JPH1067877A - Inorganic-organic composite foam and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an inorg.-org. composite foam improved in fire prevention heat insulating properties, elasticity, softness, and strengths by foaming and curing a water-base mixture contg. sulfuric acid, a specific blowing agent, and a urethane prepolymer. SOLUTION: An inorg.-org. composite foam having a thermal conductivity of 0.03kcal/m.hr. deg.C or lower is produced by foaming and curing a water-base mixture contg. sulfuric acid, calcium or barium carbonate usually in an amt. of 0.1-200wt.% of sulfuric acid, and a urethane prepolymer having a mol.wt. of 1,000-50,000 in an amt. of 5-30wt.% of the solid content of the mixture. If necessary, the mixture may further contain a compd. selected from among calcium oxide, barium oxide, calciug hydroxide, and barium hydroxide in an amt. of 1-200 vvt.% of sulfuric acid and/or an inorg. filler in an amt not higher than 1.800wt.% of sulfuric acid. In addition, the mixture may also contain up to 40wt.% (based on the prepolymer ; the same applies hereunder) flame retardant, up to 30wt.% catalyst, and up to 3 wt. % foam stabilizer.

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. The present invention relates to an inorganic-organic composite foam which can be made comparable to a foam and has fire protection 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 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 brittle because it is a completely inorganic material, and has a disadvantage that the foam formed by even a small force is broken and cannot be restored. Particularly, a large panel having a low specific gravity is used. When it is made, it cannot be said that it is a material suitable for practical use because it has problems such as the surface layer being collapsed just by touching, and the panel strength being too weak to be portable. 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. Is difficult to sufficiently modify, and it is even more difficult to obtain a foam having flexibility and resilience such as urethane foam and styrene foam.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve these problems of the conventional foams of phosphoric acids, and as a result, calcium phosphate or barium sulfate-based inorganic materials were used instead of phosphoric acids as inorganic materials. Further, unlike the above resin emulsion, a foam using a urethane prepolymer having an NCO group, which is a polymer having reactivity and elasticity, was obtained. Further, as a result of the study of the present inventors, when this prepolymer is used, when a foam having a high expansion ratio is used, it is an organic-inorganic composite,
A foam having flexibility and resilience enough to be mistaken for a soft urethane foam can be obtained, and the expansion ratio can be adjusted from soft to hard, and the finding that the brittleness is remarkably improved in both the soft and hard cases is obtained. Was.

That is, the present invention provides the following inorganic-organic composite foams <1> and <2> and a method for producing an inorganic-organic composite foam <
3>. <1> From sulfuric acid (a), a foaming agent (b1) composed of calcium carbonate or barium carbonate, and, if necessary, a compound (b2) selected from the group consisting of calcium oxide, barium oxide, calcium hydroxide and barium hydroxide. An inorganic-organic composite foam having improved brittleness by a polyurethane (polyurea) or polyurethane urea resin cured product (c) formed in situ from a urethane prepolymer (c1) having an NCO group having a foam structure of . <2> The above foam further containing an inorganic filler (d). <3> Sulfuric acid (a), a blowing agent (b1) composed of calcium carbonate or barium carbonate, a urethane prepolymer (c1) having an NCO group, water, and, if necessary, calcium oxide, barium oxide, calcium hydroxide and A method for producing an inorganic-organic composite foam which comprises mixing a component comprising a compound (b2) selected from the group consisting of barium hydroxide and / or an inorganic filler (d) and foam-curing the mixture.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The inorganic-organic composite foam of the present invention comprises:
The sulfuric acid (a) reacts with a foaming agent (b1) composed of calcium carbonate or barium carbonate and, if necessary, a compound (b2) selected from the group consisting of calcium oxide, barium oxide, calcium hydroxide and barium hydroxide. It has a foamed, inorganic foam structure. Further, since the urethane prepolymer (c1) contains an NCO group reactive with a compound having active hydrogen such as water, the foam of the present invention is an elastic polymer formed in situ from (c1). The brittleness is improved by a certain polyurethane, polyurea or cured polyurethane urea resin (c). Further, the foam of the present invention includes, for example, sulfuric acid (a),
Foaming agent consisting of calcium carbonate or barium carbonate (b
1) an urethane prepolymer (c1) and, if necessary, a component comprising a compound (b2) selected from the group consisting of calcium oxide, barium oxide, calcium hydroxide and barium hydroxide as an aqueous mixture, obtained by foaming and curing. It is. That is, by using this aqueous mixture,
The foaming and curing reaction of (a) and (b1) and, if necessary, (b2), and the curing reaction of (c1) with water proceed to obtain the foam of the present invention.

In the present invention, the sulfuric acid (a) includes various industrial sulfuric acids whose concentrations are variously adjusted by dilution with water.

In the present invention, among the foaming agents (b1),
Calcium carbonate or barium carbonate (b11) may be used alone or in combination, and reacts with sulfuric acid (a) to generate carbon dioxide gas and form the inorganic skeleton of the foam.
As the foaming agent (b1), in addition to (b11), a light metal (b12) that reacts with an acid or alkali to generate a gas may be used in combination. Specific examples of the light metal (b12) include barium, aluminum, and zinc.

In addition, other foaming agents can be used in combination with the foaming agent (b1) of the present invention. Examples of other foaming agents include an organic foaming agent [(dinitrosopentamethylenetetramine or N, N ') which decomposes by heating in (c1).
-Nitroso-based blowing agents such as -dimethyl N, N'-dinitrosoterephthalamide, benzenesulfonylhydrazide azodicarbonamide, p-toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonyl) hydrazide, 3,3 Sulfohydrazide foaming agents such as' -disulfohydrazide diphenylsulfone, azo foaming agents such as azobisisobutyronitrile, azobisformamide and diethylazodicarboxylate) are mixed in advance to obtain the foam of the present invention. After forming
Furthermore, a method of secondary foaming the added foaming agent by heating can be adopted. The prepolymer (c
In 1), carbonic acid gas is generated during the curing reaction between (c1) and water, and also functions as a part of the foaming agent.

The amount of (b1) and the other blowing agents may be determined according to a desired expansion ratio in a wide range from soft to hard. The amount of (b1) is not particularly limited as long as (a) and (b1) are well mixed in an aqueous mixture,
Usually 0.1 to 200 parts by weight per 100 parts by weight of sulfuric acid (a).
Parts by weight, preferably 1 to 100 parts by weight. The amounts of the compound (b2) selected from the group consisting of calcium oxide, barium oxide, calcium hydroxide, and barium hydroxide, which are used as necessary, are (b1) and (b2)
The total amount of (a) is usually 1
-200 parts by weight, preferably 5-100 parts by weight.

In the present invention, examples of the prepolymer (c1) include those derived from an organic polyisocyanate compound (n) and an active hydrogen-containing compound (h) and having a terminal NCO group in the molecule. Reaction (n) may be included. Examples of the organic polyisocyanate compound (n) include the following (n1) to (n5). However, the carbon number in (n1) to (n5) is a value excluding the carbon number in the NCO group. (N1) an aliphatic polyisocyanate having 2 to 12 carbon atoms (n2) an alicyclic polyisocyanate having 4 to 15 carbon atoms (n3) an araliphatic polyisocyanate having 8 to 12 carbon atoms (n4) 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), 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 [commonly known 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 modified products obtained by introducing a carbodiimide group, a uretdione group, a uretoimine group, a urea group, a buret group, an isocyanurate group, a urethane group, or the like instead of the isocyanate group of the polyisocyanate exemplified above. 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

Of 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, Neopentyl glycol, 1,6-hexanediol, 1,8-octamethylenediol and the like can be mentioned. Specific examples of the low molecular weight diols (h1-2) having a cyclic group include 1,4-bis (2-hydroxyethoxyphenyl) propane. Specific examples of the trihydric alcohols (h1-3) include glycerin, trimethylolpropane, hexanetriol and the like. Specific examples of the polyhydric alcohols having four or more functional groups (h1-4) include sorbitol and puffed rose. Specific examples of the alkanolamines (h1-5) include triethanolamine and methyldiethanolamine. The low molar adduct (h1-6)
As specific examples of (h1-1) to (h1-5)
Specific examples thereof include those obtained by adding ethylene oxide and / or propylene oxide in a low molar amount within a range where the hydroxyl value is 300 or more.

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).
Examples thereof include compounds obtained by adding an alkylene oxide to the compounds of 1-1) to (h1-5), low molecular amines, polyhydric phenols, and the like. 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 polyhydric phenols include hydroquinone, bisphenol A, bisphenol F, and bisphenol S. 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). 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 a difunctional or higher polyhydric alcohol 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 (polytetramethylenatel) adipate, polyethylene azelate, polyethylene sebate, polybutylene azelate, polybutylene sebate , Polyethylene terephthalate, polycaprolactone diol, polycarbonate diol and the like.

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.

As the polymer polyol (h2-6),
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 (c1) in the aqueous mixture is improved.

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

In order to adjust the molecular weight and viscosity of the prepolymer (c1), 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.)
Adducts and the like. The molecular weight of the monol (h3) is usually in the same range as (h1) or (h2). The proportion of the monool (h3) optionally used in the active hydrogen compound (h) is in a range where the average number of functional groups in (h) is usually 2 or more, preferably 2.5 or more.

NCO in urethane prepolymer (c1)
The content is preferably 0.5 to 30% by weight. The properties of (c1) 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 (c1) is preferably 1,000 to 50, 000. Prepolymer (c
As an example of the production method 1), it can be produced, for example, by charging an organic polyisocyanate (n) and an active hydrogen-containing compound (h) in a reaction vessel and reacting at a reaction temperature of 30 to 200 ° C.
The content of the urethane prepolymer (c1) unit in the foam of the present invention, that is, the content of (c1) based on the total solid content at the time of producing the foam is 5 to 30% by weight, particularly 10 to 2% by weight.
Preferably it is 5% by weight. If the content is less than 5%, the effect of improving the brittleness of the foam is reduced, and if it is more than 30%, the fire protection performance is reduced.

The foam of the present invention may contain an inorganic filler (d) as necessary 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 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 sulfuric acid (a) because it has low alkalinity even in cement. Inorganic fiber (d
By the addition of 4), 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 (d5) improves the fire prevention performance by being added.
Others listed as (d) are mainly cost /
It can be used as an extender for down. The amount of (d) added is not particularly limited, and is usually 1800 parts by weight or less, preferably 10 to 50 parts by weight, per 100 parts by weight of sulfuric acid (a).
0 parts by weight. 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 protection if the content of (c1) is within the above-mentioned preferred range. However, in order to impart even higher fire protection, a flame retardant is added to the component. Can be foamed and cured. As a flame retardant,
Non-halogen phosphates (triphenyl phosphate, cresyl diphenyl phosphate, ammonium polyphosphate, etc.), halogen-containing phosphates (trischloroethyl phosphate, trisdichloropropyl phosphate, tris (tribromophenyl) phosphate, Trisdibromopropyl phosphate, etc.), active hydrogen containing flame retardants (di (isopropyl) N, N-bis (2-hydroxyethyl) aminomethyl phosphate, 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 used is usually 40 parts by weight or less, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the urethane prepolymer (c1).

According to the method of the present invention, a blowing agent (b) comprising sulfuric acid (a) and calcium carbonate or barium carbonate
1) and a urethane prepolymer having an NCO group (c)
1), water and, if necessary, a compound (b2) and / or an inorganic filler (d) selected from the group consisting of calcium oxide, barium oxide, calcium hydroxide and barium hydroxide.
By mixing the components consisting of the following into an aqueous mixture, which is foam-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 usually the concentration of the aqueous mixture is 25 to 90.
It is an amount to be about weight%.

In the method of the present invention, the prepolymer (c
To control the curing speed of 1), for example,
A catalyst may be added. Catalysts include: dibutyltin dilaurate, alkyl titanate, organosilicon titanate, stannas octoate, lead octylate, zinc octylate, bismuth octylate, dibutyltin diorthophenylphenoxite, tin oxide and ester compounds Metal-based catalysts such as reaction products of (e.g., dioctyl phthalate); monoamines (e.g., triethylamine); diamines (e.g., N, N, N ', N'-tetramethylethylenediamine); triamines (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 30 parts by weight or less, preferably 0.001 to 2 parts by weight, per 100 parts by weight of the prepolymer (c1).
0 parts by weight.

In the method of the present invention, a foam stabilizer may be added in order 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 amount of the foam stabilizer added is usually 3 parts by weight or less, preferably 0.001 to 1 part by weight, based on 100 parts by weight of the urethane prepolymer (c1).

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] Sulfuric acid (a), a foaming agent (b1) composed of calcium carbonate or barium carbonate, a urethane prepolymer having an NCO group (c1), water, calcium oxide if necessary,
A method in which a compound (b2) selected from the group consisting of barium oxide, calcium hydroxide, and barium hydroxide and, if necessary, an inorganic filler (d) are added and mixed at once, and foamed and cured. [2] A method in which sulfuric acid (a), prepolymer (c1) and water are mixed, and then a foaming agent (b1), if necessary (b2), and if necessary, an inorganic filler (d) are added together, followed by foaming and curing. . [3] After mixing the sulfuric acid (a) and the prepolymer (c1), the foaming agent (b1), water and, if necessary, (b)
2) and a method in which a slurry obtained by mixing the inorganic filler (d) and, if necessary, is added and mixed, followed by foaming and curing. [4] After mixing sulfuric acid (a), the prepolymer (c1) and a part of water, the blowing agent (b1), if necessary (b2), and if necessary, the inorganic filler (d) and the rest of water are mixed. A method of mixing and slurrying, charging and mixing, and foaming and curing. Of these, the methods [1], [2] and [4] are preferable, and the method [2] is particularly preferable.

The foam of the present invention can be obtained by the method of the present invention.
It is obtained by mixing each component based on the above method under normal temperature and normal pressure conditions, and then allowing the mixture to stand. The mixed solution (slurry)
After standing, it foams within a few minutes to several tens of minutes, and then the curing is completed to form a foam. However, in 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 molded. 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 troweling.

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 (b1) composed of calcium carbonate or barium carbonate. Also,
Even when the obtained foam has a low specific gravity of 0.1 or less in specific gravity, the foam surface does not have brittleness, and foams of a wide range of materials from hard to soft can be obtained from adjustment of composition and composition. In addition, the thermal insulation performance of the foam can be given a low thermal conductivity of, for example, 0.03 kcal / m · hr · ° C. or less by controlling the specific gravity. Therefore, it can be regarded as a material having excellent properties as compared with existing heat insulating materials such as glass wool and rigid urethane foam. Therefore, the foam of the present invention can be used as a heat insulating material, 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.

[0040]

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 indicate parts by weight, and% indicates% by weight. Synthesis Example 1 [Preparation of Prepolymer (c1)] Ingredients necessary for four-port separable corvene were charged,
The following urethane prepolymers c1-1 to c1-3 having NCO groups were obtained by a method of reacting at 90 degrees for 5 hours.

C1-1: 100 parts by weight of TDI [manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate T-80], polyoxyethylene polyoxypropylene glycol [molecular weight 2188, ethylene oxide 20% by weight and propylene oxide Prepolymer obtained by reacting 420 parts by weight of a block copolymer with 80% by weight, manufactured by Sanyo Chemical Industry Co., Ltd., trade name: Newpol PE-62]. The prepolymer has an NCO content of 6.2% and a number average molecular weight of 1355, and is a viscous liquid at ordinary temperature. c1-2: 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] Manufactured by Sanyo Chemical Industry Co., Ltd., trade name: SANNIX GL-3000]
A prepolymer obtained by reacting 150 parts by weight. The prepolymer has an NCO content of 10.0% and a number average molecular weight of 12
76, viscous liquid at normal temperature. c1-3: 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:
Sanesta No. 22] 133 parts by weight and 26 parts by weight of polyethylene glycol (molecular weight: 400, manufactured by Sanyo Chemical Industries, Ltd., trade name: PEG400) were reacted to form a prepolymer. The prepolymer has an NCO content of 6.5% and a number average molecular weight of 1300, and is a viscous liquid at ordinary temperature.

Production Example 1 [Examples 1-4, Comparative Examples 1-4]
Production of Foam of Examples] Examples 1 to 4 and Comparative Examples 1, 2 and 4 are shown in Table 1 below.
Based on the above composition, the sulfuric acid (a) and the prepolymer (c1) were uniformly stirred by a homomixer. (Since water was contained in the sulfuric acid used in this example, water was not particularly added.) The obtained stirred mixture was further subjected to Examples 1 and 2, Comparative Example 1,
2 is a foaming agent (b1) composed of calcium carbonate or barium carbonate, if necessary, calcium oxide, barium oxide,
A compound (b2) selected from the group consisting of calcium hydroxide and barium hydroxide was added.
In Comparative Example 4, the foaming agents (b1) and (b2) and the inorganic filler (d) were added, and the mixture was stirred and mixed.
30 × 3 cm), and allowed to foam freely.
In addition, molded foams of Comparative Examples 1, 2 and 4 were obtained. In Comparative Example 3, a halogen-containing phosphate ester (trade name: Aranfuram 7) manufactured by NOF Corporation as a flame retardant
0) is added, and the flame retardant, which has been uniformly stirred in the prepolymer (c1) in advance, is stirred and mixed with water, then poured into a mold (50 × 30 × 3 cm) and allowed to foam freely. Thus, a molded foam was obtained.

[0043]

Note 1) The compounds indicated by the abbreviations are as follows. (A) Sulfuric acid a-1: A diluted 15% sulfuric acid aqueous solution (b) A blowing agent (b1) composed of calcium carbonate or barium carbonate and a compound selected from the group consisting of calcium oxide, barium oxide, calcium hydroxide and barium hydroxide (B2) b-1: calcium carbonate: calcium hydroxide = 60: 4
0 (weight ratio) b-2: barium carbonate: barium hydroxide = 50: 50
(Weight ratio) b-3: barium carbonate: calcium oxide = 50: 50
(Weight ratio) (c1) urethane prepolymer c1-1, c1-2, c1-3: prepolymer obtained in Synthesis Example 1 (d) inorganic filler d-1: aluminum hydroxide d-2: alumina cement d-3: Silas balloon [Sanki Industry Co., Ltd., trade name:
Sankilite Yo.2] Note 2) (C) (%) in Table 1 is the amount (% by weight) of the prepolymer (c1) based on the total solid content during the production of the foam.
Is the calculated value of

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 1 were allowed to stand in a well-ventilated room for one month, and then dried in a dryer at 40 ° C. for 48 hours. After that, what was left in a desiccator for 24 hours was subjected to a test according to the following test method. [Test Methods for Physical Properties of Foam] (1) 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). The test piece is 40 mm
Judgment was made by observing the condition when the film was wound along the circumference of the cylinder. (4) 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.

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

[0047]

[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] The foams of the present invention of Examples 1 to 4 were all tough rigid foams. 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 the strength performance enough to be used as a panel, for example, cracks occurred in the molded article.

[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 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) Although the appearance and performance are almost the same level as those of the existing polyurethane foam and polystyrene foam, the fire resistance of the material is at a level equivalent to that of non-combustible materials to semi-combustible materials that are higher than these existing organic insulating materials. The material can be supplied to the market with high safety in disaster prevention.

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, 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 conventionally used for organic foams such as polyurethane foams and polystyrene foams; for example, ceilings, walls, floors, roofs, etc. Interior / exterior insulation boards for houses and buildings, voids such as panels, tatami mats, doors, insulation backing for roof tiles and roofing materials, automobiles and trains
Roof lining materials for aircraft and ships, interior materials around engines, substitute materials for honeycomb parts, insulation materials for refrigerators, air conditioners, freezers, air conditioning equipment and air conditioning lines, thermal insulation coatings for natural gas tanks and pipelines such as LNG Insulation packing material for transportation of materials, utility line insulation in factories, frozen goods, etc. 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 railing coverings on train tracks, soundproof lining materials for engines and machinery, and housing lining materials. Applications that are required to have low biodegradability and low environmental pollution compared to organic materials, which are not foamed by organic materials; substitute for lightweight embankments, backfill materials for tunnels, blocks for vegetation, sword mountain for ikebana, horticulture For vermiculite, etc.

Claims (5)

[Claims] 1. A compound (b2) selected from the group consisting of sulfuric acid (a), a blowing agent (b1) composed of calcium carbonate or barium carbonate, and, if necessary, calcium oxide, barium oxide, calcium hydroxide and barium hydroxide. An inorganic-organic composite having improved brittleness by a polyurethane, polyurea or polyurethane urea resin cured product (c) formed in situ from a urethane prepolymer (c1) having an NCO group and having a foam structure from Foam. 2. A foam according to claim 1, wherein the aqueous mixture comprising (a), (b1), (c1) and, if necessary, (b2) is foamed and cured. 3. The foam according to claim 1, wherein the content of (c1) in the aqueous mixture in terms of solid content is 5 to 30% by weight. 4. The foam according to claim 1, further comprising an inorganic filler (d). 5. A sulfuric acid (a), a blowing agent (b1) composed of calcium carbonate or barium carbonate, a urethane prepolymer (c1) having an NCO group, water, and, if necessary, calcium oxide, barium oxide, and hydroxide. Compound (b2) selected from the group consisting of calcium and barium hydroxide
And / or a method for producing an inorganic-organic composite foam, which comprises mixing a component comprising the inorganic filler (d) and foam-curing the mixture.