JPH11269297A - Preparation of inorganic organic composite foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preparing a foam excellent in thermal insulating properties and flame retardance and, simultaneously, low in an environmental load. SOLUTION: An inorganic organic composite foam can be obtained by mixing an aqueous solution of a phosphoric acid, a metal salt of carbonic acid, a urethane prepolymer having an NCO group and, if desired, an inorganic filler; pouring the resulting mixed liquid into a mold; and effecting foaming and curing in the mold. It is preferred that the mixing is carried out by a low pressure discharging agitation mixing method or the agitation mixing is carried out by a helically rotational or pin-equipped rotational agitation mixing method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an inorganic-organic composite foam. More specifically, it is an inorganic-organic composite foam having an inorganic foam structure and markedly improved brittleness by a reactive elastic polymer, and has flexibility and rebound resilience such as urethane foam and styrene foam. Can be comparable to forms,
The present invention also relates to a method for producing an inorganic-organic composite foam having both fire prevention performance.

[0002]

2. Description of the Related Art Conventionally, as foams which can be molded by a stirring / mixing type foaming machine of low pressure discharge (low pressure foaming machine), urethane resin foam, urea resin foam, phenol resin foam and the like are known. ing.

[0003]

However, these foams generate toxic gas and soot due to incomplete combustion during combustion,
It is difficult to avoid damage to the incinerator due to excessive combustion heat generation, and there is a problem that the load on the environment is high in that respect. In addition, in the flame retardancy test (JIS A-1321), there was a problem that the temperature-time area and the smoke generation coefficient became remarkably large, and the flame retardance did not pass grades 1 to 3.

[0004]

Means for Solving the Problems The present inventors have sincerely studied a low-density foam having a low environmental load and arrived at the present invention.

That is, the present invention relates to a method of mixing a phosphoric acid (a) aqueous solution, a metal carbonate (b), a urethane prepolymer having an NCO group (c) and, if necessary, an inorganic filler (d). Is injected into a mold and foamed and cured in the mold to produce an inorganic-organic composite foam.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The inorganic-organic composite foam obtained by the production method of the present invention has an inorganic foam structure formed by reacting phosphoric acid (a) with a metal carbonate (b) to foam. The brittleness is improved by the urethane prepolymer (c) having an NCO group. The metal carbonate (b) reacts with the phosphoric acids (a) to form an inorganic skeleton and simultaneously generate carbon dioxide. This carbon dioxide causes foaming. The rate of generation of carbon dioxide varies depending on the specific surface area of the metal carbonate, and is high when the specific surface area is large and low when the specific surface area is small. If the generation rate of carbon dioxide is too high, foaming occurs before the strength of the inorganic skeleton is obtained, and thus collapse of the foam occurs. Therefore, it is necessary to limit the specific surface area of the metal carbonate.
It is preferably at most 5 m ² / g. The 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 curing of the prepolymer (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 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, or a metal compound chemically active with phosphoric acid or phosphorous acid, for example, oxidation. Polyvalent metal oxides such as magnesium and calcium oxide and polyvalent metal hydroxides such as aluminum hydroxide gel, magnesium hydroxide and calcium hydroxide are separately added to the system together with phosphoric acid and phosphorous acid. 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.

[0008] The content of the phosphoric acid (a) is usually 3 to 5 in all the components constituting the foam obtained by the production method of the present invention.
0% by weight, and in a preferred range in terms of the content of phosphorus atoms in the foam of the present invention, it is 3 to 20% by weight, particularly 4 to 18% by weight. Content of phosphorus atom is 3
When the amount is less than the weight%, the fire prevention performance of the obtained foam decreases.
When the phosphorus atom content exceeds 20% by weight, the dispersibility of the prepolymer (c) is reduced, and a uniform foamed structure may not be obtained.

In the present invention, the metal of the metal carbonate (b) is an alkali metal (eg, sodium, potassium, rubidium) as a monovalent metal; an alkaline earth metal (eg, magnesium, calcium, barium) as a polyvalent metal, IIIa , IVa metals (eg, aluminum, germanium, tin) and transition metals (eg, iron, cobalt, nickel, copper, zinc). Of these, polyvalent metals are preferred, and calcium is more preferred.
At least one polyvalent metal selected from the group consisting of magnesium, barium, zinc, aluminum and iron. Specific examples of the metal carbonate (b) include sodium carbonate, sodium hydrogen carbonate, potassium carbonate, ammonium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, basic zinc carbonate and the like.
Basic magnesium carbonate and calcium carbonate. 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 (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 1-1
00 parts by weight. Also, in combination with the metal carbonate (b),
Other blowing agents may be used. As another foaming agent, the prepolymer (c) may be part of foaming by generating carbon dioxide gas by water in the system. Further, in (c), an organic blowing agent which decomposes by heating (a nitroso blowing agent such as dinitrosopentamethylenetetramine or N, N'-dimethyl-N, N'-dinitrosoterephthalamide);benzenesulfonylhydrazide; Azodicarbonamide, p
-Sulfohydrazide-based blowing agents such as toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide), and 3,3'-disulfohydrazidediphenylsulfone; azobisisobutyronitrile, azobisformamide, diethylazo An azo foaming agent such as dicarboxylate) is preliminarily mixed and subjected to secondary foaming by heating. Examples of other foaming agents include gases such as freon gas, butane gas, and liquefied carbon dioxide gas, low-boiling solvents, and water.

In the present invention, examples of the prepolymer (c) include those derived from an organic polyisocyanate compound (n) and an active hydrogen-containing compound (h) and having NCO in the molecule. Examples of the organic polyisocyanate compound (n) include the following (n1) to (n)
5). 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) having 6 to 20 carbon atoms Aromatic polyisocyanate (n5) Modified polyisocyanate of (n1) to (n4)

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,-methylcyclohexane-2. , 4-diisocyanate (hydrogenated TDI), 1,4-bis (2-isocyanatoethyl) cyclohexane and the like.

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 [commonly referred to as crude M
DI: an aromatic amine such as aniline or a mixture thereof;
It is a phosgenated product of a condensate with formaldehyde (to be a mixture of diaminodiphenylmethane and a small amount, for example, 1 to 20% by weight of a polyamine having three or more amino groups). And the like.

Specific examples of the modified polyisocyanate (n5) of (n1) to (n4) include (n1) to (n)
Examples of 4) include, in place of the isocyanate group of the polyisocyanate exemplified above, modified products in which a carbonamide group, uretdione group, uretoimine group, urea group, buret group, isocyanurate group, urethane group, or the like is introduced. . The selection of the organic polyisocyanate compound (n) is not particularly limited, and it can be used alone or in any combination as a component for inducing a urethane prepolymer in accordance with the physical properties and cost of the foam.

Examples of the active hydrogen-containing compound (h) include a low molecular weight polyol (h1) and a high molecular weight polyol (h2). Here, (h1) and (h
When the range of each molecular weight in 2) is represented by a hydroxyl value,
The hydroxyl value of (h1) is usually from 300 to 1,000.
Or more, preferably 350-800. or,
The hydroxyl value of (h2) is usually less than 300, preferably 20 to 250, especially 50 to 200. The number of functional groups of the active hydrogen-containing compound (h) is (h1), (h
In each case of 2), it is usually 2 to 8 or more.

The low molecular weight polyol (h1) includes 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) Polyfunctional alcohols having four or more functional groups (h1-5) ) Alkanolamines (h1-6) Of the compounds of (h1-1) to (h1-5),
Low molar adduct of ethylene oxide and / or propylene oxide

On the other hand, 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

Among the low molecular weight polyols (h1), specific examples of the aliphatic dihydric alcohols (h1-1) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, Pentyl glycol, 1,6 hexane diol, 1,8 octamethylene diol and the like can be mentioned.
Specific examples of the low molecular weight diols (h1-2) having a cyclic group include 1,4bis (2-hydroxyethoxyphenyl) propane. Trihydric alcohols (h
Specific examples of 1-3) include glycerin, trimethylolpropane, hexanetriol and the like. 4
Specific examples of the polyhydric alcohols having functionalities or higher (h1-4) include sorbitol and shoux rose. Specific examples of the alkanolamines (h1-5) include triethanolamine and methyldiethanolamine. Specific examples of the low-molar adduct (h1-6) include, in addition to those listed as specific examples of (h1-1) to (h1-5), ethylene oxide and / or propylene oxide having a hydroxyl value of 300.
Those having a low molar addition within the above range can be mentioned.

On the other hand, among the high molecular weight polyols (h2), the polyoxyalkylene polyol (h2-1) has been described in the section of the low molecular weight polyol (h1) (h2).
1-1) to (h1-5), low molecular weight amines,
Examples thereof include those obtained by adding an alkylene oxide to polyhydric phenols. Examples of low molecular amines include low molecular polyamines such as ethylenediamine, tetramethylenediamine, and hexamethylenediamine, n-butylamine,
Low molecular weight monoamines such as stearylamine are exemplified.
Examples of polyhydric phenols include hydroquinone, bisphenol A, bisphenol F, and bisphenol S. As the alkylene oxide to be added,
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). Specific examples of the polyoxyalkylene polyol (h2-1) include polyoxypropylene glycol, polyoxypropylene triol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene triol, polyoxypropylene tetraol, and polyoxytetraol. Methylene glycol and the like can be mentioned.

Examples of the polyester polyol (h2-2) include the following (h2-21) to (h2-23). (H2-21) Condensed polyester polyol obtained by reacting polyfunctional alcohols having two or more functional groups with dicarboxylic acids (h2-22) Polylactone polyol obtained by ring-opening polymerization of lactone (h2-23) ethylene carbonate Polycarbonate polyol obtained by reaction of 1,6 hexanediol

Condensed polyester polyol (h2-2)
Examples of the dicarboxylic acids constituting 1) include:-aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.);-aromatic dicarboxylic acids (terephthalic acid, Examples thereof include anhydrides, lower alkyl (C1-4) esters or acid halides (such as acid chloride) of these dicarboxylic acids, and mixtures of two or more of these. Examples of the lactone used for the polylactone polyol (h2-22) include ε-caprolactone.

These polyester polyols (h2-
Specific examples of 2) include 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, polybutylene azelate, polybutylene sebacate, Examples include polyethylene terephthalate, polycaprolactone diol, and polycarbonate diol.

Specific examples of the polyolefin polyol (h2-3) include polybutadiene polyol, hydrogenated polybutadiene polyol, and polyisoprene polyol. Specific examples of the acrylic polyol (h2-4) include a copolymer of hydroxyethyl acrylate and ethyl acrylate, and a copolymer of hydroxyethyl acrylate, ethyl acrylate and styrene. The castor oil-based polyol (h2-5) includes (h2
2-51) Castor oil; (h2-52) Polyester polyol of castor oil fatty acid with polyhydric alcohol or polyoxyalkylene polyol, and a mixture of two or more thereof. Specific examples of (h2-52) 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 (h2-6) includes
Among the high molecular weight polyols exemplified as (h2-1) to (h2-5), those obtained by polymerizing ethylenically unsaturated monomers described in U.S. Pat. No. 3,383,351, such as acrylonitrile and styrene. Is mentioned. The content of the ethylenically unsaturated monomer units constituting the polymer polyol (h2-6) is usually 0.1 to 90% by weight, preferably 5.0 to 80% by weight. Polymer polyol (h2
As a production method of -6), 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, US Pat.
383351).

Among the compounds exemplified above as the active hydrogen-containing compound (h), particularly preferred are the ethylene oxide adducts of the polyoxyalkylene polyol (h2-1). It is preferable to use as a part of the 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 prepolymer (c) in forming an 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 ratio of (h1) to (h2) is not particularly limited. In order to enhance the effect of improving body brittleness and enhance the effect of imparting flexibility, the weight ratio is (h1) :( h2) = (0-50) :( 50-1)
(00), the usage ratio of (h2) should be increased. On the other hand, in order to further increase the rigidity of the foam, the weight ratio is (h1) :( h2) = (50-100) :( 0-5)
It is preferable to increase the usage ratio of (h1) so as to be 0).

In order to adjust the molecular weight and viscosity of the 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; alkylene oxides of alkylphenols (octylphenol, nonylphenol, dodecylphenol, etc.) Ethylene oxide, propylene oxide, etc.)
And adducts. The molecular weight of the monol (h3) is usually in the same range as (h1) or (h2). Monool (h) used as necessary in the active hydrogen compound (h)
The ratio of 3) is within a range where the average number of functional groups in (h) is usually 2 or more, preferably 2.5 or more.

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 the 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 obtained by the present invention, that is, the content of (c) with respect to the total solid content at the time of producing the foam is 5 to 30% by weight, particularly 10 to 25% by weight. % By weight. When the content is less than 5% by weight, the effect of improving the brittleness of the foam decreases,
If the content is more than 30% by weight, the fire protection performance is reduced.

In the present invention, an inorganic filler (d) may be used if necessary in consideration of physical properties and cost. Examples of the inorganic filler (d) include the following (d-1) to (d-
5). (D-1) Clay mineral: montmorillonite, bentonite, mica, sericite, kaolin, talc, phyllite, zeolite, etc. (d-2) Lightweight inorganic aggregate: pearlite, shirasu balloon, etc. (d-3) Inorganic fiber: carbon fiber , Asbestos, rock wool, glass fiber, ceramic fiber, potassium titanate fiber, steel fiber, etc. (d-4) Other water-insoluble inorganic powder materials: fly ash, silica fume, silica stone powder, ceramic powder, aluminum hydroxide, alumina , Calcium carbonate, calcium sulfate, sodium borate, boric acid and the like. (D-5) Other water-insoluble inorganic powder materials: fly ash, silica fume, silica powder, ceramic powder, aluminum hydroxide, alumina, calcium sulfate, sodium borate, boric acid, etc.

There is no particular limitation on the selection of those exemplified as (d) above, and they may be added alone or in any combination according to the requirements of the physical properties, cost and the like of the foam. By the addition of the inorganic fiber (d-3), 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. Also, (d-5)
Of these, aluminum hydroxide and calcium carbonate improve the fire protection performance by being added. Others exemplified as (d) can be used as a bulking agent mainly for cost reduction. (D) is preferably (d-4), and particularly preferably aluminum hydroxide, alumina and calcium sulfate. 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 (d-3). 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 obtained by the production method of the present invention has a considerably high fire protection if the content of (d) is within the above-mentioned preferable range. A foaming hardening can also be performed by adding a flame retardant to the components. 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 (tribromophosphate). Phenyl) phosphate, trisdibromopropylphosphate, etc.), active hydrogen-containing flame retardant {di (isopropyl) N, N bis (2hydroxyethyl) aminomethyl phosphate, alkylene oxide adduct of brominated bisphenol A, etc.}, Examples include antimony oxide, antimony pentoxide, and zinc oxide.
One of the above examples may be used alone or two or more of them may be used. The amount of flame retardant used is usually urethane prepolymer (c)
40 parts by weight or less, preferably 100 parts by weight,
0.1 to 30 parts by weight.

In the present invention, (a), (b), (c)
The medium used for (d) includes water. The amount of water used in the present invention is determined by the amount of phosphoric acid (a)
As long as the mixture of the inorganic filler (d) and the inorganic filler can be slurried, it is not necessary to add water more than necessary. The amount of water is not particularly limited, but usually the concentration of the mixture is 50 to 90.
It is an amount to be about weight%. Further, the metal carbonate (b) may be used in the form of a powder without being made liquid.

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. Examples of the catalyst include dibutyltin dilaurate, alkyl titanate, organosilicon titanate, stannas octoate, lead octylate, zinc octylate, bismuth octylate, dibutyltin diorthophenylphenoxite, tin oxide and an ester compound ( Metal-based 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') , N ", N" -pentamethyldiethylenetriamine and the like, and amine catalysts such as 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 10 to 100 parts by weight of the prepolymer (c).
It is not more than 5 parts by weight, preferably 0.01 to 5 parts by weight.

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. For example, SH-192 and SH-19 manufactured by Toray 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. F-121, F-122, etc., manufactured by Shin-Etsu Chemical Co., Ltd. The amount of the foam stabilizer is usually 5 parts by weight or less, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the urethane prepolymer.

In the present invention, (a), (b), (c)
The mixing of (d) and (d) is not particularly limited,
Static mixing etc. are mentioned. Of these, stirring and mixing are preferred, and stirring and mixing with low-pressure discharge are particularly preferred. As a foaming machine (low-pressure foaming machine) for stirring and mixing by low-pressure discharge, it is a low-pressure type foaming machine for polyurethane foam molding. The polyurethane resin handbook (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun, published in 1987)
A foaming machine described on pages 32 to 141 can be used. Low pressure discharge is the discharge pressure during mixing, usually 10 kg.
f / cm ² or less, and preferably from normal pressure to 7 kgf /
cm ² . As a specific example of the helical rotary stirring and mixing foaming machine, a multi-component foaming machine 30 manufactured by Gasmer Admiral Co., Ltd.
K-6PF, MEG-E-24 type low-pressure foaming machine manufactured by Maruka Processing Machine Co., Ltd., and MP-303N type low-pressure foaming machine manufactured by PEC Corporation. Specific examples of the pin-type rotary stirring and mixing foaming machine include a spiral pin mixer manufactured by Taiheiyo Kiko Co., Ltd., and a PU mechanical floss foaming machine manufactured by Toho Kikai Kogyo.

An example of the manufacturing method is shown here. (A),
(B), (c) and, if necessary, liquid (d) are blended, and uniformly stirred. The liquid is put into a raw material tank of a multi-component low-pressure foaming machine, and each liquid is adjusted to 10 to 25 ° C. After confirming that the mixture is discharged at a predetermined mixing ratio, the discharge pressure is 4 to 7 kgf /
The mixture is discharged and mixed in cm ² and injected into a mold adjusted to 40 ° C. After holding at the same temperature for 20 minutes, the mold is removed to obtain a predetermined foam.

The expansion ratio of the foam of the present invention can be arbitrarily selected according to the purpose, but is usually 5 to 50 times, preferably 10 to 40 times, from the quality of the foam.

The foam of the present invention can be made into a molded article, plate, rod, cylinder, or the like having an arbitrary shape by using the above foaming machine. Further, the foam of the present invention can be appropriately subjected to post-treatments such as surface treatment such as painting and impregnation with fragrance. Foams are used for structural materials, protective materials, heat insulating materials,
Sound insulation materials and the like.

The thermal insulation performance of the foam can be controlled by controlling the density so that a low thermal conductivity of, for example, 60 mW / m · K or less can be imparted. Compared to existing insulation materials such as glass wool and rigid urethane foam, it is positioned as a material having excellent properties, such as a grade 2 (quasi-noncombustible material). 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.

[0039]

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-3 having NCO groups were obtained by a method of reacting at 90 degrees for 5 hours.

C-1: TDI [Nippon Polyurethane Co., Ltd.
(Trade name: Coronate T-80), 100 parts by weight of polyoxyethylene polyoxypropylene glycol [molecular weight 2188, block copolymer of 20% by weight of ethylene oxide and 80% by weight of propylene oxide], Sanyo Chemical Industries, Ltd. Product name: New Pole PE
-62] A prepolymer obtained by reacting 420 parts by weight. A prepolymer having a NCO content of 6.2% and a number average molecular weight of 1355, and a viscous resin solution at normal temperature. c-2: 100 parts by weight of crude MDI (manufactured by Nippon Polyurethane Co., Ltd., trade name "Millionate MR-100"), and ethylene oxide added to polyoxyethylene polyoxypropylene triol (molecular weight 3000, glycerin propylene oxide adduct) (Sannicks GL-3000, manufactured by Sanyo Chemical Industries, Ltd.) 1
A prepolymer obtained by reacting 50 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. c-3: MDI (manufactured by BASF: trade name: Luplanate M)
I) 100 parts by weight of ethylene butylene adipate [molecular weight 1000, manufactured by Sanyo Chemical Industries, Ltd., trade name:
Sun Ester No. 22) A prepolymer prepared by reacting 133 parts by weight with 26 parts by weight of polyethylene glycol [molecular weight: 400, manufactured by Sanyo Chemical Industries, Ltd., trade name: PEG400]. The NCO content of the prepolymer is 6.5%,
A resin solution having a number average molecular weight of 1300 and viscous at room temperature.

Examples 1 to 6 One example of the manufacturing method is shown here. (A) and, if necessary, (d), (b) and (c) solutions were blended based on the composition shown in Table 1 below and uniformly stirred. Put into the raw material tank of the multi-component foaming machine 30K-6PF manufactured by Gasmer Admiral Co., Ltd.
Each liquid was adjusted to 20 ° C. After confirming that the mixture is discharged at a predetermined mixing ratio, the mixture is discharged and mixed at a discharge pressure of 5 kgf / cm ² ,
It was poured into a mold (300 × 400 × 50 mm) adjusted to 40 ° C. After maintaining at the same temperature for 20 minutes, the mold was removed to obtain a predetermined foam.

The obtained foam was left in a well-ventilated room for one month, then dried in a dryer at 40 ° C. for 120 hours, and then left in a desiccator for 24 hours. Was served. [Test Methods for Physical Properties of Foam] (1) Density (unit: g / cm ³ ) (2) Compressive strength (unit: kPa) JIS K-7220 (Compression test method for rigid foamed plastic) (3) Heat conduction Rate (unit: mW / m · K) JIS A-1412 (Method of measuring thermal conductivity of heat insulating plate) (4) Flame retardancy test Measured in accordance with JIS A-1321 (Test method of flame retardancy).

[Test Results] Table 1 shows the formulations and the results of the physical properties tests of Examples 1 to 6.

[0044]

[Table 1]

[0045]

The inorganic-organic composite foam obtained by the production method of the present invention has the following effects. (1) To significantly improve brittleness, which has been a problem of the conventional foam of phosphoric acids. (2) Even a foam having a low specific gravity and a high expansion ratio has a strength that does not cause any problem in operation, so that a lightweight heat insulating material can be produced. (3) In terms of appearance and performance, existing urethane foam,
Although almost at the same level as styrene foam, the fire resistance of the material is higher than those of existing organic insulation materials.
It is a material of a level corresponding to a grade (non-combustible material) to a second class (quasi-combustible material), and is a material having high safety in disaster prevention.

Because of the above effects, the foam obtained by the production method of the present invention makes use of its properties of fire protection, heat insulation, elasticity, flexibility, strength, low density, etc.
For example, it is suitable for use in the following applications.
For applications requiring heat 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, interior and exterior insulation boards and panels of houses and buildings such as ceilings, walls, floors and roofs, tatami core materials, gap filling materials such as doors, roofing tiles and insulation materials of roofing materials, automobiles, trains, aircraft and ships Lining materials, interior materials around engines, substitute materials for honeycomb parts, insulation materials for refrigerators, air conditioners, freezers, air conditioning equipment and air conditioning lines, insulation coating materials for natural gas tanks and pipelines such as LNG, factories It is suitable as a thermal insulation packing material for the utility line in Japan and as a thermal insulation packing material for transporting frozen goods.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3/00 C08K 3/00 3/26 3/26 3/32 3/32 C08L 75/04 C08L 75/04 // (C04B 28/34 24:24) (C08G 18/00 101: 00) B29K 105: 04 (72) Inventor Tadaaki Yamazaki 1-11, Hitotsubashi-Honcho, Higashiyama-ku, Kyoto Inside Sanyo Kasei Kogyo Co., Ltd. (72) Inventor Hideyuki Nishida 1 Sanyo Kasei Kogyo Co., Ltd., 11-11, Hitotsubashi Nohonmachi, Higashiyama-ku, Kyoto

Claims (7)

[Claims] 1. A phosphoric acid (a) aqueous solution, a metal carbonate (b), a urethane prepolymer having an NCO group (c)
And a method for producing an inorganic-organic composite foam, in which an inorganic filler (d) is mixed if necessary, and the mixed liquid is poured into a mold and foamed and cured in the mold. 2. The method according to claim 1, wherein the mixing is carried out by low pressure discharge stirring type mixing. 3. The method according to claim 1, wherein the stirring and mixing is performed by a helical rotation type, or
3. The method according to claim 1, wherein the mixing is performed by a rotary stirring type mixing with a pin.
Production method as described. 4. 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. The production method according to any one of the above. 5. The method according to claim 1, wherein the metal carbonate (b) is a polyvalent metal carbonate. 6. The expansion ratio is from 5 to 50 times.
5. The production method according to any one of the above items 5. 7. A foam obtained by the production method according to any one of claims 1 to 6 and having a first or second class flame retardant performance according to JIS A-1321.