis (2-hydroxyethyl) aminomethyl phosphate, an alkylene oxide adduct of brominated bisphenol A, etc.), antimony trioxide, antimony pentoxide, zinc oxide, and the like. The above examples are
One type or two or more types may be used. The amount of the flame retardant used is usually 0.1 to 40 with respect to 100 parts by weight of the urethane prepolymer.
Department.

According to the method of the present invention, phosphoric acids (a),
By mixing a foaming agent (b), a urethane prepolymer having an NCO group (c), a powdery polyvalent metal borate (d) and, if necessary, an inorganic filler (e) into an aqueous mixture. When foamed and cured, the foam of the present invention 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 is usually such that the concentration of the aqueous mixture becomes about 50 to 90% by weight.

In the method of the present invention, in order to control the curing speed of the prepolymer (c), for example, a catalyst may be added. As the catalyst, dibutyltin dilaurate, alkyl titanate, organosilicon titanate, stannas octoate, lead octylate, zinc octylate, bismuth octylate, dibutyltin diorthophenylphenoxite, tin oxide and an ester compound ( Metal catalysts such as reaction products of dioctyl phthalate, etc., monoamines (such as triethylamine), diamines (such as N, N, N ', N'-tetramethylethylenediamine), and triamines (such as N, N, N', Amine catalysts such as N ", N" -pentamethyldiethylenetriamine) and cyclic amines (such as triethylenediamine). The catalyst may be used alone or in combination of a metal and an amine. The amount of the catalyst is usually 0.00.0 parts per 100 parts of the prepolymer (c).
01 to 30 parts.

In the 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, and for example, SH-19 manufactured by Tore Silicone Co., Ltd.
2, SH-193, SH-194, etc .; TFA-4200, manufactured by Toshiba Silicone Co., Ltd .; L-53, manufactured by Nippon Unicar Co., Ltd.
20, L-5340, L-5350, etc., and F-121, F-122 manufactured by Shin-Etsu Silicon Co., Ltd. The amount of the foam stabilizer is usually 0.001 to 3 parts by weight based on 100 parts by weight of the urethane prepolymer.

In the method of the present invention, as a method of foaming and curing by mixing each component, the following [1] is used.
To [4]. [1] After mixing phosphoric acid (a), the prepolymer (c) and water, a foaming agent (b), a powdered polyvalent metal borate (d) and, if necessary, an inorganic filler (e) are combined. And mixing, foaming and curing. [2] Component (a) which is a mixture of phosphoric acid (a) and water
And a prepolymer (c), a foaming agent (b), and a powdery polyvalent metal borate (d) and, if necessary, a mixture (b) of an inorganic filler (e). Method to make. [3] Component (c), which is a mixture of phosphoric acid (a), water and polyvalent metal borate (d) in powder form, prepolymer (c), blowing agent (b), and inorganic if necessary A method in which (d), which is a mixture of the filler (e), is mixed and foam-hardened. [4] Phosphoric acid (a), the prepolymer (c) and a part of water are mixed, and then a metal carbonate (b), a powdery polyvalent metal borate (d) and an inorganic filler as necessary A method in which (e) and the rest of water are mixed to form a slurry (e), and the mixture is charged and foamed and cured. Of these, the methods [1], [2] and [4] are preferred.

The foam of the present invention can be obtained by mixing the components according to the above-mentioned method under normal temperature and normal pressure conditions by the method of the present invention, and then allowing the mixture to stand. After standing, the mixed solution (slurry) foams within a few minutes to several tens of minutes, and then the curing is completed to form a foam. However, in a case where the temperature is low in winter or a case where the foam hardening time is desired to be shortened in the process, it may be heated to about 50 ° C. during standing.

According to the method of the present invention, the foam of the present invention can be formed by pouring the mixture into a mold, and the foam of the present invention can be applied to an arbitrary base material such as a wall surface or filled in an arbitrary space. 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). In the case of application, a mixture obtained by the above method may be formed into a foam by spraying or trowel coating.

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). In addition, even when the obtained foam has a low specific gravity of 0.1 or less in specific gravity, the foam surface is not brittle, and from the adjustment of composition and composition, foams of a wide range of materials from hard to soft can be obtained. . Also, the thermal insulation performance of the foam is controlled by controlling the specific gravity, for example, 0.03 kcal / m ·
In addition to being able to provide a low thermal conductivity of less than hr. ° C., the fire resistance is also at a level equivalent to a quasi-noncombustible material from noncombustible materials, such as glass wool, even when compared to existing heat insulating materials such as rigid urethane foam, It is positioned 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.

[0041]

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 Prepolymer (c)] A raw material component required for a 4-port separable corvene was charged,
The following urethane prepolymers c-1 to c-2 having NCO groups were obtained by a method of reacting at 90 ° C. for 5 hours.

C-1: TDI [Nihon Polyurethane Co., Ltd.
Polyoxyethylene polyoxypropylene glycol [manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: Newpole PE]
-62] A prepolymer obtained by reacting 420 parts by weight. The prepolymer has an NCO content of 6.2% and is a viscous resin solution at room temperature. c-2: 100 parts by weight of crude MDI (manufactured by Nippon Polyurethane Co., Ltd., trade name "Millionate MR-100"), and polyoxyethylene polyoxypropylene triol (manufactured by Sanyo Chemical Industry Co., Ltd., trade name: Sannics GL) −
3000) 150 parts by weight reacted to obtain a prepolymer. NCO content of prepolymer is 10.0%, viscous resin solution at normal temperature.

Examples 1-4, Comparative Examples 1-2 Examples 1-4, Comparative Examples 1-2 Based on the compositions shown in Table 1 below, phosphoric acid (a), the prepolymer (c) and tap water were used. The mixture was uniformly stirred with a homomixer. Examples 1 and 3 further include a blowing agent (b) and a powdered polyvalent metal borate (d) in Examples 1 and 3, and Examples 2 and 4 illustrate a blowing agent (b).
Powdered polyvalent metal borate (d) and inorganic filler (e)
In Comparative Example 1, the foaming agent (b) was added, and in Comparative Example 2, the foaming agent (b) and the inorganic filler (e) were added, and the mixture was stirred and mixed, and then poured into a mold (50 × 30 × 3 cm). The foam was free-foamed to obtain molded foams of Examples 1 to 4 and Comparative Examples 1 and 2.

[0044]

[Table 1]

Note 1) The compounds indicated by the abbreviations are as follows. (A) Phosphates a-1: Calcium monophosphate a-2: Magnesium monophosphate a-3: Phosphoric acid (b) Blowing agent b-1: Basic magnesium carbonate (c) The prepolymer c-1, c-2: Prepolymer obtained in Production Example 1 (d) Powdery polyvalent metal borate d-1: Zinc borate d-2: Barium borate (e) Inorganic filler e-1: Aluminum hydroxide

Test Example 1 [Examples 1-4, Comparative Examples 1-2]
Evaluation of foam of Example 1] 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 Method for Physical Properties of Foam] (1) Thermal Conductivity JIS A-1412 (Method of Measuring Thermal Conductivity of Heat Insulating Plate) (2) Flexibility of Foam Specified in JIS Z1536 (A cushioning material for polystyrene foam packaging). Compliant with the flexibility test. 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. Further, the foam after the combustion test was cut into a 30 mm square, and the compressive strength was measured. (4) Compressive strength JIS K-7220 (Compression test method for hard foamed plastic)

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

[0048]

[Table 2]

[0049]

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 the conventional phosphoric acid foam, and when a foam having a high expansion ratio is used, it is an inorganic-organic composite. Nevertheless, it is a foam having flexibility and resilience enough to be mistaken for a soft urethane foam, and this expansion ratio can be adjusted from soft to hard, and 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.

Because of the above effects, the foam of the present invention can be used for the following applications, taking advantage of its properties of fire protection, heat insulation, elasticity, flexibility, strength and the like. It is suitable for. In applications where fire protection performance is required, such as trains, cars, houses, buildings, etc., alternatives to those in which organic foams such as urethane foam and styrene foam have been used conventionally;
Insulation for exterior and interior panels, sound insulation for floors and walls, and fire protection. In addition, insulation materials for fire-resistant safes, freezers, refrigerators, etc., fire-resistant coating materials, lightweight aggregates, void fillers, synthetic wood with fire-proof performance, etc.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tsuyoshi Tomosada 11-11, Hitotsubashi Nohonmachi, Higashiyama-ku, Kyoto Inside Sanyo Chemical Industry Co., Ltd.

Claims (6)

[Claims] 1. A phosphoric acid foam structure comprising a phosphoric acid (a) and a foaming agent (b), wherein brittleness is improved by a cured product of a urethane prepolymer (c) having an NCO group, and An inorganic-organic composite foam comprising a powdery polyvalent metal borate (d) and optionally another inorganic filler (e). 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. Foam. 3. The foam according to claim 1, wherein the foaming agent (b) is a carbonate compound. 4. The foam according to claim 1, wherein the content of the powdery polyvalent metal borate (d) is 1 to 50% by weight. 5. The powdery polyvalent metal borate (d) is at least one powdery compound selected from the group consisting of zinc borate, calcium borate, magnesium borate, aluminum borate and iron borate. 5. The foam according to any one of items 4 to 4. 6. Phosphoric acid (a), blowing agent (b), NCO
Urethane prepolymer having a group (c), powdered polyvalent metal borate (d), water and optionally inorganic filler (e)
A method for producing an inorganic-organic composite foam which is foamed and cured by mixing components consisting of: