JPH08176259A - Organic-inorganic hybrid flame-retardant foam composition and composite building material produced therefrom - Google Patents

Abstract

PURPOSE: To obtain an org.-inorg. hybrid thermosetting, flame-retardant foam compsn. which is lightweight and excellent in elasticity, heat resistance, and fire resistance by reacting a specific org. component with a specific inorg. aggregate under specified conditions. CONSTITUTION: 2-8mol of formaldehyde is subject to an addition reaction with 1mol of a polyamine component comprising 100-1mol% compd. of the formula and 0-99mol% mono-ε-triazine compd. and/or (thio)urea, giving a monomer or a precondensate. An org. component is prepd. by compounding 39.98-80wt.% available resin component of an aq. diguanamine-based polyvalent aminoplast resin precursor soln. contg. 10-85wt.% above-obtd. monomer or precondensate with 19.98-60wt.% org. poyisocyanate, 0.01-3wt.% urethanizing tert. amine catalyst, and 0.01-5wt.% anionic surfactant and/or silicone foam stabilizer 100 pts.wt. the org. component is reacted with 70-850 pts.wt. inorg. aggregate selected from amomg anhydrous gypsum, etc., in the presence of water in an amt. of 0.5-2 times the theoretical amt. for hydrating and hardening the aggregate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting organic-inorganic hybrid flame-retardant foam composition which is useful as a flame-retardant material for building materials and has excellent toughness, and a method for producing the same.

More specifically, a specific polyvalent aminoplast resin precursor aqueous solution containing an aqueous medium, an organic polyisocyanate, a rehydratable inorganic aggregate powder excluding cement and quicklime, a urethanization catalyst and a foam stabilizer are used. After mixing in the presence of water, by foaming and curing reaction, it is hydrated and hardened in the form of having a foaming organism mainly composed of thermosetting polyvalent aminoplast resin-modified urethane curing resin phase and sufficient crystal water. Which is a so-called organic-inorganic hybrid type foam / cured material composition in which a foamed composite phase structure is formed integrally with the inorganic material, which is tough, tough, and water resistant. The present invention relates to a thermosetting organic-inorganic hybrid flame-retardant foam composition characterized by having high flame retardancy of class 3 or higher, and light weight, and a method for producing the same.

[0003]

2. Description of the Related Art Calcined gypsum has hitherto been known as a material that is hardened by water, and is a material that is well known in the form of a casting for fixing. And the set gypsum is stabilized in the form of dihydrate, it is hard and brittle without water resistance, but it shows noncombustibility, and gypsum is an industrial product that has been put to practical use by effectively utilizing its properties. There is a board.

There have been many technical introductions on gypsum compositions, but among them, some attempts have been made to improve the properties of gypsum having poor water resistance.

For example, JP-A-5-213645 discloses a gypsum material characterized by containing a polyether polyol within 5% by weight, and optionally a polyurethane and / or a polyurethane-urea aqueous dispersion. A gypsum composition in which a thermoplastic organic additive is used in combination and a method for producing the gypsum composition have been proposed, and the gypsum composition is said to be dense and have good workability and improved water absorption. It is described that it can be preferably used for planks and decorative plaster.

However, the composition obtained by this technique is extremely dense and is not suitable as a heavy and lightweight building material. Further, since it is a composition made of a thermoplastic organic substance addition system, it lacks water resistance and is extremely difficult in heat resistance and rigidity.

Further, regarding a reinforced gypsum board composition, Japanese Patent Laid-Open No.
No. 3-40751 describes a method for producing a gypsum board obtained by mixing a rehydratable gypsum-based binder with water and optionally a reinforcing material (cellulose particles or wood chips) and subsequently pressing. A method for producing a reinforced gypsum board characterized by adding polyisocyanate to a mixture before pressing and / or applying polyisocyanate on the surface of the gypsum board after pressing has been proposed.

The reinforced gypsum board produced by the disclosed technique has improved flexural strength and water resistance, and the polyisocyanate added exerts some chemical action effect with the cellulose particles, thereby significantly improving flexural strength. There is.

However, the gypsum board obtained by this technique is basically a non-self-foaming hardened material and is heavy and unsuitable as a lightweight construction material.

Among the examples proposed and disclosed as a method for improving water resistance and weight saving, there are representatives such as JP-A-49-134722 and JP-A-5-105544, which are known as a method for producing a foamed gypsum board. .

In JP-A-49-134722, a mixture of calcined gypsum and general aggregate is mixed with an aqueous solution of a phenol resin initial condensate or a melamine resin initial condensate as a water-soluble thermosetting resin, and the mixture is kept at room temperature. After setting the calcined gypsum with, then 8
After the resin is semi-cured in an atmosphere of 0 ° C or lower, it is heated to 80 ° C or higher, and the expansion caused by vaporization of water generated during heat curing is used to make the space between the resin layer, gypsum, and aggregates. It is a method for producing a foamed gypsum board characterized by completely curing while expanding the gypsum board, and the gypsum board obtained by this method is characterized by being able to have low thermal conductivity and low water absorption.

In Japanese Unexamined Patent Publication (Kokai) No. 5-105544, sulfuric acid or a salt thereof is added to calcium carbonate, then anhydrous gypsum is added, and the mixture is kneaded with water while foaming due to carbon dioxide gas generated, and then anhydrous gypsum is converted to dihydrate gypsum. A gypsum-containing composition for producing a cured gypsum foam by-product and a method for producing the foam are disclosed.

However, in any of the light-weight foamed gypsum board manufacturing methods, the bulk specific gravity of the gypsum board obtained is as high as about 0.7 to 0.8, which is not a stable and reproducible manufacturing technique. .

Looking at the current state of gypsum compositions other than gypsum board, a composite of gypsum and a thermoplastic organic substance is being studied, mainly for applications such as plaster.

For example, JP-A-59-227919 discloses that
As a composition of a so-called organic-inorganic composite material and a method for producing the same, a composition mainly based on plaster and a polyurethane thermoplastic organic material for plaster applications is shown,
It has been proposed as a technique for improving the water resistance and brittleness of gypsum.

According to the disclosure, in the presence of a polyurethane or polyurethane-urea thermoplastic resin (thermoplastic 100% suspension resin aqueous solution) which can disperse calcined lime or calcined anhydrite in water, and optionally 20 wt. %, It is said to be a method for producing a composite by allowing water to act in the presence of an organic solvent such as alcohol and the like, followed by molding, drying, and solidifying, and particularly rubber elasticity of the entire cured product (non-foaming). The proportion of plastic polyurethane used is 1 to 50% by weight, preferably 5 to
By setting the content to 45% by weight, a non-foaming plastic gypsum composite material rich in elasticity is provided.

Moreover, the composition is characterized by high impact resistance and water resistance, but the biggest drawback is that it is an apparently air-enclosed structure for construction materials, but it is a positive foam structure. However, it is rather a non-self-foaming structure, is heavy and lacks rigidity, and is extremely limited in the practical range in fields other than plaster, and flame retardancy is also limited. In particular, it is not suitable as a foam-type lightweight construction material member, and it has water resistance, heat resistance,
It is still necessary to solve many problems at the same time, such as weight reduction, JIS-flame retardant class 3 or higher flame retardancy, physical strength and rigidity retention.

Thus, it can be said that in the field of flame-retardant and non-combustible lightweight building materials, there is a continuing need to develop an inexpensive composition having a low bulk specific gravity and excellent water resistance and toughness.

In recent years, outer wall siding products have been known as one of the major building material products. Among them, metal siding is drawing attention, and hard urethane foam, hard isocyanurate foam, phenol foam, or the like is used as the core material. In these building materials, the metal coating material and the core material are integrated, making it ultra-light as a whole,
It is noted that the design, workability on site, and water resistance are excellent.

However, the rigid urethane foam core material technology used for the metal siding material has the following problems.

That is, the rigid urethane foam core material has major problems such as cost reduction, defluorocarbonization, and imparting flame retardancy.

According to JP-A-57-18721, in order to reduce the cost of the rigid urethane foam core material and impart flame retardancy, it is possible to add melamine and formaldehyde in the ratio of 1: 1.1 to 1: 1.1.
A melamine-formaldehyde precondensate aqueous solution previously prepared to an active ingredient content ratio of 40 to 85% by weight obtained by addition condensation in an aqueous solution at a molar ratio of 1: 1.75, a polyol, and an organic poly It proposes a method for producing a rigid urethane foam substance obtained by reacting an isocyanate with an additive such as a catalyst and a blowing agent.

The foamed and hardened material disclosed in Japanese Patent Laid-Open No. 57-18721 contains a large amount of combustible organic matter, so that although it has some degree of ignition and fire resistance, it has the property of burning violently once ignited, and it is a construction panel. As a core material, there are still problems unsuitable. In particular, it cannot be said that the material is a material that satisfies the flame-retardant class 3 or higher single unit noncombustibility or flame-retardant characteristics of building material products specified by JIS.

In the art, if desired, one of antimony trioxide, ammonium phosphate, and calcium sulfate is added as an inorganic flameproofing auxiliary additive in an amount of 5 to 50 parts by weight per 100 parts by weight of the resin component of the melamine precondensate. It has been proposed that it is preferable to add some of them in a similar manner.
There is a problem that it does not show flame retardancy of S certified grade 3 or higher, and even if a large amount of inorganic flameproofing component is simply added, foam shrinkage occurs rather remarkably and frequently, and the bulk specific gravity is substantially 0.7 or less. It is not possible to obtain the lightweight foamed flame retardant substance.

Therefore, any of the hard urethane foam substances reported so far or the metal siding material when the substance is applied and used as a panel core material, any of the products and the core material which conform to JIS flame retardancy class 3 or higher. There are no known examples of how the composition was made.

Particularly, in the conventional technique of the hard urethane foam material, it is sufficient that it can be applied as the core material of the metal siding material at the same time as the flame retardant property of the flame retardant grade 3 or higher in the bulk density range of 0.1 to 0.65. Up to now, no disclosure has been made of a composition having core material strength characteristics and a building material product thereof.

The only core siding material that has a proven track record as quasi-incombustible is a metal siding material, which is prepared by cutting a core material made of a separately prepared double-sided paper-coated gypsum board and then bonding the gypsum board and a steel plate to each other. I know how to do it,
The product obtained by this method had a problem that the specific gravity of the core material was extremely heavy at around 0.7, the site workability was difficult, and the water resistance was extremely poor.

In recent years, it is particularly hard to burn and rich in fire resistance,
At present, there is a strong demand for lightweight and inexpensive building material products that are rich in water resistance and heat insulation properties. In addition, a new structure for building materials or a composite structure that satisfies the requirements of easy workability and high designability at the same time. Body / metal siding The advent of new flame-retardant lightweight core materials is particularly desired.

[0029]

As described above, in the field of lightweight flame-retardant building materials, many flame-retardant building material products based on rehydrated and sinterable inorganic aggregates such as gypsum board are available. The practicable gypsum board products still have a high bulk specific gravity, and those having a bulk specific gravity of 0.65 or less have not been practically used.

Regarding metal siding products, it is noted that hard urethane foam, phenol foam, and polyisocyanurate foam are known in consideration of ease of construction and lightweight insulation properties even if their fire protection performance is sacrificed. .

That is, at present, the bulk specific gravity is 0.6.
There is no organic-inorganic hybrid type light weight foamed cured body that is as light as 5 or less and exhibits sufficient mechanical strength, water resistance, elasticity and excellent fire protection performance, and development of a new lightweight flame retardant core material is strongly desired. ing.

Therefore, the problem to be solved is to provide a novel flame-retardant lightweight foam for building materials and a method for producing the same in order to meet the above-mentioned demand.

More specifically, the present invention is to provide a novel thermosetting flame-retardant foamed lightweight cured product composition which can simultaneously satisfy the following problems 1 to 6, and the cured foam is inexpensive. In addition, a novel organic-inorganic hybrid type thermosetting lightweight foamed cured product that can be continuously produced as needed and can be applied as a lightweight flame-retardant core material for metal siding, and a method for producing the same. .

1. The organic matter content in the cured composition is 10 to 10.
Even if it is compounded in a high concentration of 60% by weight, it must exhibit sufficient flame retardant fireproof performance as a building material member.

2. At relatively low temperatures in the range of around room temperature to less than 85 ° C, self-foaming exothermic curing reaction by organic components and inorganic rehydration exothermic curing reaction proceed in parallel, and easily subjected to secondary processing within 1 hour. To express the possible primary strength.

3. The foamed composite cured product composition is obtained by the composite reaction shown in the above-mentioned 2 which is only the foaming and curing reaction, and after foaming without causing a large amount of excess water to be dried and discharged in the dryer as in the conventional gypsum board production example. A foamed cured product that has completed the curing reaction in an unsealed system must have sufficient toughness and have sufficient compressive fracture strength and water resistance properties.

4. The flame-retardant properties of the foamed cured product and its composite building material product to be produced shall be flame-retardant grade 3 or higher in the flame-retardant test prescribed in JIS-A-1321 (1975).

5. The water resistance of the foamed cured product is 48
Retention rate of compressive strength after immersion in room temperature water for at least 80%
That is all.

6. The expansion ratio can be adjusted arbitrarily so that the cured product has a bulk density of 0.01 (ultra high foam) to 0.65 (high foam), more preferably 0.25 to 0.65. To provide a method for producing a composite cured product composition which is a highly foamed composition and is highly reproducible and rich in elasticity.

[0040]

[Means for Solving the Problems] As a means for solving the above-mentioned problems together, as a result of extensive studies, a specific polyvalent aminoplast resin precursor aqueous solution previously produced and prepared in an aqueous medium, and an organic poly Isocyanate and rehydration-curable inorganic aggregate powder are collectively mixed in the presence of a urethane-forming catalyst, a foam stabilizer, and water which is also used as a medium for the polyvalent aminoplast resin precursor, and then foam-cured. By reacting, the organic matter-hardened phase mainly consisting of the thermosetting flame-retardant modified urethane resin phase and the inorganic matter-phase hydrated and hardened in the form of retaining a sufficient amount of water of crystallization are integrated to form a foamed composite phase structure. By forming a so-called organic-inorganic hybrid type thermosetting foam-cured composition that forms a polymer, a foam material that can be cured at low temperature for a short time and is basically very bulky is formed. ,That Quality excellent tough elastic, rich in water resistance, and found that to obtain combines extremely high flame retardancy properties and light weight construction materials suitability was achieved the present invention.

That is, in the present invention, 39.98 to 80% by weight of the effective resin component of the diguanamine-based polyvalent aminoplast resin precursor aqueous solution represented by the following (a) is used as an organic component, and an isocyanate in one molecule. 19.98 to 60% by weight of an organic polyisocyanate having at least two groups, 0.01 to 3% by weight of a tertiary amine urethanization catalyst, and a silicon type foam stabilizer and / or an anionic surface active foam stabilizer. 1 of the organic component consisting of 0.01 to 5% by weight of the agent
70 parts to 850 parts by weight of a rehydration-curable inorganic aggregate composed of one kind or a mixture selected from anhydrous gypsum, hemihydrate gypsum, and α-tricalcium phosphate per 100 parts by weight, and the inorganic bone. 50-20 theoretical water required for rehydration hardening of wood
It is a thermosetting organic-inorganic hybrid flame-retardant foam composition obtained by mixing and reacting in the presence of water corresponding to 0 mol%.

(A) 3,9-bis (3,5-diamino-6-ethyl-1,3,5-triazine) -2,4,8.10-tetraoxaspiro [represented by the following formula 1] 5,
5] -100 to 1 mol% of undecane and 0 to 9 of mono-ε-triazine compound and / or urea or thiourea
A di-ε-triazine system containing 10 to 85% by weight of a monomer obtained by adding 2 to 8 mol of formaldehyde to 1 mol of a total of 9 mol% of a polyvalent amino compound and / or an initial condensation product thereof. Aqueous solution of polyvalent aminoplast resin precursor.

[0043]

Embedded image In addition, the production method means a diguanamine-based polyvalent aminoplast resin precursor aqueous solution represented by (a), a tertiary amine urethanization catalyst and, if necessary, an organometallic urethanization co-catalyst, and a silicon-based preparation. In the presence of a foaming agent and / or an anionic surfactant foam stabilizer and water corresponding to 50 to 200 mol% of theoretical water necessary for rehydrating the inorganic aggregate, anhydrous gypsum, hemihydrate gypsum, α- A liquid containing a rehydration-curable inorganic aggregate consisting of at least one or more selected from the group consisting of tricalcium phosphate, and containing at least two isocyanate groups in one molecule. Two liquids consisting of B liquid of organic polyisocyanate are quantitatively supplied to the mixing tank at the same time, high speed stirring is performed, and the mixture is rapidly mixed at a temperature of room temperature to 40 ° C. for 1 to 40 seconds, and then discharged to the outside of the mixing tank to a certain degree. Jo to a method for producing an organic-inorganic hybrid type flame heat foam composition, wherein the foaming curing reaction.

The composite building material panel of the present invention comprises a surface material made of any one of an inorganic fiber board, a steel plate, a cement board and a gypsum board. The organic-inorganic hybrid flame-retardant foam composition of the present invention is used as a backup core material. It is a composite building material panel characterized by:

The sandwich building material panel of the present invention means that the surface material is a steel plate and the back material is paper or aluminum foil laminated paper, and the organic-inorganic hybrid flame-retardant foam composition of the present invention is used as a core material. This is a characteristic sandwich building material panel.

The present invention will be described in more detail below.

The organic component means 39.98 to 80% by weight of the effective resin component of the diguanamine-based polyvalent aminoplast resin precursor aqueous solution represented by (a) above, and at least 2 of isocyanate groups in one molecule. 19.98 to 60% by weight of an organic polyisocyanate having a ke, 0.01 to 3% by weight of a tertiary amine-based urethane-forming catalyst, and a silicone-based foam stabilizer and / or an anionic surface-active foam stabilizer of 0. 01-
5% by weight.

Here, the effective resin component (a) is referred to as a diguanamine-based aminoplast resin precursor, and the diguanamine-based aminoplast resin precursor aqueous solution is 3,9-bis (3,3) in an aqueous medium under alkali. 5-diamino-6-ethyl-1,3,5-triazine) -2,4,8.10-
Tetraoxaspiro [5,5] -undecane 100-
It is represented by a product obtained by adding and condensing 2 to 8 mol of formaldehyde to 1 mol in total of 1 mol% and 0 to 99 mol% of a mono-ε-triazine compound and / or urea or thiourea.

Here, 3,9-bis (3,5-diamino-
6-ethyl-1,3,5-triazine) -2,4,8.
10-Tetraoxaspiro [5,5] -undecane will be simply referred to as CTU guanamine.

The term "adding 2 to 8 mol of formaldehyde" as used herein means that the maximum amount of a monomer and / or its initial condensate obtained by adding 8 mol of formaldehyde to 1 mol of CTU guanamine. Of the CTU guanamine and 99 mol% of melamine, and 2 mol of formaldehyde added to 1 mol of CTU guanamine and 99 mol% of melamine. It is to be an adder.

Generally, it is known that CTU guanamine can be obtained by reacting dicyandiamide with 3,9-bis (2-cyanoethyl) -2,4,8.10-tetraoxaspiro [5,5] -undecane as a starting material. Has been.

A constituent unit derived from a CTU guanamine skeleton is essential in the constituent units constituting the precursor substance of (a) above, and is highly elastic and has excellent water resistance and is defined in JIS according to the object of the present invention. It is essential as a requirement to combine the flame retardancy of grade 3 or higher of the building material products. The relationship between the amount used and (a) is as described above.

Typical examples of the above-mentioned mono-ε-triazine compound include the following, for example, melamine, benzocarboguanamine, acetocarboguanamine, cyclohexylcarboguanamine, norbornenecarboguanamine, norbornanecarboguanamine and the like. Yes, they can be used alone or in combination of two or more.

Melamine is a preferred example of the mono-ε-triazine compound.

In the present invention, the effective resin content concentration of the digamine-based aminoplast resin precursor aqueous solution (a) is 10 to 10.
Although the range of 85 wt% is said to be good, after obtaining a di-ε-triazine type aminoplast resin precursor aqueous solution, dehydration treatment is carried out at an extremely low temperature such as freezing vacuum drying and room temperature vacuum drying,
It is stored at low temperature in a solid state, and when it is used as an aqueous solution when carrying out the present invention, at the time of adding a water component for rehydration, which is essential for complexation with a rehydration-curable inorganic aggregate. As a result, even if the solid diguanamine-based aminoplast resin precursor is redissolved in water to form an aqueous solution having a resin concentration of 10 to 85% by weight, it is included in (a) of the present invention. It

The important point is that the solution concentration range is determined from the relationship that the storage stability of the diguanamine-based aminoplast resin precursor aqueous solution and the miscibility with other essential components for a short time can be secured. The above range is preferable as the concentration of the resin solution that can be easily handled in a liquid or dilute suspension solution having a viscosity.

In general, the formalin addition reaction to a mono-ε-triazine type polyvalent amino compound represented by melamine, urea, thiourea, etc. is carried out in an aqueous medium or a water / lower alcohol mixed medium at an initial PH value of 7 It is well known that it is carried out under the above alkaline conditions.
Can be easily obtained by the same method.

In the case of proceeding the initial condensation of (a), the method of continuing the heating under the condition that the alkalinity is maintained,
Initial alkalinity-a method can be adopted in which the dehydration condensation reaction is promoted under so-called mid-acidity, such as in the middle of weak acidity, then made alkaline again and the quenching is stopped.

Therefore, there is no restriction on the method of obtaining the component (a). The aqueous solution (a) means a solution mainly composed of an aqueous medium, and includes a so-called water-alcohol mixed medium in which a lower alcohol medium such as methanol is used in combination.

In the present invention, preferable examples of the diguanamine-based aminoplast resin precursor, which is the active ingredient of (a), will be described below in order.

First of all, the diguanamine-based aminoplast resin precursor is 1 to 100 mol, preferably 30 to 95 mol%, most preferably 50 to 90 mol% of CTU guanamine, and 0% of melamine and / or urea. ~
A monomer obtained by adding 2 to 6 mol of formaldehyde to 1 mol in total of a polyvalent amino compound composed of 99 mol, preferably 5 to 70 mol%, and most preferably 10 to 50 mol%, and / or Examples of the initial condensate include those in which 1 to 50 mol% of the methylol group produced at that time is modified with an aliphatic alkyl ether having 1 to 4 aliphatic groups. It is preferable because it can impart excellent elasticity and flame retardant property balance to the inorganic hybrid type thermosetting flame-retardant foamed product.

More preferably, 10 of CTU guanamine is used.
~ 100 mol%, more preferably 50-95 mol%
2 to 4.5 of formaldehyde to 1 mol in total of a polyvalent amino compound composed of 0 to 90 mol% of melamine and / or urea, and most preferably 5 to 50 mol%.
A monomer obtained by adding moles and / or an initial condensate thereof, and 2-3 mol%, more preferably 5-25 mol%, of the produced methylol group is modified with methyl ether. .

Further, the diguanamine-based aminoplast resin precursor contains 1 to 100 mol%, preferably 10 to 100 mol%, most preferably 5 mol of CTU guanamine.
0-90 mol% and mono-ε-triazine compound and /
Alternatively, 2 to 6 mol of formaldehyde is added to 1 mol in total of a polyvalent amino compound consisting of 0 to 99 mol% of urea or thiourea, preferably 0 to 90 mol%, and most preferably 10 to 50 mol%. And the initial condensate thereof, and then a part of anion group obtained by sulfonating less than 0.6 to 15 mol% of the introduced methylol group by acting sodium sulfite on the same system is introduced. It is much more preferable that it is a thing made from.

By using (a) in which a part of the anionic modified methylol group has been introduced, in the mixture slurry system consisting of the following organic aggregate capable of being hydrated with the organic component and water, the initial fluidity with reduced water Characteristic can be added.

Furthermore, the diguanamine-based aminoplast resin precursor is an initial condensate, and the water dilutability as a measure of the degree of condensation is such that the condensation solution: diluting water ratio is 1:
It is preferable that the condensation reaction proceeds to 0.5 to 1: 5.

By promoting the degree of condensation, the organic-inorganic hybrid flame-retardant foam composition of the present invention can exhibit a stable foam-curing property by promoting the expansion ratio and immediately increasing the film thickness of foam cells. In addition, the diguanamine-based aminoplast resin precursor aqueous solution (a) is composed of an initial condensate aqueous solution and has an aqueous solution viscosity of 500 cp or less at 20 ° C., and a resin concentration of 40 to 40.
The viscosity of the 20 ° C. aqueous solution when measured as 85% by weight is 45
Most preferably, the precursor solution is 0 cp or less.

In particular, by setting the initial viscosity of (a) to 500 cp or less, quick miscibility of each component of the organic-inorganic hybrid flame-retardant foam composition of the present invention at high speed mixing can be secured, and it is stable. The reason is that it is possible to obtain the reproducible organic-inorganic hybrid flame-retardant foam composition of the present invention.

Furthermore, the diguanamine-based aminoplast resin precursor (a) is a simple mixture of the following (b) and (c) or (d) prepared in advance, or after the initial cocondensation product or the introduced methylol group thereof is mixed. 0.6-15 mol%
The most preferable example is a modified product obtained by introducing a part of an anion group obtained by further sulfonating.

The reason for (c) and (d) below is that they can be easily obtained at low cost in the market, and even if (a) remains as it is, the stability in aging at room temperature is difficult. This is because the compounding arbitrariness and cost reduction can be achieved by separately preparing the following (b) and (c) or (d).

(B) 4 to 8 mol of formaldehyde is added to 1 mol of CTU guanamine, and 1 to 50 mol% of the methylol group produced at that time is modified with an aliphatic alkyl ether having 1 to 5 carbon atoms. A monomer and / or an initial condensation product thereof.

(C) 1.1 to 4 mol of formaldehyde is added to 1 mol of melamine, and 1 to 50 mol% of the methylol group produced at this time is formed by an aliphatic alkyl ether having 1 to 5 carbon atoms. Modified monomers and / or their initial condensation products.

(D) 1.1 to 2.5 mol of formaldehyde is added to 1 mol of urea, and 1 to 35 mol% of the methylol group produced at that time is an aliphatic alkyl having 1 to 5 carbon atoms. A monomer modified with ether and / or an initial condensate thereof.

In the diguanamine-based aminoplast resin precursor solution (a), the number of free carbon atoms is 1 to 1.
It is very preferable that the amount of the aliphatic alkoxylating agent of 5 is 5% by weight or less, and in particular, the diguanamine-based aminoplast resin precursor aqueous solution (a) is an aliphatic alkoxylating agent having 1 to 5 carbon atoms which is freely present. The most highly preferred example is that the amount of the above is 1% by weight or less and the viscosity of the aqueous solution at 20 ° C. is 300 cp or less, and the aqueous solution is transparent or semi-suspended.

In the present invention, it is known that the introduction of an alkyletherified methylol group is an effective means in the method of (a) for realizing the stability over time and the transparent solution. In the case where the residual amount of the alkoxylating agent used for the alkyl etherification is increased more than necessary (a),
Although the stability over time is ensured, the defoaming effect remarkably occurs as an effect on the bubbles during the urethane water-foaming reaction, and therefore it is important to set the content within the above range.

That is, by defining the amount of the aliphatic alkoxylating agent having 1 to 5 carbon atoms which is freely present in the system, the foam stability of urethane water foaming can be secured and the flame retardancy of the present invention is reproducible. A foam composition can be obtained.

Basically, in the present invention, the concentration of the active ingredient of the diguanamine-based aminoplast resin precursor of (a) is 10 to 8.
The amount of 5% by weight, preferably 30 to 80% by weight, and more preferably 50 to 75% by weight is important for providing the foam composition of the present invention.

Water is an essential component of the composition of the present invention. Therefore, by also using the water component as the medium of (a) above, the active ingredient of (a) can be handled mainly as a liquid, and as a result, the This is because it is possible to promote rapid homogenization of the respective components such as hydratable inorganic aggregates and organic polyisocyanates, which are one of the essential components, and to form a relatively uniform reaction field.

The water dilutability expressed as a measure for the degree of initial condensation of the precursor of (a) means that the non-fluid viscous resin is precipitated and aggregated when the reaction product aqueous solution is diluted with water. Measure the maximum amount of water dilution until it is observed that the surface of the container for dilution measurement is contaminated, or that a resin component that can be filtered and separated into the solution at the bottom or top of the container is separated and deposited. The value expressed by means that the whole system can be handled uniformly and stably in a turbid and suspended state, which means that it can be further diluted with water. The same applies to the following description.

Regarding the water dilutability, in the diguanamine-based aminoplast resin precursor aqueous solution (a) of the present invention, there are not many examples prepared with a condensation solution: diluting water ratio of 1: 0.2 or less. Not preferable.

The reason is that a relatively high concentration solution having an active ingredient concentration of 60 to 85% by weight expressed in terms of solid content and a water dilutability of 1: 0.2 or less as a measure of the degree of condensation is used. In (a), the uncured slurry containing inorganic aggregate lacks fluidity, and lumps often occur when mixing and blending each of the essential components, making them miscible with other components. It is not preferable in general because it tends to be significantly chipped.

This can also be said from the fact that the foaming stability upon foaming and hardening causes a slight lack of foaming phenomenon, and there is a strong tendency to finally give a foamed and cured product having a large bulk specific gravity. On the other hand, the diguanamine-based aminoplast resin precursor aqueous solution having an extremely high degree of condensation tends to be preferably used as a means for producing the foamed cured product of the present invention having a relatively high density, but in the present invention, It does not particularly limit the degree of initial condensation of the precursor (1).

Similarly, the ratio of condensation solution: diluting water is 1:
It cannot be said that the diguanamine-based aminoplast resin precursor aqueous solution (a) prepared with a condensation degree of 10 or more cannot be used at all, and in the present invention, such a precursor is a polyvalent aminoplast resin monomer. It is judged that the degree of initial condensation is about

The diguanamine-based aminoplast resin precursor (a) is produced at an active ingredient concentration of 60 to 85% by weight, and the dilution water ratio thereof is particularly 1: 0.5 to 1: 5.
When the degree of condensation is in the range of 1, the occurrence of lumps caused by the lack of water solubility of the polyvalent aminoplast resin precursor when mixing the respective components is hardly observed, and therefore it is a very preferable example.

In the present invention, the diguanamine-based aminoplast resin precursor (a) contains 100 to 1 mol% of CTU guanamine and 0 to 99 mol of a mono-ε-triazine compound and / or urea or thiourea. %, A substance obtained by allowing 2 mol or less of formalin to act on a total of 1 mol of a polyvalent amino compound consisting of 10% is not included and is not preferably used in the present invention.

The reason is that the single system does not show sufficient water solubility at room temperature (becomes solid and is difficult to handle).
In addition, the flame-retardant foam composition of the present invention thus produced tends to lack elasticity, heat resistance and water resistance.

Another reason is that the foaming phenomenon often occurs remarkably during foaming and curing, and reproducibility of cured foaming is remarkably lacking, so that weight reduction cannot be achieved.

Further, in the present invention, as (a), a formaldehyde addition of a polyvalent aminated compound comprising 1 mol% or less of CTU guanamine and 99 mol% or more of a mono-ε-triazine compound and / or urea or thiourea is added. Monomers and aqueous solutions of their initial condensates were excluded from the present invention. The reason is that the content of the polyvalent amino compound as the raw material is 1 mol% or less of norbornane carbodiguanamine, and the target flame-retardant foam of the present invention is typified by the compression followability exceeding 10%. This is because it tends to lack high elasticity performance.

Further, 100 to 1 mol% of norbornane carbodiguanamine and a mono-ε-triazine compound and /
Alternatively, in the case of a precursor substance obtained by allowing 8 mol or more of formalin to act on 1 mol of a polyvalent amino compound consisting of 0 to 99 mol% of urea or thiourea, a large amount of free formaldehyde remains in the system. Therefore, it is excluded from the precursors of (a) because there is concern about the environmental pollution caused by the generation of odors and the effects on humans when handled.

However, the free formaldehyde remaining in the system after being obtained under the above-mentioned conditions is excessively known by a known method, for example, a method for deodorizing and removing free formalin by steam distillation, a vacuum concentration and purification method, an adsorbent charging / discharging method. As a result, free formaldehyde is removed out of the system by appropriately using a method typified by a superpurification method and the like, and the purified aqueous solution has a norbornane carbodiguanamine concentration of 30 to 85%.
A precursor obtained by appropriately adding 2 to 8 mol of formalin to 1 mol of a polyvalent amino compound consisting of 0 to 1 mol% and a mono-ε-triazine compound and / or 0 to 99 mol% of urea or thiourea. Examples such as obtaining a body water solution are included in the present invention.

Next, in order to obtain (a) above, (b)
A method for preparing and using (b), (c) and (d), which are separately prepared and mixed or immediately after use, mixed or mixed and then partially anionized, is used.

CTU guanamine 1 shown in (b) above
A monomer in which 4 to 8 mol of formaldehyde is added to 1 mol, and 1 to 50 mol% of the methylol group produced at that time is modified with an aliphatic alkyl ether having 1 to 5 carbon atoms and / or The initial condensate is basically one component of (a), but one of the (a) of the present invention is arbitrarily selected depending on the relationship between the above (c) and (d) and the blending / reaction method thereof. I defined (b) to make it clear that I could get it.

The item (b) can be prepared in the same manner as the item (a). In particular, (b) has 2 to 35 mol% of the methylol group, more preferably 5 to 25 mol% has 1 to 5 carbon atoms.
It is good that it is modified with the aliphatic alkyl ether of.

In addition, (c) is obtained by adding 1.1 to 4 mol of formaldehyde to 1 mol of melamine,
It means that within 1 to 50 mol% of the methylol group formed at that time is a monomer modified with an aliphatic alkyl ether having 1 to 5 carbon atoms and / or an initial condensation product thereof, (b) :( 10:90 to 90: 1 in weight ratio with c)
The content of CTU guanamine is at least 1 mol% in terms of the basic unit of the polyvalent amino compound unit in the final mixture / reactant, etc.
A compound having formaldehyde in an average range of 2 to 8 mol per mol is preferably included as (a) in the present invention.

Also in the above (d), similarly, (d)
1.1 mol of formaldehyde to 1 mol of urea
A monomer and / or an initial condensate thereof, which is obtained by adding 2.5 moles, and within which 1 to 35 mole% of the methylol groups formed at that time are modified with an aliphatic alkyl ether having 1 to 5 carbon atoms A preferred method for preparing (a) is a system obtained by separately obtaining the product separately from (b), reheating after mixing, or an initial cocondensation product.

(B): (d) or (b): [(c) +
(D)] in a weight ratio of 10:90 to 90:10, and the final mixture / reactant thereof contains at least 1 mol% of CTU guanamine in terms of the basic unit of the polyvalent amino compound unit. It is constituted as described above, and if the average amount of formaldehyde is in the range of 2 to 8 mols per 1 mol, it is preferably included in (a) of the present invention.

The above-mentioned precursors (b), (c) and (d) may be solid or aqueous solution in advance. The handling form is not particularly limited, but preferably 30 to 85% by weight. It is preferably an aqueous solution having a concentration.

Known mono-, which is generally represented by melamine
1. Formalin is added to 1 mol of the ε-triazine compound.
In the case of a precursor produced at a reaction molar ratio of 1 mol or less,
Basically, it lacks water solubility, and when it is used for simple blending with (a), the stability of the aqueous solution of the entire system tends to become a problem. However, this is not the case when they are used in combination through cocondensation.

Next, in the present invention, the diguanamine-based aminoplast resin precursor, which is the essential component (a) of the organic component, is converted from other (c) and / or (d) to (a) based on the above (b). It is summarized below as a concrete method of obtaining.

A: A method in which the monomers (b), (c) and (d) or the initial condensates are separately prepared and simply mixed as appropriate.

B: A method in which the monomers (b), (c), and (d) are separately prepared, and appropriately mixed with (b), and then the initial cocondensation is carried out.

C: A method in which the monomers (b) and (c) are mixed, cocondensation is advanced, and then the monomers (d) or the initial condensate are blended.

D: A method in which the monomers (b) and (d) are mixed, cocondensation is advanced, and then the monomers (c) or the initial condensate are blended.

E: The initial condensate of (b), the initial condensate of (c) and / or the initial condensate of (d) are appropriately mixed and then the co-condensation is advanced, and the monomer of (b), (h) ) Monomer,
A method of appropriately blending or co-condensing any one kind or two or more kinds of the monomer (d) in one step to multiple steps.

F: After appropriately mixing the initial condensate of (b) with the monomer of (c) and / or the monomer of (d), the initial condensate of (c) and or A method in which either the initial condensate (d) or the monomer (b) is mixed and blended or cocondensed in multiple stages.

And the like.

In the present invention, (a) may be a transparent or partially suspended aqueous solution, and there is no restriction on the form of the initial aqueous solution.

In (a), the product obtained by the following method is also included.

When a large excess of formaldehyde was allowed to act on 1 mol of the mono-ε-guanamine compound and / or urea or thiourea to promote sufficient methylolation of the polyvalent amino compound, CTU guanamine was initially charged. Is added in an amount of 5 mol% or more with respect to the polyvalent amino compound of 1), reacted with free formaldehyde, and co-condensed in one step or in multiple steps to finally obtain (a) of the present invention. Obtaining is also a preferred method.

In the present invention, the amount of free formaldehyde in (a) is not particularly limited, but preferably 1% by weight or less,
More preferably 0.5% by weight or less, and most preferably 0.
By setting the content to 1% by weight, environmental pollution due to odor during handling can be reduced. The diguanamine-based aminoplast resin precursor substances of (a) are represented by the following formula 2
~ Any group of formula 9 may be bonded.

Formula 2: --CH ₂ OR Formula 3:-(CH ₂ CH ₂ O) nR Formula 4:-[CH ₂ C (CH ₃ ) CH ₂ O] nR Formula 5: --SO ₃ M Formula 6: —CH ₂ —NH— Formula 7: —CH ₂ 0CH ₂ —NH— Formula 8: —CH ₂ —N (CH ₂ OR) — Formula 9: —CH ₂ 0CH ₂ —N (CH ₂ OR) — However, R in the formulas 2 to 9 is methyl, ethyl, ethyl,
M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an amine group or an ammonium group, and each functional group such as butyl, propyl, and phenyl.

As a method for introducing the groups represented by the above formulas 3 to 9 as the functional groups of the precursor molecule in the diguanamine-based aminoplast resin precursor, a known method may be adopted, particularly There are no restrictions.

Examples of the method of introducing the group of formula 3 include a method of reacting an active amino group with a necessary amount of ethylene oxide.

As a method of introducing the group of formula 4, for example, a method of adding a necessary amount of propylene oxide to the active amino group can be mentioned.

As a method for introducing the group represented by the formula 5, for example, a method in which a necessary amount of acidic sulfite is allowed to act on an active methylol group is known.

The method of introducing the groups represented by the formulas 6 to 9 includes dehydration condensation reaction between methylol groups or dehydrochlorination.
This can be achieved by appropriately advancing the HO reaction.

Generally, workability in water dilution tends to largely depend on the degree of lower alkyl etherification of the active methylol group in the molecule of the polyvalent aminoplast resin. Therefore, even if the degree of condensation is the same, the alkyl of the methylol group It is known that the higher the ratio of etherification (represented by methyl etherification), the higher the water dilution stability. Therefore, the value specified for the water dilution ratio is within 50 mol% of all methylol groups. Preferably, the aqueous solution of the polycondensation aminoplast resin initial condensate containing 35 mol% or less, and more preferably 25 mol% or less is, for example, methyl etherified and modified to advance the condensation reaction to satisfy the water dilution ratio within the above range. It means that it can be preferably adopted.

In the diguanamine-based aminoplast resin precursor, the compounding ratio with the following organic polyisocyanate is preferably a ratio of the active isocyanate group equivalent of the organic polyisocyanate to 1 equivalent of the active methylol group of the diguanamine-based aminoplast resin precursor. Is 1: 0.25-
The range of 1: 3 is preferable, and the range of 1: 0.5 to 1: 2 is more preferable.

The reason for this is that the thermosetting organic-inorganic hybrid type flame-retardant foam material of the present invention is excellent in the balance between water swelling resistance and compressive strength. Not something to do.

What is essential is that the foam-hardening composition of the present invention is used in J
IS-A-1321 standard ・ Flame retardancy In order to secure flame retardant properties of class 3 or higher and to reduce production costs, the above conditions are appropriately selected and the reactivity with organic polyisocyanate, which is one of the essential components, is required. Considering it, it is desirable to use it selectively.

In the diguanamine-based aminoplast resin precursor aqueous solution (a), especially at PH value of 8 or more, 60 to 130 ° C.
In the water dilutability at a temperature of 1, the condensation solution: diluting water ratio is 1: 0.2 to 1:10, preferably 1: 0.5 to 1:
It is preferable to proceed the condensation reaction to 5, and most preferably 1: 1 to 1: 3.

The reason therefor is a preferable condition for reducing the bulk density of the organic-inorganic hybrid flame-retardant foam composition of the present invention having an inorganic content of 50% by weight or more to 0.65 or less. Because.

Further, P used in preparing the precursor solutions of (a), (b), (c) and (d) in advance.
As the H regulator or catalyst, known substances may be used, for example, inorganic salts such as an aqueous solution of caustic soda or caustic potash and / or an organic base such as a tertiary amine,
Mono-, di- and triethanolamine, N-alkyl-
Also, N, N-dialkylalkanolamines, N-alkyldialkanolamines, and the like can be used, and there is no particular limitation.

A publicly known stabilizer may be used in combination for the purpose of ensuring the storage stability of the aqueous diguanamine aminoplast solution.

For example, from the initial stage of the reaction, or during the course of the condensation, or at any stage at the end of the condensation, a known combination of, for example, lower alcohols, toluenesulfonamide and an alcohol or saccharose, ramatam, caprolactam, etc. The amount of addition may be 25% by weight or less, preferably 15% by weight or less, and more preferably 0.1 to 5% by weight, based on 100 of the active ingredient in terms of solid content of the NDG aminoplast solution.

Among them, the most preferable stabilizers are lower alcohols, lactams and caprolactams.

In the present invention, the diguanamine-based aminoplast aqueous solution [abbreviation of diguanamine-based aminoplast resin precursor solution] (a) is used in an amount of 39.98 to 80% by weight in terms of the active ingredient in the organic component. It is characteristic to use.

When the amount of the diguanamine aminoplast aqueous solution used is 39.98% by weight or less of the organic component, the flame retardancy specified in the building material product of the organic-inorganic hybrid flame-retardant foam composition of the present invention. Is lacking.

If the amount of the diguanamine-based aminoplast aqueous solution used in terms of the active ingredient is 80% by weight or more in the organic component, the weight reduction purpose of the organic-inorganic hybrid flame-retardant foam composition of the present invention tends not to be achieved. Because.

The above-mentioned aqueous solution of diguanamine-based aminoplast can be mixed with other organic components except the following polyisocyanate, if necessary, immediately after its production.

More specifically, the (foaming) foam stabilizer and the tertiary amine urethane catalyst may be added immediately after the production of the diguanamine-based aminoplast aqueous solution and stored in the form of a mixed solution. Further, advantageously, the mixed system is further adjusted to an acidity of 2 to 6.5 with a known inorganic acid or a diluted aqueous solution thereof, an organic acid or the like immediately before use.

By the way, the modification with the aliphatic alkyl ether having 1 to 4 carbon atoms means that methanol, ethanol, isopropyl alcohol, n-butanol, and n are added to a part of the methylol group of the precursor substance in the NDG aminoplast solution. It is represented by the introduction of a so-called alkoxymethylol group formed by reacting lower alcohols such as -propyl alcohol and t-butanol.

Further, the aliphatic alkyl ether having 1 to 4 carbon atoms is a group formed by adding ethylene oxide and / or propylene oxide to a part of the methylol group of NDG aminoplast, or polyethylene glycol or polypropylene glycol. A group formed by dehydration condensation of, a group modified by a so-called polyalkylene glycol ether, and a group formed by a ring-opening addition of a cyclic lactam compound represented by ε-caprolactam. It is meant to be included here.

In the present invention, a transparent and viscous diguanamine-based resin is prepared in advance for the purpose of finally obtaining a flame-retardant cured product having a relatively large bulk density by controlling the foaming probability during curing and foaming of an organic component and water to some extent. It is possible to select, for example, heating the aminoplast aqueous solution to proceed the condensation reaction, resulting in a stable precursor resin aqueous solution in a suspended state.

Generally, when a transparent and viscous aqueous solution of diguanamine-based aminoplast is heat-treated for a long time, the system naturally changes, and the condensation reaction proceeds. As a result, the original water solubility of the precursor substance is decreased. It tends to change to a turbid state.

Therefore, a diguanamine-based aminoplast solution gel or a gelling solution of its cocondensation product in the case of reaching a so-called gel state lacking fluidity is excluded from the present invention, but it is achieved by selecting the above-mentioned means. Good.

There is no particular limitation on the condensation catalyst that can be used when proceeding the condensation reaction of the precursor substance in the aqueous solution of diguanamine-based aminoplast described above, and it is possible to add a known inorganic acid or organic acid in a small amount. The purpose can be achieved easily.

For example, as the inorganic acid, hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, nitric acid and salts thereof, and as the organic acid, acetic acid, succinic acid, malic acid, oxalic acid, lactic acid, alkylbenzene sulfonic acid, and alkyl group. Phosphonic acid, alkylphosphinic acid, their alkali metal salts, their alkaline earth metal salts, their amine salts, their ammonium salts, etc. can be used.

By the way, in the present invention, when obtaining the above (a), it is permitted to use norbornane diguanamine already known as a diguanamine compound in combination with CTU guanamine.

As described above for the diguanamine compound,
It is possible to use a known norhornenediguanamine by substituting 50 mol% of the equivalent amount of all CTU guanamine used, and even in that case, it is preferably included in the present invention.

The organic polyisocyanate essential as one of the organic components of the present invention is a monomer and / or polynuclear compound having at least two active isocyanate groups in the molecule, or a urethane prepolymer thereof as required. Therefore, a known material may be used.

The organic polyisocyanate is used in the organic component of the present invention in the range of 19.98 to 60% by weight.

At that time, when the content of the organic component in the thermosetting foam is 19.98% by weight or less, the mechanical strength of the thermosetting foam material of the present invention is insufficiently expressed and the water resistance is remarkably lacking. In the use of, the thermosetting foam material of the present invention is rich in ignitability and continues to burn as it is even after removing a small flame.
This is because it exhibits so-called flammability.

That is, 0.5 mol of the active isocyanate group of the organic polyisocyanate to 1 mol of the active hydroxyl group and / or amino group of the precursor substance in the above-mentioned diguanamine type aminoplast aqueous solution which is an essential component.
The compounding ratio is equivalent to 1.5 mol, and most preferably 0.
It is important to use in the range of 8 to 1.5 mol.

The reason why there is no problem even if more than the theoretical amount of organic polyisocyanate is used for the effective active groups of the precursor substance in the diguanamine-based aminoplast solution is that there is no problem. This is because a part of it is consumed. Most preferably, at a compounding ratio corresponding to 0.5 to 1.5 mol of the active isocyanate group of the organic polyisocyanate, relative to 1 mol of the active hydroxyl group of the diguanamine-based aminoplast resin precursor,
The most important thing is that it is preferably used in the range of 0.8 to 1.5 mol.

Typical examples of the organic polyisocyanate monomer include aliphatic polyvalent, alicyclic, aromatic-aliphatic, heterocyclic and preferably aromatic polyvalent isocyanate compound monomers.

Among the aliphatic monomers, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,
6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate and the like and polynuclear compounds thereof, and in the alicyclic monomer, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, norbornene diisocyanate, norbornane diisocyanate, Also, typical examples thereof include any mixture of those isomers and the polynuclear bodies thereof.

Examples of the araliphatic monomer include 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane, 2,4-hexahydrotoluylene diisocyanate, 2,6-hexahydrotoluylene diisocyanate, 4,4′-diisocyanate dicyclohexylmethane, 2,4′-diisocyanate dicyclohexylmethane, tetramethylxylylene diisocyanate and the like, and polynuclear compounds thereof, and typical examples of the aromatic monomer include 1,3- Phenylene diisocyanate, 1,4-phenylene diisocyanate,
2,4-tolylene diisocyanate and its polynuclear compounds, 2,
6-tolylene diisocyanate and its polynuclear body, 2,
2'-diphenylmethane diisocyanate and its polynuclear body, 2,4'-diphenylmethane diisocyanate and its polynuclear body, 4,4'-diphenylmethane diisocyanate and its polynuclear body, naphthalene 1,5-diisocyanate, 4,4 ', 4 “-Triphenylmethane triisocyanate, 2,4,6-triisocyanate benzene and the like can be mentioned.

Examples of the heterocyclic monomer include, for example, carbodiimide group-containing polyisocyanate, alphanate group-containing polyisocyanate, isocyanurate group-containing polyisocyanate and the like. In many cases, these are known diisocyanates. Alternatively, a polyisocyanate obtained by a polynuclearization reaction in the presence of a trimerization catalyst is generally included.

Further, the urethane prepolymer has at least two active isocyanate groups introduced into one molecule derived from the above polyisocyanate monomer and / or polynuclear compound and the following organic polyol. Refers to a prepolymer.

Examples of the organic polyol include known diols (polyhydric alcohols) and the following compounds obtained by other known methods such as polyether polyol, polyester polyol, polyether polyester polyol, polysiloxane polyol, polybutadiene polyol and hydrogenation thereof. Products, polyisoprene polyols and hydrogenated products thereof,
Acrylic polyols, polycarbonate polyols, and complex or mixed polyols thereof can be preferably used and are not particularly limited, but the weight average molecular weight thereof is in the range of 200 to 10,000, preferably 2
00-8,000, particularly preferably 250-6,000
It is preferably 0, and most preferably 300 to 3,000, and among them, diol or polyether polyol and / or polyester polyol are particularly preferable.

Typical examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2- or 1,3-propylene glycol, di- or tripropylene glycol,
1,4-butanediol, 1,5-pentanediol,
There are 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, 1,10-decanediol and the like.

When the linear and / or branched urethane prepolymer prepared by using the above-mentioned organic polyol is used as the organic polyisocyanate component of the present invention, 80
It is preferable that it is a liquid or a viscous fluid in a temperature atmosphere of less than ° C because it is easy to handle.

The urethane prepolymer has an isocyanate content of 5% by weight or more, preferably 10% by weight.
As described above, it is preferable that the prepolymer is as high as possible at 15% by weight or more. The reason is that it is excellent in microdispersibility and reactivity during mixing.

As a matter of course, in the organic polyisocyanate of the present invention, polyisocyanate monomers and / or polynuclear compounds represented by dimers and trimers thereof are used rather than the urethane prepolymer. It is clear that prioritized use is superior. Here, the latter so-called polynuclear organic polyisocyanate component has a higher isocyanate content per unit weight, so the minimum amount is required, it is economical, and the flammability of the foamed cured product This is due to things such as the tendency to decrease.

As the organic polyisocyanate of the present invention, 2,2'-, 2,4'-, 4,4'-diphenylmethane diisocyanate which is an industrially easily available di- or polyisocyanate monomer (collectively It will be simply referred to as diphenylmethane diisocyanate), tolylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, tetramethylene diisocyanate, norbornane diisocyanate, and it is highly preferable to use one or more thereof.

Particularly in the present invention, in the aspect of preventing environmental pollution and health marginalization due to the generation of isocyanate vapor during handling of organic polyisocyanate, crude diphenylmethane type polymeric isocyanate containing a triazine skeleton is greatly It can be said that it is a good organic polyisocyanate. The crude diphenylmethane type diisocyanate is generally a substance that partially contains diphenylmethane diisocyanate, its polynuclear body, and its polymeric body.

Particularly in the present invention, a prepolymer containing two or more isocyanate groups in one molecule containing almost no free tolylene diisocyanate derived from tolylene diisocyanate and an organic polyol as an organic polyisocyanate and its water addition The thing is also a very preferable example.

In the present invention, a tertiary amine-based urethane-forming catalyst is used as a so-called urethane-forming catalyst used to accelerate the curing reaction between the diguanamine-based aminoplast resin precursor aqueous solution of the present invention and an organic polyisocyanate. The thing is characteristic.

As the tertiary amine-based urethane-forming catalyst, any known one may be used without any particular limitation. Preferably, triethylenediamine, N, N, N ', N',
N'-pentamethyldipropylenetriamine, N, N,
N ', N', N'-pentamethyldiethylenetriamine, N, N, N ', N'-tetramethylhexamethylenediamine, bis (dimethylaminoethyl) ether, 2
-(N, N dimethylamino) -ethyl-3- (N, N dimethylamino) propyl ether, N, N'-dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, methylenebis (dimethylcyclohexyl) amine, triethylamine, N , N-dimethylacetylamine, N, N-dimethyldodecylamine, N, N-dimethylhexadecylamine, N, N, N ′, N′-tetramethyl-1,3-butanediamine, N, N-dimethylbenzyl Amine, morpholine, N-methylmorpholine, N
-Ethylmorpholine, N- (2-dimethylaminoethyl) morpholine, 4,4'-oxydiethylenedimorpholine, N, N'-dimethylpiperazine, N, N'-diethylpiperazine, N, -methyl-N'-dimethyl Aminoethylpiperazine, 2,4,6-tri (dimethylaminomethyl) phenol, tetramethylguanidine, 3-dimethylamino-N, N-dimethylpropionamide,
N, N, N ', N'-tetra (3-dimethylaminopropyl) methanediamine, N, N-dimethylaminoethanol, N, N, N', N'-tetramethyl-1,3-diamino-2- Propanol, N, N, N'-trimethylaminoethylethanolamine, 1,4-bis (2-hydroxypropyl) -2-methylpiperazine, 1- (2
-Hydroxypropyl) imidazole, 3,3-diamino-N-methylpropylamine, 1,8-diazobicyclo (5,4,0) -undecene-7, N-methyl-N-
It is preferable to use one kind or two or more kinds selected from hydroxyethylpiperazine and the like.

Among them, triethylenediamine, 2,
4,6-tri (dimethylaminomethyl) phenol,
1,8-diazobicyclo (5,4,0) -undecene-
It is preferable to use one kind or two or more kinds selected from No. 7, and the initial curing reaction of the organic-inorganic hybrid flame-retardant foam composition of the present invention is strong and highly tough while carbon dioxide gas foaming in a short time. This is a highly preferable example because it forms a semi-hard urethane cured phase.

In the present invention, the proportion of the tertiary amine urethanization catalyst used is 0.01 to 0.01% based on the organic components described in the present invention.
3% by weight, more preferably in the range of 0.05 to 2% by weight,
Most preferably, it is used in the range of 0.1 to 1.5% by weight. There is no particular problem even if the amount of use is 3% by weight or more, because the action and effect do not change remarkably even if the amount is increased, and if it is 0.01% by weight or less, urethane foaming does not occur smoothly. Is.

In the present invention, a known organometallic urethanization promoter may be used in combination with the tertiary amine urethanization catalyst, if necessary. There is no limitation on the combination ratio of the organometallic urethane-forming cocatalyst, but the addition concentration to the organic component of the present invention excluding rehydratable inorganic aggregate and water is preferably 100 parts by weight of the organic component. It may be used in an amount of 0.01 to 1 part by weight, more preferably 0.05 to 0.5 part by weight.

When it is necessary to accelerate the curing rate of the foam composition system having the same basic composition of the present invention, it tends to be easily achieved by using the urethanization promoter together. It is used to cover.

The tertiary amine urethanization catalysts and the like described in the present invention are preliminarily blended with either the aqueous solution of the polyvalent aminoplast resin of the present invention or the polyisocyanate component or both before use. Is also good.

As the above-mentioned organometallic urethane-forming catalyst, examples of organotin catalysts include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide,
Dibutyltin thiocarboxylate, dimethyltin mercaptide, dimethyltin dimaleate, dimethyltin carboxylate, dioctyltin thiocarboxylate, dioctyltin mercaptide, and lead octoate, lead oleate, lead stearate, etc. But,
Examples of the organic cobalt type include cobalt stearate.

In addition to the above-mentioned urethanization catalyst, for example, a known acid urethanization catalyst for ensuring "acidity of reaction field" may be used in combination.

As the acidic urethane-forming catalyst, P-toluenesulfonic acid, amidosulfonic acid, Lewis acid such as boron trifluoride, phosphorus trichloride, phosphorus oxychloride, etc., and further organic carboxylic acid chlorides such as benzoyl chloride, and chloride 0.1 to 3% by weight of ammonium or magnesium chloride in the organic component of the present invention,
More preferably, it may be used together in the range of 0.1 to 1% by weight.

However, in the case where the polyhydric aminoplast resin aqueous solution prepared immediately before use and used in advance has already mixed the foam stabilizer and the urethanization catalyst under acidic conditions, the above-mentioned acidic urethanization catalyst is intentionally used in combination. Obviously, it is not necessary.

The so-called foam stabilizer used for smoothly foaming during the curing reaction between the diguanamine-based aminoplast resin precursor aqueous solution of the present invention and an organic polyisocyanate is used in the present invention as a silicone-based and / or surface active agent. It is characteristic to use anionic and / or cationic and / or nonionic soaps which are agents.

As the silicone type foam stabilizer, any known one may be used, and there is no particular limitation.

Typically, a liquid modified silicone oil of the type that forms self-emulsifying micelles can be mentioned.

A pendant branched chain of polyalkylene glycol which has a weight average molecular weight of at most 30,000 and which may be actively blocked with a hydroxyl group or a lower alkyl having 1 to 6 carbon atoms at the end of the main chain of dirotylpolysiloxane. The modified silicone oil obtained by introducing is most commonly used, but it may be of a type in which a part of the methyl groups of the dimethylsiloxane main chain is replaced with a phenyl group, and if added in a small amount to pure water. Any silicon-based surfactant compound exhibiting low surface tension properties can be preferably used.

Among the silicon-based foam stabilizers, propylene oxide and / or ethylene oxide act on active hydrogen in the molecule to finally obtain a modified silicon compound having a polyalkylene glycol pendant group. The modified silicon compound is As dimethylsiloxane, 0.
05-0.2 mole fraction, ethylene oxide as 0.
3 to 0.8 mole fraction, and propylene oxide as 0.
3 to 0.8 mole fraction, and its weight average molecular weight is in the range of 5,000 to 25,000, and most preferably 7,500 to 15,000.
In the flame-retardant foam composition of the present invention, the main component is carbon dioxide gas, the foaming effect of generated bubbles is particularly high, and it is a particularly good example because the addition of a relatively small amount produces an excellent foaming effect. is there.

In the present invention, the above-mentioned silicon type foam stabilizer is used in a concentration of 0.0 in the organic component of the present invention.
It is used in the range of 1 to 5% by weight, more preferably 0.25 to 2% by weight, and most preferably 0.5 to 1% by weight. If the amount is less than 0.01% by weight, the foam-stabilizing effect cannot be obtained and the carbon dioxide gas bubbles generated will be broken.
This is because the effect does not change much in the above.

In the present invention, the foam stabilizer may be an anion, a cation, a nonion, or a complex or amphoteric surfactant, which may be used or used in combination as a foam stabilizer, and the soap is preferably an anion. Sex soap is good.

In particular, an anionic surfactant selected from an alkali metal salt of an aliphatic monoalkyl polyalkylene glycol ether sulfonic acid having 10 to 12 carbon atoms and an alkali metal salt of alkyl sulfonic acid having 8 to 18 carbon atoms. One kind is good.

Similar to the silicone type foam stabilizer, the proportion of the soap type foam stabilizer used is the concentration in the organic component of the present invention. When soap is used alone, it is preferably 0.01 to 5% by weight. Is in the range of 0.2 to 3% by weight, more preferably in the range of 0.5 to 1.5% by weight, and when used in combination with the silicone-based foam stabilizer, 0.01 to 1% by weight, It is preferably used in the range of 0.25 to 1% by weight.
The reason for the preferable range of the amount used is the same as for the silcon foam stabilizer.

The two types of foam stabilizers described in the present invention may be used individually or in combination, and either the diguanamine-based aminoplast resin precursor aqueous solution component or the polyisocyanate component of the present invention may be used before use. It may be pre-compounded in advance in one or both and stored.

However, when pre-blended with the polyisocyanate component and stored, it is important to limit to those which do not react with the active isocyanate group, and it is chemically inert to the isocyanate compound and It is important to properly select and use a material that exhibits a stable foam stabilizing effect.

The organic-inorganic hybrid type flame-retardant foam composition of the present invention refers to 100 parts by weight of the above-mentioned organic components.
70 to 850 parts by weight of a rehydration-curable inorganic aggregate composed of at least one kind or two or more kinds selected from the group consisting of anhydrous gypsum, hemihydrate gypsum and α-tricalcium phosphate, and its rehydration The organic component and the inorganic component obtained by the batch mixing reaction in the presence of water corresponding to 50 to 200 mol% of theoretical water necessary for rehydrating the possible inorganic aggregate are integrally complex-cured. It is a flame-retardant foam composition, and the most characteristic feature of the present invention is to hybridize a rehydratable inorganic aggregate.

The definition of "hybrid" is a term representing a state in which the inorganic aggregate exists in a complex state with the organic phase in a sufficiently hydrated solid state.

The rehydratable inorganic aggregate of the present invention is one or more selected from anhydrous gypsum powder and / or hemihydrate gypsum powder and tertiary calcium phosphate powder, excluding cement, quicklime and slaked lime. It is a mixed powder of.

In particular, β-type hemihydrate gypsum powder or α-type hemihydrate obtained by previously preliminarily subjecting dihydrate gypsum particles, which are naturally and / or industrially by-produced, to fluid calcination at 130 to 150 ° C. and drying and pulverization. The one selected from the group consisting of gypsum powder, anhydrous gypsum powder and α-tribasic calcium phosphate powder means that the foam material of the present invention has flame retardant properties and mechanical properties that allow it to pass the standard certification for building material products. This is because it is possible to impart physical strength and weather resistance.

Particularly preferable rehydratable inorganic aggregates include α-type and / or β-type hemihydrate gypsum powder.

Here, the anhydrous gypsum means type III β-anhydrite, and excludes type I to type III stable and hydrated anhydrous gypsum.

The average particle size of the rehydratable inorganic aggregate is not particularly limited, but it is 0.1 to 50 μm, preferably 1 to 3 μm.
It is preferable that the thickness is in the range of 0 μm, and as a result, handling workability, dispersibility, and formation of an inorganic phase composite of the resulting composite cured foam material tend to be excellent in uniformity.

The Blaine value of the rehydratable inorganic aggregate is 2,000 to 7,000 cm ² / g, which is preferable because it gives an appropriate hydration rate of the inorganic aggregate. .

The proportion of the rehydratable inorganic bone agent used is
70-8 based on 100 parts by weight of the organic component described in the present invention.
The amount is preferably 50 parts by weight, more preferably 155 to 480 parts.

What is essential is that the organic-inorganic hybrid ratio of the present invention is 45 to 90% by weight as the ratio of the inorganic bone substance present in the rehydrated state in the hybrid cured product. This is preferably 55 to 85% by weight, more preferably 60 to 75% by weight.

If the amount of the rehydrated bone agent present in the hybrid cured product is 45% by weight or less, JIS-A-1321 is sufficient.
This is because the specified building material products cannot exhibit the properties of Class 3 or higher of flame retardancy, and when it is 90% by weight or more, the cured product is unlikely to be a high foam, and it is also brittle when water resistant and easily loses practicality. .

[0191] More advantageously, the use of the above-mentioned diguanamine-based aminoplast resin precursor aqueous solution mixed and added at an alkaline pH value of 8 to 12 markedly accelerates the hydration rate of the inorganic aggregate. It is very preferable because the tendency to be formed is recognized. On the contrary, in an acidic system, the hydration rate of the hydratable inorganic aggregate may be greatly delayed, so that it is necessary to pay attention. Therefore, it can be said that the optimization of the PH value of the system is important to deal with after fully knowing in advance the effect of the pH adjusting agent to be used and the hydration rate of the inorganic aggregate.

In the present invention, a known inorganic filler may be partially used in combination with the above-mentioned rehydratable inorganic aggregate, within a range in which nonflammability of Class 3 or higher flame retardancy defined by JIS can be secured. Can be used together as appropriate.

Examples of the inorganic filler include silver, copper, iron,
Fine metal powder or metal-plated powder represented by nickel, brass, aluminum, stainless steel, lead, etc., alkali metal hydroxides such as aluminum hydroxide and magnesium hydroxide, carbonates such as magnesium carbonate, calcium carbonate and lithium carbonate. , Silicon oxide, iron oxide, copper oxide, aluminum oxide, magnesium oxide, calcium oxide, sodium oxide, tin oxide, silver oxide, zinc oxide, nickel oxide,
Metal oxides such as lead oxide, antimony oxide, titanium oxide and cobalt oxide, and mixtures or composite oxide foams thereof, shell powder, egg shell powder or bone powder which are apatite components,
Other common sands, volcanic ash, naturally occurring mineral powder and short fibers, ash ash, glass powder and short glass fibers, short carbon fibers,
Examples include short metal fibers.

The inorganic filler can be used within the same amount, preferably within 50 parts by weight, relative to 100 parts by weight of the hydratable inorganic aggregate of the present invention. Needless to say, the optimum combination ratio in that case is a range that can naturally satisfy the above-mentioned flame retardant properties of the foamed cured material of the present invention, and as a result of the combination, a secondary new additional function, That is, for example, a high-grade hue, texture, sound insulation / silence, or conductivity may be improved.

In particular, the combined use of an inorganic lightweight aggregate represented by shirasu balloon, glass balloon, synthetic mica plate, perlite, etc. makes the organic-inorganic hybrid flame-retardant foam composition of the present invention flame-retardant and lightweight. This is an example of the preferable inorganic filler because it can be expected that the application balance can be provided.

Although the rehydratable inorganic aggregate of the present invention does not include cement powder, quick lime, etc., it is not used in the present invention as an auxiliary material for intentionally reducing the bulk density of the hardened product. I don't care.

Particularly, since the foaming mechanism of the present invention is carbon dioxide gas (carbon dioxide gas) generated by the reaction of water and polyisocyanate as already described, so-called carbon dioxide gas such as cement powder or quick lime is contained in the cured composition. It is clear that foaming is controlled if there is an inorganic aggregate having a property of absorbing carbon dioxide, and it is not the intention of the present invention to have a large amount of carbon dioxide-absorbing aggregate until unfoamed. Excluded. However, since it can be used as a method for producing an appropriate bulk density, cement powder or quick lime can be used together as a rehydratable inorganic aggregate.

When the inorganic aggregate component is 100, the maximum is 30.
%, Preferably 10% by weight, most preferably 0.1 to 5% by weight, and one or more carbon dioxide-absorbing inorganic bones selected from cement powder, quicklime powder and slaked lime powder. Material can be used together.

In the organic-inorganic hybrid flame-retardant foam composition of the present invention, if necessary, known pigments, thixotropy imparting agents, weather resistance auxiliary agents, ultraviolet stabilizers, organometallic coupling agents, Water repellent, plasticizer, high boiling point solvent, foaming agent,
A viscosity imparting agent, a dispersion stabilizer, a PH buffering agent, a PH adjusting agent, a cement-based water reducing agent and the like may be added as appropriate. These auxiliary material components are used alone, preferably within 5% by weight, more preferably 3% by weight, based on the total composition of the present invention.
It should be within weight%.

Examples of the pigment include carbon black and organic pigments, and examples of the thixotropy-imparting agent include ultrafine powder of colloidal silica and other polyvalent aliphatic mercaptan compounds and polyamine compounds. Examples of weather resistance aids include phenothiazine, hydroquinone derivatives, hindered phenolic antioxidants and phosphites, UV stabilizers for hindered amines, and organometallic coupling agents for trimethoxysilane, dimethoxysilane. Examples thereof include silane coupling agents such as methylsilanes or titanate coupling agents.

As the water repellent, each emulsion of paraffin wax, microcrystalline wax, natural wax, synthetic polyethylene wax, polypropylene wax, silicone oil for fiber treatment, its micro dispersion or vinyl chloride emulsion, vinylidene chloride latex solution, styrene- Examples thereof include a butadiene-based latex liquid and an acrylic emulsion liquid.

Examples of the plasticizer include known substances capable of plasticizing vinyl chloride and polystyrene, and examples of the high boiling point solvent include minerals such as paraffin oil, naphthene oil, kerosene, light oil, and heavy oil. Examples thereof include oils, linseed oils, tung oils, rapeseed oils, persimmon oils, sesame oils, and other vegetable oils, aromatic oils such as α-pinene and β-pinene, and various solvents having a boiling point of 200 ° C. or higher.

Known examples of the viscosity-imparting agent include polyacrylic acid salts, soluble starch, soluble alginate, guar gum and its derivatives, and cellulose derivatives represented by methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and the like. .

As the foaming agent, organic azo compounds which decompose thermally to release nitrogen gas, and water-soluble or emulsifiable low-boiling solvents having a boiling point of less than 80 ° C., such as dimethyl ether,
Examples include acetone, methyl ethyl ketone, ethyl acetate, and alternative CFC compounds that do not substantially destroy the ozone layer, such as CFC-141b.

Examples of the dispersion stabilizer include known water-soluble polymers such as polyacrylamide polymer, resol type phenol resin, and styrene-maleic acid alternating polymer.

Examples of the cement water reducing agent include naphthalene sulfonic acid water reducing agent, melamine water reducing agent, polyacrylamide water reducing agent, and polycarboxylic acid water reducing agent. The present invention refers to 39.98 to 80% by weight of the effective resin component of the diguanamine-based aminoplast resin precursor aqueous solution (a) as an organic component, and an organic polyisocyanate containing at least two or more isocyanate groups in one molecule. 19.98 to 60% by weight, 0.01 to 3% by weight of tertiary amine urethanization catalyst, and 0.01 to 5% by weight of silicon type foam stabilizer and / or anionic surfactant foam stabilizer.
Of 100 parts by weight of an organic component containing and of a rehydration-curable inorganic aggregate composed of at least one kind or two or more kinds selected from anhydrous gypsum, hemihydrate gypsum and α-tricalcium phosphate. 60 to 850 parts by weight of organic-inorganic hybrid flame retardant obtained by mixing and reacting 60 to 850 parts by weight in the presence of water corresponding to 50 to 200 mol% of theoretical water necessary for rehydrating the inorganic aggregate. The most characteristic is that it is a foam composition.

In order to simultaneously and sufficiently satisfy the above problems to be solved by the present invention, each of the components in the above-mentioned organic-inorganic hybrid type composition of the present invention is indispensable.

The water necessary for rehydration of the rehydration-hardenable inorganic aggregate comprising at least one or two or more selected from anhydrous gypsum, hemihydrate gypsum and α-tribasic calcium phosphate is Water, which is a medium of the NDG-based aminoplast resin precursor, which is one of the essential organic components of the invention, may be applied as it is, and when it is insufficient with respect to the theoretical amount of water, fresh water may be additionally added.

The amount of water required for rehydration of the hydratable inorganic aggregate of the present invention is preferably 50 to 200 mol% of the theoretical hydration requirement, preferably 80 to 120 mol%. Most preferably, it is 90 to 110 mol%. This is because if it is 50 mol% or less, the flame-retardant property of the foamed cured product of the present invention is insufficient and a tough composite cured product having high practicality cannot be obtained.
This is because when 0 mol% or more is used, the stability of aggregate separation in the reaction system is lacking, and a large amount of excess water remains after the low temperature curing, and a long drying step is essential.

In the present invention, from the gist of the invention, the water necessary for rehydration of the hydratable inorganic aggregate is preliminarily adjusted so that the water medium amount of the diguanamine-based aminoplast aqueous solution is sufficient. It is essential that the concentration of the active ingredient is appropriately determined and used, and that care is taken so that there is almost no excess water in the cured composition after low-temperature foaming and curing.

In obtaining the organic-inorganic hybrid flame-retardant foam composition of the present invention, a urethane curing foaming reaction and a hydration curing reaction of the inorganic aggregate component are arbitrarily progressed to be achieved.

The initial setting PH value in the curing system, the PH value during curing, and the like may be set arbitrarily, and may be alkaline, neutral, or acidic.

Preferably, each curing reaction system at that time has a PH value of an organic component mixture system and / or water for addition, etc., which is added as necessary, under any conditions such as immediately before or at the time of mixing the respective components. Is preferably 8 or more and 12 or less in alkalinity.

That is, a foamed and cured product having an appropriate bulkiness is obtained in the alkaline system than in the cured system in which the initial PH value of the mixed system is acidified to be 6 or more under the same composition conditions. This is because at the same time as generally giving, the hydration rate of the inorganic aggregate in the cured product is further improved, and the combined curing time in the primary curing step can be shortened.

The method for producing an organic-inorganic hybrid flame-retardant foam of the present invention means that anhydrous gypsum, hemihydrate gypsum, and 100 parts by weight of the organic components containing the above-mentioned organic components are used.
6 of a rehydration-hardenable inorganic aggregate comprising at least one kind or two or more kinds selected from α-tricalcium phosphate
0 to 850 parts by weight are collectively compounded in the presence of water corresponding to 50 to 200 mol% of theoretical water necessary for rehydrating the inorganic aggregate, and mixed at a high speed for 5 to 30 seconds. Carry out urethanization reaction and rehydration reaction of inorganic aggregates at a temperature of ℃, and at the same time, the compounding system is foamed and cured by carbon dioxide gas generated by the reaction between polyisocyanate and water, and dried by touch. This is a method in which curing and foaming are advanced to such an extent that cutting processing is carried out at that stage, if necessary, and then a sufficient aging reaction is carried out at a temperature from room temperature to 130 ° C.

As a preferable production method which has particularly good reproducibility and high productivity, the rehydratable inorganic aggregate powder 100 can be used.
A good method is to make the total amount of the organic component and water for rehydration to be 40 to 100 parts by weight based on parts by weight, and the initial fluidity during mixing of the composition is smooth. Good because it is secured.

As an even more preferable manufacturing method, immediately after mixing and stirring, the mixture is appropriately discharged into a molding jig or a molding belt prepared in advance, and free-foamed and / or constrained-foamed to foam at a predetermined thickness. A manufacturing method for obtaining a molded body can be mentioned.

[0218] Further, as high-speed stirring conditions for batch mixing,
Arrange a heat-retaining bath with a temperature ranging from room temperature to 40 ° C and a stirring blade,
Using a mixing stirrer with a plurality of supply ports that can supply each component (quantitatively) in the upper part, and a built-in discharge port or discharge port in the lower part or the lateral part, The mixture was stirred at 1,000 to 10,000 revolutions per minute and discharged so that the average residence time was 5 to 40 seconds. The discharged product was stirred at room temperature to 80 ° C without stirring.
The primary curing and the foaming reaction are performed for 5 minutes to 5 hours in an atmosphere of a temperature lower than 5 minutes. Then, it is aged at room temperature / several days to 85 [deg.] C./24 hours under either condition of being hermetically closed or open to the atmosphere.

The method of producing by the above-mentioned steps is a highly preferable method since it can reproducibly and continuously produce a foamed cured product having a bulk density in the range of 0.01 to 0.65. It is mentioned as a manufacturing method of the invention.

Further, in the production method of the present invention, the ratio of complete hydration of the inorganic aggregate particle component capable of being rehydrated under the aging conditions of the primary and / or secondary reaction fields is based on the theoretical fully hydrated amount. At least 50 mol% or more, preferably 70 mol% or more,
The most preferable method is to combine 80% by mole or more with a dehydration / drying step and a complete hydration reaction step.

In the production method of the present invention, one or more kinds selected from cement powder, quick lime powder and slaked lime powder are used within 30% by weight when the rehydratable inorganic aggregate particle component is 100. A method of controlling the foaming and curing ratio of the reaction product by using the carbon dioxide absorbing aggregate together is one of the most preferable manufacturing methods.

As a further simple production method of the present invention, (a) an aqueous solution of a diguanamine-based aminoplast resin precursor, a tertiary amine urethanization catalyst, and optionally an organometallic urethanization promoter, and a silicon-based A foam stabilizer and / or an anionic surface active foam stabilizer, and water corresponding to 50 to 200 mol% of theoretical water necessary for rehydrating the inorganic aggregate, anhydrous gypsum, hemihydrate gypsum, α-second A liquid containing a rehydration-curable inorganic aggregate composed of at least one or more selected from calcium triphosphate, and an organic polyisocyanate containing at least two isocyanate groups in one molecule The two liquids consisting of the liquid B are quantitatively supplied to the mixing tank at the same time with high-speed stirring, mixed for 5 to 40 seconds at a temperature of room temperature to 40 ° C., and then discharged to the outside of the mixing tank.
There is a production method characterized by foaming and curing reaction in a fixed shape, and this production method is an example of the most industrially suitable method.

Any one of the above-mentioned methods may be optionally combined to finally obtain a bulk density of 0.8 or less, and most preferably 0.
In the range 01 to 0.65, and most most preferably 0.2.
Most highly preferred is also a method of making an organic-inorganic hybrid flame retardant foam in the range of 5 to 0.65.

[0224]

[Examples] Examples of the present invention will be described below. However, the present invention is not particularly limited to or restricts the present invention, and parts and% in Production Examples, Examples and Comparative Examples mean parts by weight and% by weight, respectively. Is.

What is a surface combustion test? A JIS certified building material combustibility tester manufactured by Toyo Seiki Seisaku-sho, Ltd. was used as an evaluation device conforming to JIS-A-1321. that time,
The judgment items of the surface combustion test were deformation, melting, afterflame time, exhaust temperature, and smoke coefficient, and the flame retardancy grade was judged and displayed from the overall result.

The evaluation of the compressive fracture strength of the cured product was carried out with a universal tensile compression tester manufactured by Intesco,
The compression speed was 2 mm / min, and the compression load per unit area was calculated from the maximum compression load value detected at the time when a compression crack or compression yield value was observed in the measurement sample, and the value was taken as the compression fracture strength value. In addition, the compressibility until fracture was obtained and used as a measure of elasticity.

The hydration rate% of the inorganic aggregate in the organic-inorganic composite cured product was measured by finely pulverizing the cured product and measuring the sample amount of 5 m.
TG / DTA measurement (differential thermal analysis / thermogravimetric analysis) in g at 110 ° C to 145 ° C from the region where the endothermic dehydration curve is observed is calculated from the following formula from the weight reduction ratio (weight reduction%). I asked.

Hydration rate% = (Dehydration weight% from TG / DTA measurement / Theoretical hydration weight% necessary for rehydration) × 100 The water immersion volume expansion coefficient was measured by the following method. Using the test body of the same size as the sample for measuring the compressive strength of the cured product obtained in each example, after measuring the dimension of each side before the test, 20
Put the test piece in city water at ℃, leave it for 48 hours with the dropping lid so that it is completely immersed in water, take it out, and immediately re-measure the dimensions of each side after immersion. Was calculated by volume% and displayed as volume expansion coefficient. At the same time, the test piece whose volume change rate measurement has been completed is subjected to compressive fracture strength measurement at 20 ° C. in a short time within 5 minutes after immersion in water to measure the compressive fracture strength before the water resistance test. The change rate of the compressive fracture strength after the water resistance test was defined as the water resistance strength retention rate%.

In measuring the elastic recovery rate, the above-mentioned thickness of 25 mm,
A 25% x 50 mm prismatic test piece was released by applying a constant compressive load of 10% for 5 hours at room temperature in the vertical thickness direction, and the resulting strain rate was calculated and displayed according to the JIS method. .

Production Examples of Diguanamine-Based Polyvalent Aminoplast Resin Precursor Aqueous Solution, Melamine Resin Precursor, and Urea-Based Resin Precursor: Production Example 1 3245 parts of 56% formalin, 4340 parts of CTU guanamine, and 1880 parts of water was charged and 20 ml of a 20% potash solution was added with stirring to adjust the initial PH to 8.7.

Then, the temperature of the system was raised to 50 ° C., and the reaction was continued at the same temperature until the whole became a transparent solution. Further, after becoming a clear solution, a 20% potency potassium solution was added in 1.0 to 1.5 ml portions in such a manner that the pH value was between 8.5 and 9, and the reaction was carried out at a reaction temperature of 55 ° C. for about 45 minutes. Continue, 20
Quenched to ℃. Further, it was treated at a high vacuum of 100 mmHg for 10 minutes at room temperature to remove and concentrate free formalin to obtain 9460 parts of a resin precursor aqueous solution as a whole. The final solution had a PH value of 8.8.

The reaction molar ratio of formalin / CTU guanamine was 6.03 in terms of the reaction molar ratio calculated in consideration of the amount of recovered formalin. The solution viscosity is 180c at 25 ℃.
It was about p. A resin aqueous solution DG- having an effective diguanamine-based aminoplast resin precursor concentration of 65% in terms of solid content
Got 1.

In water dilution ratio measurement of DG-1 1: 1.
It was the NDG-based aminoplast monomer solution of No. 5. Production Example 2 3280 parts of a low meta 37% formalin solution containing 6% methanol in a reaction vessel and 4340 CTU guanamine.
And 3330 parts of water were charged, and 28 parts of a 20% aqueous solution of caustic soda was charged and stirred.

Then, the temperature of the system was raised to 60 ° C., and the reaction was continued at the same temperature until the whole became a transparent solution. After becoming a clear solution, a pH value of 5.5 to 6 was prepared with a 20% aqueous solution of acetic acid, and the reaction was carried out at 60 ° C. for about 15 minutes. Was set to 9, and the mixture was immediately cooled to 20 ° C.

30 under high vacuum of 100 mmHg at 45 ° C.
It was treated for minutes to remove and concentrate free formalin, and cooled to obtain 11,000 parts of an aqueous resin precursor solution in total.

The reaction molar ratio of formalin / CTU guanamine was 3.97 in terms of the reaction molar ratio calculated in consideration of the amount of recovered formalin. The solution viscosity is 97c at room temperature.
p, a resin precursor aqueous solution DG-2 having an effective NDG-based aminoplast resin concentration of 50% in terms of solid content was obtained. 13C-N
Approximately 2 mol% of all produced methylol groups calculated from MR measurement were modified to methyl etherified methylol groups.

In the water dilution ratio measurement of DG-2, it was 1:
It was an initial condensate solution of 0.5. Production Example 3 16% of a high meta 37% formalin solution containing 1125 parts of 56% formalin and 8% methanol in a reaction vessel.
Charge 22 parts, 630 parts (5 mol) of melamine, 2170 parts (5 mol) of CTU guanamine and 1300 parts of water, and add 15 ml of 40% potency potassium solution under stirring,
The initial PH was adjusted to 9.5.

Then, the temperature of the system was raised to 65 ° C., and the reaction was continued at the same temperature until the whole became a transparent solution. After becoming a transparent solution, the reaction is continued for about 60 minutes at a reaction temperature of 80 ° C. while adding a 40% potency potash solution in a pH value of 9.0 to 9.5 as appropriate, until the temperature reaches 20 ° C. Quenched. Further, at room temperature to 45 ° C., under a vacuum of 250 mmHg, 20
It is processed for 20 minutes to remove and concentrate free formalin.
After cooling to 0 ° C., 6670 parts of aqueous resin solution was obtained in total. And the PH value of the final solution was 9.4 final. The formalin addition molar ratio was 3.98 in terms of reaction molar ratio calculated in consideration of the amount of recovered formalin. The solution viscosity is 100
An aqueous solution DG-3 having an effective diguanamine-based aminoplast resin precursor concentration of 59.8% in terms of solid content in cp level was obtained.

DG-3 was an initial monomer solution having a water dilution ratio of about 1: 2.

Production Example 4 As in Production Example 1, 2% of 56% formalin was added to the reaction vessel.
140 parts, 2530 parts of melamine, and 2130 parts of water were charged, and the pH of the system was adjusted to 11 with a 40% potash aqueous solution.
The temperature was raised to 5 ° C, the reaction was performed for about 90 minutes, and the temperature was rapidly cooled to 40 ° C. The mixture was further concentrated at the same temperature under a vacuum of 100 mmHg and cooled to obtain 6680 parts.

A solution of the melamine-based aminoplast resin precursor M- which is an initial condensate having a solution viscosity of 55 cp, an active ingredient resin concentration of solid content of 50.2%, and a formalin / melamine reaction molar ratio of 1.98. 1 was obtained in advance. The water dilution ratio of M-1 was 1: 2.5.

Then, 2000 parts of M-1 and Production Example 2
As a result of simply blending 3000 parts of NDG-2 obtained in step 3 at room temperature, the mixed aminoplast resin aqueous solution is DG-4 having a colorless and transparent viscosity of 83 cps and a pure content of 50%, which is a diguanamine-based polyvalent aminoplast resin precursor. A solution was obtained.

Production Example 5 In the M-1 production example of Production Example 4. The reaction was performed in the same manner except that 56% formalin was used as 3120 parts, and sufficient concentration under reduced pressure at 40 ° C. was performed to obtain 5600 parts. The solution viscosity is 79 cp, and the active ingredient resin concentration in terms of solid content is 6
A melamine-based aminoplast resin precursor aqueous solution M-2, which is an initial condensate having a 5% formalin / melamine reaction molar ratio of 2.97, was obtained in advance. The water dilution ratio of M-2 was 1: 1.5.

2500 parts of M-2 and ND obtained in Production Example 1
DG obtained by simply blending 2500 parts of G-1 at room temperature
The diguanamine-based aminoplast resin precursor aqueous solution of -5 was colorless and transparent, had a viscosity of 145 cps and a pure content of 65%.

Production Example 6 139 parts of a low-meta 37% formalin solution containing 6% methanol in a reaction vessel, 350 parts of 56% formalin, 345 parts of melamine, and a 20% aqueous solution of caustic soda.
8 parts were charged and stirred. Further, 68 parts of methanol and 1 part of vine crystals were added to the system and reacted at 75 ° C. until the whole became transparent. The reaction is continued for 4 hours at the same temperature and 40
The solution was rapidly cooled to ℃ and treated with 100% Hg vacuum to perform free methanol treatment and dehydration concentration to obtain a final solution pH of 10
The effective resin component concentration in terms of solid content is 63%, the solution viscosity is 105 cp at 20 ° C., the water dilution ratio is 1:10, the formalin / melamine reaction molar ratio is 3, proton NMR and 13 C-
Approximately 3 of all produced methylol groups calculated from NMR measurements
Modified melamine-based aminoplast resin precursor aqueous solution M in which 4 mol% was modified to methyl etherified methylol groups
-3 was prepared.

2000 parts of M-3 and 3000 parts of NDG-1 obtained in Production Example 1 were simply blended at room temperature to give a DG-6 diguanamine-based polyfunctional fuminoplast resin having a viscosity of 155 cps and a pure content of 64%. A precursor mixed solution was obtained.

Production Example 7 A reaction vessel was charged with 536 parts of 56% formalin solution, 273 parts of granular urea, 5 parts of methanol and 0.28 part of 20% aqueous caustic soda solution and 12 parts of water, and the initial PH value was adjusted. The system was stirred as 8.7. The system was heated to 85 ° C., reacted for 50 minutes, and then rapidly cooled to a final solution PH of 8.2, a solid content-based effective resin component concentration of 70%, a solution viscosity of 43 cp at 20 ° C., and a water dilution ratio of 1: 3, a formalin / urea reaction molar ratio of 2.15, and a suspension type urea at room temperature in which approximately 1.5 mol% of all methylol groups produced by proton NMR measurement were modified to methyl etherified methylol groups A system aminoplast resin aqueous solution U-1 was prepared in advance. Methanol was appropriately additionally prepared so that 0.5% of methanol was present in U-1 in a free state, and the following operation was performed.

1000 parts of U-1 and 4000 parts of DG-3 obtained in Production Example 3 were simply blended at room temperature to give a viscosity of 8
A diguanamine-based polyvalent fuminoplast resin precursor mixed solution containing DG-7 having a pure content of 62% at 8 cps was obtained.

Production Example 8 2500 parts of M-1 obtained in Production Example 4 in a reaction vessel,
After 2500 parts of DG-2 obtained in Production Example 2 was simply blended at room temperature and charged, the pH value was adjusted to 5.0 to 5.5 with paratoluenesulfonic acid, and the temperature of the system was raised by raising the temperature. 65
The temperature was set to 0 ° C., the condensation reaction was allowed to proceed for about 30 minutes, and then the PH value was neutralized to 8 again with 20% aqueous ammonia. As a result, a polyvalent aminoplast initial condensate aqueous solution DG-8 having a water dilution ratio of 1: 0.1 was prepared, and the active ingredient concentration was 48%.

Production Example 9 1 / of the granular urea used in the preparation of U-1 in Production Example 8
A urea-thiourea complex having a concentration of active ingredient of 70% and a reaction molar ratio of 2.18 represented by formalin / [total of urea and thiourea] was carried out by substituting thiourea for 3 mol equivalent amount. A type aminoplast resin aqueous solution U-2 was obtained.

1000 parts of U-1 and 4000 parts of DG-2 obtained in Production Example 2 were simply blended at room temperature to give a pure content of 5
A diguanamine-based polyvalent fuminoplast resin precursor mixed solution containing 4% DG-9 was obtained.

Production Example 10 1000 parts of DG-4 obtained in Production Example 4 was charged into a reaction vessel, 200 parts of sodium bisulfite was added at 78 ° C., and the mixture was reacted at a PH value of 10.6 for 2 hours. Then, it is rapidly cooled to room temperature, neutralized with a 60% aqueous solution of phosphoric acid to a pH value of 7 to 8 and diluted with water, and anionized modified diguanamine-based aminoplast resin solution DG- having an active ingredient concentration of 50%.
Got 10.

Example 1 A cup was prepared, and each of the component proportions shown in Table 1 was added to each of the diguanamine-based aminoplast resin precursor aqueous solutions obtained in Production Examples 1 to 4 to prepare a foam stabilizer, a urethanization catalyst, and a necessary amount. According to the above, after adding and dispersing a pH adjusting agent which is a diluted solution of inorganic acid, crude diphenylmethane diisocyanate (product of Mitsui Toatsu Chemicals, Inc .: trade name / CR-200) and natural gypsum are fired in a fluidized firing furnace at 138 ° C. The average primary particle size is 1.
2μm, β-type hemihydrate gypsum (product of Santo Gypsum Board Co., Ltd.) powder having a Blaine value of about 6,500 cm 2 / g was added all at once, and the mixture was mixed with a stirrer having a turbine blade with a diameter of 70 mm to 1000
The mixture was agitated by rotation for 20 seconds, and immediately transferred to a molding cup having a thickness of 12 mm and a bottom of 300 mm square, which was subjected to mold release on the entire surface, and was molded and cured. The slurry temperature at the initial stage of liquid transfer was 23 ° C. for the cured product numbers (b) to (g) except that the cured product number (a) in Table 1 was 50 ° C.

Free foaming was carried out in a polycup under the same compounding conditions, and the cured foaming behavior characteristics were measured. As the measurement results at that time, the cream time, the rise time and the touch tack free time are shown in Table 1. It is displayed in the section of behavior result.

Molded products and free foam cured products are room temperature cured 3
After the time, secondary curing was carried out for 8 hours in a 75 ° C. thermostat under a sealed condition to obtain organic-inorganic hybrid foamed cured products (a) to (g) shown in Table 1.

From (a) to (g) obtained by free foaming,
Each piece was cut into a square piece having a thickness of 25 mm and a base of 50 × 50 mm, and the compression strength test, the water resistance test, the bulk density, and the closed cell ratio were measured on the test piece, and the results are shown in Table 1.

Each of (a) to (g) obtained as a molded foam having a thickness of 12 mm had a size of 220 mm square, and JIS
It was subjected to a surface combustion test according to -A-1321, and the results are shown in Table 1.

Example 2 A cup was prepared, and each diguanamine-based aminoplast resin aqueous solution obtained in each of Production Examples 5 to 10 was preliminarily heated to 42 ° C. with the respective component ratios shown in Table 2 therein to prepare bubbles. Agent and urethanization catalyst, and if necessary, PH solution which is an aqueous solution of inorganic acid is added and dispersed, and 40 ° C crude diphenylmethane diisocyanate is Mitsui Toatsu Chemicals: MD
I-CR-300 and natural gypsum lumps were fired in a continuous fluidized bed type kiln at 138 [deg.] C. in an atmosphere of half water to give an average primary particle diameter of 12 [mu] m and a Blaine value of about 6,500 cm <2> / g at 40 [deg.] C. Beta-type hemihydrate gypsum powder and, if necessary, water for additional addition were added all at once, and the mixture was stirred for 20 seconds at 850 rotations with a stirrer having a turbine blade with a diameter of 55 mm, and the entire surface was immediately demolded. The liquid was transferred into a molding cup having a thickness of 12 mm and a bottom of 300 mm square to mold and cure. The slurry temperature at the initial stage of liquid transfer was 45 ° C.

Free foaming was carried out in a polycup under the same compounding conditions, and the curing foaming behavior characteristics were measured. As the measurement results at that time, the cream time, the rise time and the tact free tack time are shown in Table 2. It is displayed in the section of behavior result.

[0260] Curing of molded products and free-foam cured products begins 1
After 0 minutes, the cured sample body was subjected to secondary curing for 8 hours in a thermostatic chamber at a temperature of 75 ° C. in a state where water evaporation was prevented, and then demolded, and each organic-inorganic hybrid type foamed and cured body (see Table 2) as a foamed and cured body ( Chi) to (Mo) were obtained.

From (H) to (F) obtained by free foaming,
Each piece was cut into a square piece having a thickness of 25 mm and a bottom of 50 × 50 mm, and the test piece was used to measure the compressive strength test, the water resistance test, the bulk density and the closed cell rate, and the results are shown in Table 2.

Further, each of (H) to (F) obtained as a molded foam having a thickness of 12 mm had a size of 220 mm square, and JIS
It was subjected to a surface combustion test according to -A-1321, and the results are shown in Table 2.

Example 3 Each aminoplast obtained in each of Production Examples 1, 3, 5, 5 and 10 was prepared by preparing a cup and preliminarily heating it to 35 ° C. in the ratio of each component shown in Table 3. After adding a foam stabilizer, a urethanization catalyst and a 20% sulfuric acid aqueous solution to the resin aqueous solution at once,
The system is further comprised of 31% NCO-containing Mitsui Toatsu Chemicals'"MDI-CR-200" crude diphenylmethane diisocyanate, and an average primary particle diameter of 17 μm, and a Blaine value of about 5,100 cm 2 / g α-type semi-water. Gypsum powder and other inorganic aggregates listed in Table 3 were added together in a hydratable manner, and the mixture was stirred for 20 seconds at 850 rotations with a stirrer having a turbine blade with a diameter of 55 mm, and the entire surface was immediately released from the mold. The liquid was transferred to a molding cup having a thickness of 12 mm and a bottom of 300 mm square to mold and cure. The slurry temperature at the initial stage of liquid transfer was 36 ° C.

Free foaming was carried out in a polycup under the same compounding conditions, and the curing foaming behavior characteristics were measured. As the measurement results at that time, the cream time, the rise time and the tact free tack time are as shown in Table 3. It is displayed in the section of behavior result.

The molded product and the free-foamed cured product were sealed while completely preventing the diffusion of water from the stage after the foaming touch drying during curing, allowed to stand at room temperature for 24 hours, and then taken out and subjected to the organic treatment shown in Table 3. Inorganic hybrid foamed and cured products (Yo) to (n) were obtained. From (Yo) to (N) obtained by free foaming, each piece was cut into a square piece having a thickness of 25 mm and a base of 50 × 50 mm, and the test piece was independent of the compression strength test, water resistance test, and bulk density. The bubble ratio was measured, and the results are shown in Table 3.

Further, each of (Yo) to (N) obtained as a molded foam having a thickness of 12 mm had a size of 220 mm square, and JIS
It was subjected to a surface combustion test according to -A-1321, and the results are shown in Table 3.

Example 4 A flat decorative steel sheet having a thickness of 0.27 mm and a size of 30 cm was prepared, in which a gray polyester paint was baked on the top coat and a rust preventive service paint was similarly applied as the back coat material. Two sets of foam hardening molds were prepared in which the steel plate was placed with the service coat surface as the upper surface and the steel plate was surrounded by a wooden frame of a square quadrangle having a thickness of 12 mm and a side length of 28 cm.

On the other hand, the aminoplast resin DG-2 was preliminarily silicone-containing with a 2 liter beaker in exactly the same proportion except that the sulfuric acid solution for PH preparation shown in Experiment No. (C) of Example 1 was not used. Foam stabilizer and urethane catalyst X
1: Triethylenediamine, dimethylaminoethanol and N, N-dimethylbenzylamine 1: 1: 1 70
% Pure mixed catalyst solution, X2: dibutyltin dilaurate and β-type hemihydrate gypsum powder (Blaine value is 5,800 c
m2 / g) was prepared in advance to prepare 840 parts of liquid A paste.

Solution # 5 within 5 minutes after the preparation of solution A. As solution B, Mitsui Toatsu Chemicals CR # 200 containing 33% of isocyanate groups as a polyisocyanate component.
Of 125 parts was added, and the mixture was stirred at 1000 rpm for 20 seconds with a stirrer having a turbine blade with a diameter of 70 mm.

Immediately, 250 parts ± 10 parts of the slurry was immediately poured onto the back surface of the steel plate in the two sets of the foam hardening molding jigs, and after the aluminum laminated paper was placed thereon, 5
A 50 ° C. heated stainless steel plate having a thickness of 5 mm was covered, and the same 5 mm thick 50 ° C. heated stainless steel plate was also applied to the lower part of the steel plate. Then, the four sides between the stainless steel plates were pressure-fastened with clips or the like, and the foaming and hardening reaction of the internally filled slurry liquid was allowed to proceed while keeping horizontal.

The slurry temperature at the initial stage of liquid transfer was 45 ° C., and the highest exothermic state inside was observed at 78 ° C. after 2 minutes and 40 seconds from the time of filling, as measured by a thermocouple.

35 minutes after the filling, when the wooden frame and the holding lid were removed, it was visually observed that the entire portion regulated by the wooden frame was foamed and fluidized to be primary cured. And thickness 12m
Two primary foam-hardened panel test pieces bonded to the surface steel sheet laminate having m and a width of 24 cm were obtained.

[0273] The foamed core material had been cured to such an extent that it could be sufficiently carried.

Two of the primary foam-cured panel test pieces were wrapped with a wrap material and the vapor diffusion of water vapor was completely prevented at 75 ° C.
Put it in the oven for 3 hours, take it out, cool it to room temperature, then remove the wrap material, and use the surface-coated steel sheet as a backup core material with an inorganic-organic hybrid type composite foamed and cured product having a composition according to (c) of Table 1. As a result, a steel sheet laminated body shaped as (c) was obtained.

(C) Two pieces of steel sheet laminating bodies were cut into 22 cm square test pieces, and the steel sheet surface was used as the surface according to JIS-A-1321. As a result of conducting a surface combustion test for judging pass / fail of flame retardant class 2 with a through hole for 10 minutes, the exhaust temperature characteristics are expressed by the area of the curve deviating from the reference temperature curve for 3 to 10 minutes after the start of the JIS standard test. As a result of the tdθ value being about 50 for both sheets and the JIS specified CA value of smoke emission coefficient being 56 and 58, the afterflame time was 1 second for both sheets, and there were no other problems such as melting of all thickness and remarkable deformation abnormality. Not recognized, it was found to be a material that passed the standard of flame retardancy class 2 for building material products.

(C) The core material bulk specific gravity calculated from the core material weight obtained by subtracting the steel plate weight from the total weight of the laminated steel sheet and its occupied volume was 0.29 and 0.31, respectively.

[0277] Also, a width of 2.5 x taken from a cut piece
The core material itself using a 5 cm square block piece had a compressive fracture strength of 2.8 to 3.3 kg / cm @ 2, and the strength retention rate after immersion in water for 48 hours was 96% at the minimum, showing good water resistance strength characteristics. .

Example 5 (C) Gypsum lamella obtained in the same manner as in Example 4 except that the decorative steel plate used in Example 4 was replaced with a gypsum plate having a specific gravity of 0.88 and a thickness of 3 mm, and the gypsum laminate was 22 cm square. In the test piece after cutting so as to be as follows, a surface combustion test was performed for 10 minutes with a gypsum plate as the surface according to JIS-A-1321. The tdθ value represented by the area of the curve deviating from the standard temperature curve for up to 10 minutes is about 45, and the smoke emission coefficient specified by JIS
The CA value was 41, the afterflame time was 0 seconds, and other total thickness melting and remarkable deformation abnormality were not observed at all, and it was proved that the material passed the second-class flame retardancy standard for building material products.

[0279] (c) A crushed sample of 5 m collected from the inorganic-organic hybrid type composite foam-hardened core material part of the gypsum laminating body
As a result of TG / DTA measurement using g, the dihydrate gypsum hybridization ratio was found to be 71%. The hydration rate of hemihydrate gypsum determined from the same result was 96%.

Example 6 The same procedure as in Example 4 was carried out except that the decorative steel plate used in Example 4 was replaced with an asbestos slate plate having a thickness of 3 mm (C).
The asbestos slate laminar body is a 22 cm square test piece after cutting, and in accordance with JIS-A-1321, the asbestos slate is used as a combustion test surface and through holes of 25 mm diameter are provided at three predetermined places. As a result of performing the provided combustion test for 10 minutes, the exhaust gas temperature characteristic is 3 to 1 after the JIS standard test is started.
The tdθ value represented by the area of the curve that deviates from the standard temperature curve up to 0 minutes is about 10, the smoke emission coefficient of JIS standard CA value is 52, the afterflame time is 0 seconds, and other total thickness melting and significant deformation No abnormalities were observed, and it was found that the material passed the flame-retardant Class 2 standard for building material products.

(C) The bulk specific gravity of the inorganic-organic hybrid type composite foam-hardened core material portion of the asbestos board laminate is 0.30, the compressive fracture strength is 2.8 Kg / cm 2, and the compressive displacement during compression fracture is 12. It was at the time of 9% compression.

Example 7 The top coat was baked with a gray polyester paint, and the rust preventive service paint was similarly applied as the back coat material. Thickness 0.27 mm, 30 cm
A square flat decorative steel plate is prepared, and the steel plate is placed with the service coat surface as the upper surface, and the steel plate is surrounded by a square rectangular wooden frame having a thickness of 15 mm and a side length of 28 cm.
Two sets of foam hardening molds were prepared.

On the other hand, in a 2 liter beaker, the ND obtained in Preparative Example 15 was prepared in the same manner as shown in Experiment No. (F) in Table 2 of Example 2 with the same blending ratio except for the polyisocyanate component.
To the 200 parts of G-10, 1 of the silicone foam stabilizer L-5305
Parts and urethanization catalyst X3: 2 parts of 2,4,6-tri (dimethylaminomethyl) phenol, X2: 1 part of dibutyltin dilaurate and β-type hemihydrate gypsum powder (Blaine value is 5,800 cm 2 / g) And 265 parts of Mitsui Toatsu Chemicals CR # 300 with 31% of isocyanate group content, which is a polyisocyanate component, are added all at once and stirred at 600 rpm for 5 seconds with a stirrer having a turbine blade with a diameter of 70 mm. Let

Immediately, 350 parts ± 10 parts of the slurry was immediately poured onto the back surface of the steel plate in the two sets of foam hardening molding jigs, and after the aluminum laminated paper was placed thereon, 5 parts were further placed thereon.
A 50 ° C. heated stainless steel plate having a thickness of 5 mm was covered, and the same 5 mm thick 50 ° C. heated stainless steel plate was also applied to the lower part of the steel plate. Then, the four sides between the stainless steel plates were pressure-fastened with clips or the like, and the foaming and hardening reaction of the internally filled slurry liquid was allowed to proceed while keeping horizontal.

The slurry temperature at the initial stage of liquid transfer was 45 ° C., and the highest internal exothermic state was 80 ° C. after 2 minutes 25 seconds from the time of filling, as measured by a thermocouple.

35 minutes after the filling, when the wooden frame and the holding lid were removed, it was visually observed that the entire portion regulated by the wooden frame was foamed and fluidized to be primary cured. And thickness 15m
Two pieces of primary foam-cured sandwich panel test pieces were obtained in which a m-sided steel sheet having a width of 24 cm and a aluminum laminated paper were bonded as a covering material.

[0287] The foamed core material of the test piece was cured so that it could be sufficiently carried.

Two primary foam-cured sandwich panel test pieces were wrapped in a wrap material, placed in a 75 ° C. oven for 12 hours under the condition that vapor diffusion was completely prevented, taken out, cooled to room temperature, and then removed from the wrap material. Then, an inorganic-organic hybrid type composite foam cured product having a composition according to (f) in Table 2 is formed on the surface decorative steel sheet as a sandwiched core material / organic-inorganic hybrid composite foam comprising (f) A cured core material / aluminum laminated paper sandwich body [abbreviated as sandwich building material of (f)] was obtained.

Two pieces of (f) sandwich building materials are provided in 22c.
JIS-A-1 in the test piece after cutting so that it becomes m square
According to 321, use the steel plate surface as the surface, and
As a result of performing a surface combustion test for judging pass / fail of Class 2 flame retardant having a through hole with a diameter of 5 mm for 10 minutes, the exhaust gas temperature characteristic is JI
The value of tdθ represented by the area of the curve deviating from the reference temperature curve within 3 to 10 minutes after the start of the S-specified test is 0 for both the two sheets,
Moreover, as a result of the JIS standard CA value of 38, which is the smoke emission coefficient, the afterflame time was 0 seconds for both two sheets, and there was no noticeable melting or deformation of the entire thickness. It was found to be a material that passed the standard.

The core material bulk specific gravity calculated from the core material weight obtained by subtracting the weights of the steel plate and the aluminum laminated paper from the total weight of the sandwich building material of (f) and its governing volume is 0.
It was with 26.

[0291] Also, a width of 2.5 x taken from a cut piece
The core material itself using a 5 cm square block piece had a compressive fracture strength of 1.8 to 2.0 kg / cm @ 2, and the strength retention rate after immersion in water for 48 hours was 95% at a minimum, showing good water resistance properties. .

Example 8 An organic-inorganic hybrid consisting of cement board / (f) obtained in the same manner as in Example 7 except that the decorative steel sheet used in Example 7 was replaced with a cement board having a specific gravity of 1.3 and a thickness of 3 mm. The composite foam-hardened core material / aluminum laminated paper sandwich body is a test piece after being cut so as to have a 22 cm square, in accordance with JIS-A-1321, the core material is used as the surface and the surface combustion test is performed for 10 minutes. As a result, the exhaust temperature characteristic is J
The tdθ value represented by the area of the curve deviating from the standard temperature curve within 3 to 10 minutes after the start of the IS standard test is 0, the JIS CA value, which is the smoke emission coefficient, is 42, and the afterflame time is 0.
Secondly, no melting of the entire thickness or remarkable deformation abnormality was observed at all, and it was found that the material passed the second-class flame retardancy standard for building material products.

Also, as a result of TG / DTA measurement using 5 mg of a crushed sample taken from the core material part of the organic / inorganic hybrid composite foam / hardening core material / cement board / (f) / aluminum laminated paper sandwich body, dihydrate gypsum Hybridization ratio was found to be 70%. The hydration ratio of hemihydrate gypsum obtained from the same result was 93%.

Example 9 200 μ was used in place of the decorative steel plate used in Example 7.
Semi-hard vinyl chloride film laminated steel sheet obtained in the same manner except that a semi-hard vinyl chloride film laminated steel sheet having a thickness of m /
22 cm of the organic-inorganic hybrid composite foam cured core material / aluminum laminated paper sandwich consisting of (f)
In the test piece after cutting so that it becomes a corner, JIS-A
According to -1321, a surface combustion test was conducted for 6 minutes with the vinyl chloride-coated steel sheet material as the surface.

As a result, the exhaust temperature characteristic was about 100 at the tdθ value represented by the area of the curve deviating from the standard temperature curve within 3 to 10 minutes after the start of the JIS standard test, and the JIS standard CA that was the smoke emission coefficient. The value is 57, the afterflame time is 0 seconds,
In addition, no melting of the entire thickness or remarkable deformation abnormality was observed at all, and it was determined that the material passed the second-class flame retardant standard for building material products.

Example 10 In Example 4, the composition shown in Experiment No. (C) of Table 1 of Example 1 was used, and the phosphoric acid solution for PH adjustment was not used. Instead of the silicone foam stabilizer, an anionic interface was used. The decorative steel sheet / organic-inorganic hybrid foam-hardening core material composite board obtained in exactly the same manner as in JIS except that 5 parts of Kao's product "Emar E-70C", which is sodium polyoxyethylene lauryl ether sulfate as the activator, was used. According to -A-1321, a surface combustion test was performed for 10 minutes to determine pass / fail of flame-retardant class 2 with a steel plate surface as a surface and through holes with a diameter of 25 mm provided at three predetermined places. The tdθ value represented by the area of the curve deviating from the standard temperature curve within 3 to 10 minutes after the start of the specified test is in the range of 40 to 45, and the smoke emission coefficient, the JIS CA value, is 34. During 1 sec, all other thicknesses melting or significant deformation was not observed at all such abnormal was found to pass the standard of flame retardancy grade 2 regarding building materials.

As in Example 4, the core material bulk specific gravity calculated from the weight of the core material obtained by subtracting the weight of the steel sheet from the total weight of the laminated steel sheet and its governing volume was 0.31. The core material itself has an average compressive fracture strength of 2.2 kg / c.
m2, the strength retention rate after immersion in water for 48 hours is at least 96
%, Showing favorable water resistance strength characteristics.

Production Comparative Example 1 2390 parts of 40% formalin solution, melamine 2590
Parts, 2100 parts water, 130% 0.7% potassium hydroxide solution
Parts are mixed and the reaction temperature is raised to 85 ° C. to adjust the PH value to 10
The reaction was carried out for 3 hours while maintaining at ˜10.5 to obtain a transparent liquid.

The solution viscosity was 33 cp at room temperature, and 1.5 mol of formaldehyde was added to 1 mol of melamine having a solid content of 50% and a water dilution ratio of 1: 2.
It was a low-F melamine aminoplast resin aqueous solution (MF-1) in which the formaldehyde-added monomer represented by the triazine skeleton unit determined by 96% occupied 96%.

The abbreviation for low F means that a low molar number of formaldehyde is added.

Production Comparative Example 2 3200 parts of 56% formalin, 2520 parts of melamine and 3250 parts of water were charged in a reaction vessel, and the mixture was heated with stirring.
25 ml of 40% aqueous potassium hydroxide solution was added, and the pH value was kept at 11 to 11.5 and reacted at 80 ° C. for 1 hour. After cooling to 45 ° C, decompression under 100 mmHg.
Concentrated and 58 cp melamine resin precursor solution A at 20 ° C
-1 was obtained.

50% formaldehyde / solid content /
The resin aqueous solution was composed of initial monomers with a reaction molar ratio of melamine of 2.96 and a water dilution ratio of the A-1 solution of 1: 4. Comparative Example 1 200 parts of the aqueous solution of low F melamine aminoplast resin (MF-1) obtained in Comparative Example 1 prepared in a 1 liter capacity polycup, and glycerin as a starting material as a polyether polyol having a weight average molecular weight of 535 A product of Mitsui Toatsu Chemicals, which is a triol compound obtained by adding polypropylene oxide; 20 parts of MN-500, 5 parts of dimethylbenzylamine as a urethane-forming catalyst, 0.1 part of dibutyltin dilaurate, a foam stabilizer. NOF products as an anionic surfactant which is a kind of sodium alkyl sulfonate as; as 2 parts of Emal 20C, active isocyanate content as polyisocyanate component 3
3% of Mitsui Toatsu Chemical Co., Ltd .; 100 parts of CR # 200 was weighed and added, and the mixture was batch mixed at a high speed for 600 seconds per minute with a turbine impeller agitator for 15 seconds, then allowed to stand and the cream temperature was 23. Free-foamed in a polycup at 0 ° C.

The cream time of the mixed composition is 32.
Seconds, the rise time was 1 minute 57 seconds, and the tack free time was 2 minutes.

After 1 hour, place in an oven at 75 ° C. for 24 hours.
After aging and curing, a melamine-modified hard urethane foam of Comparative Example 1 was obtained. The bulk specific gravity of the foam is 0.085.
And the compressive strength was 197 g / cm 2.

On the other hand, the above-mentioned uncured high speed mixed composition was newly prepared, and 100 parts of the composition was immediately put into a 25 cm square 12 mm thick release box, and the top surface of the box was laminated with release paper. After covering with a steel plate lid and foaming with pressure fastening, it is demolded after 1 hour, and similarly after curing and drying for 24 hours in an oven at 75 ° C., a 22 cm square foam sheet with a bulk specific gravity of 0.09 is obtained. When subjected to a surface combustion test on the product, the value of 0 to 3 minutes of the exhaust temperature curve already showed a behavior exceeding the reference temperature, and it failed the flame retardant class 3.

[0306] Furthermore, the smoke emission coefficient CA value is 120 at 6 minutes.
167, which is far higher than the above, was completely rejected as a flame retardant material for building materials.

Comparative Example 2 Manufactured in a polycup having a capacity of 1 liter 200 parts of the aqueous solution of the low-F melamine-based aminoplast resin (MF-1) obtained in Comparative Example 1, glycerol as a starting material was used as a polyether polyol having a molecular weight of 535. A product produced by Mitsui Toatsu Chemicals, which is a triol obtained by adding polypropylene oxide; 20 parts of MN-500, 5 parts of dimethylbenzylamine as a urethane-forming catalyst, 0.1 part of dibutyltin dilaurate, and a foam stabilizer. Nippon Oil & Fats Products which are anionic surfactants; 2 parts of Emal 20C, 1 part of 60% phosphoric acid aqueous solution, Mitsui Toatsu Chemical Co., Ltd. product with active isocyanate content of 33% as polyisocyanate component; CR
100 parts of # 200 and 2 having an average particle size of about 35 μm
100 parts of natural gypsum powder which is hydrated gypsum is weighed and added,
15 at once with a turbine blade type agitator at 600 rpm
After high-speed mixing for 2 seconds, the mixture was left to stand to allow free foaming in a polycup at a cream temperature of 23 ° C.

The cream time of the mixed composition is 37.
Seconds, the rise time was 2 minutes and 42 seconds and the tack free time was 2 minutes and 30 seconds, but the foaming phenomenon was noticeable during foaming, and foaming fracture hardening shrinkage was observed.

After 1 hour, place in an oven at 75 ° C. for 24 hours.
After time-drying and curing, a natural gypsum of Comparative Example 2 and a low F melamine-modified hard urethane foam composite were obtained. The bulk specific gravity of the composite foam was 0.76.

On the other hand, the above-mentioned uncured high-speed mixed composition was newly prepared, and the whole amount thereof was immediately put into a 25 cm square and a thickness of 12
It is placed in a 3 mm release box, free-foamed, demolded 1 hour later, similarly cured and dried in an oven at 75 ° C for 24 hours, and then foamed 22 cm square with a bulk specific gravity of 0.81 and a thickness of 7 mm. A composite foamed sheet containing 30% natural gypsum with a rough surface having a finely wavy upper surface was obtained.

When a building material product / surface combustion test was performed on the lower surface of the foamed sheet of the sheet, the exhaust temperature curve of 0 to
The 6-minute tdθ value exceeded 120, showing 325, and failed flame retardant class 3. Similarly, the smoke emission coefficient CA was 6 minutes, far exceeding 120, which was 133, and was completely unsuitable as a flame retardant material for building materials.

Comparative Example 3 Aluminum hydroxide and a low-F melamine-modified hard urethane foam composite obtained in exactly the same manner as in Comparative Example 2 except that fine powder of reagent grade aluminum hydroxide was used instead of the natural gypsum powder. Shows a curing behavior similar to that of Comparative Example 2, and the undried cured product after 1 hour of the reaction contained a large amount of excess water and exhibited a property of being completely brittle and easily bent. Further, the bulk specific gravity after drying carried out under the same conditions as in Comparative Example 2 was as high as 0.84, and a lightweight foamed cured product was not produced.

Similarly, J with respect to the back surface of the aluminum hydroxide and the low F melamine-modified hard urethane foam composite sheet
The result of the flame-retardant test prescribed by IS-A-1321 was a flame-retardant grade 3 or lower.

Comparative Example 4 A melamine resin precursor aqueous solution A-1 obtained in Production Comparative Example 2 was prepared by preparing a cup and using the respective component ratios shown in Table 4 therein, a foam stabilizer, a urethanization catalyst, and if necessary. After adding and dispersing a pH adjusting agent which is a diluted solution of inorganic acid, crude diphenylmethane diisocyanate (product of Mitsui Toatsu Chemicals Inc .: trade name /
CR-200) and β-type hemihydrate gypsum (manufactured by Santo Gypsum Board Co., Ltd.) in large amounts, if necessary, with the addition of the preceding components all at once with a stirrer having a turbine blade with a diameter of 70 mm.
Immediately after stirring at 000 rpm for 20 seconds, the liquid was transferred into a mold cup having a thickness of 12 mm and a bottom of 300 mm square, which was subjected to mold release treatment, to mold and cure.

The slurry temperature at the initial stage of liquid transfer is 50 ° C. for the cured product number (Y1) and 2 for the cured product number (Y2) in Table 4.
Performed at 3 ° C.

Free foaming was carried out in a polycup under the same compounding conditions, and the cured foaming behavior characteristics were measured. As the measurement results at that time, the cream time, the rise time and the tact-free tack time were as shown in Table 4. It is displayed in the section of behavior result.

Molded products and free foam cured products are room temperature cured 3
After the time, secondary curing was carried out for 8 hours in a 75 ° C. dryer to obtain foamed cured products (Y1) and (Y2) shown in Table 4. (Y1) and (Y2) obtained by free foaming each have a thickness of 25 mm,
After cutting into square pieces having a bottom of 50 × 50 mm and measuring the bulk density of each of the test pieces, the pieces were subjected to a compressive strength test and a water resistance test, and the results are shown in Table 4.

Further, each (Y1) and (Y2) obtained as a molded foam having a thickness of 12 mm had a size of 220 mm square and J
It was subjected to a surface combustion test in accordance with IS-A-1321, and the results are also shown in Table 4.

Comparative Example 5 A cup was prepared, and each of the component ratios shown in Table 4 was added to the melamine resin precursor aqueous solution A-1 obtained in Production Comparative Example 2 to prepare a foam stabilizer, a urethanization catalyst, and if necessary. And a pH adjusting agent which is a diluted solution of inorganic acid are added and dispersed, and then crude diphenylmethane diisocyanate (product name: CR-200, manufactured by Mitsui Toatsu Chemicals, Inc.) and the same β-type hemihydrate gypsum as used in Example 1 (three Togypsum board company product) is added all at once, and the diameter is 70
A thickness of 12 after being stirred at 1000 rpm for 20 seconds with an agitator having a turbine blade with a diameter of mm, and immediately released from the entire surface.
mm, and the liquid was transferred to a 300 mm square base cup and molded and cured.

The slurry temperature at the initial stage of liquid transfer is 50 ° C. for the cured product number (Z1) and 2 for the cured product number (Z2) in Table 4.
Performed at 3 ° C.

Free foaming was carried out in a polycup under the same compounding conditions, and the cured foaming behavior characteristics were measured. As the measurement results at that time, the cream time, the rise time and the tact free tack time are shown in Table 4. It is displayed in the section of behavior result.

Molded products and free foam cured products are room temperature cured 3
After the time, secondary curing was carried out for 8 hours in a dryer at 75 ° C. to obtain foamed cured products (Z1) and (Z2) shown in Table 4. (Z1) and (Z2) obtained by free foaming have a thickness of 25 mm,
After cutting into square pieces with a base of 50 × 50 mm and measuring the bulk densities of the test pieces, respectively, compressive strength test, 10%
It was subjected to elasticity observation and water resistance test by compression for 5 hours of compression and the results are shown in Table 4.

Further, each of (Z1) and (Z2) obtained as a molded foam having a thickness of 12 mm has a size of 220 mm square and J
It was subjected to a surface combustion test in accordance with IS-A-1321, and the results are also shown in Table 4.

[0324]

[Table 1]

[0325]

[Table 2]

[0326]

[Table 3]

[0327]

[Table 4] Explanation of symbols and words in Tables 1 to 4 Silicon foam stabilizer L-5302; For urethane foam, which is a product of Nippon Yunika Co., Ltd., in which dimethylpolysiloxane having a hydroxyl value of about 30 and polyalkylene glycol are bonded in a block form. Silicon foam stabilizer L-5305; Silicon foam stabilizer for hard urethane foam manufactured by Nihon Unica Co., Ltd., which is a continuous foam stabilizer having a hydroxyl value of 375; Silicon foam stabilizer YY; 1
A dimethylpolysiloxane main chain type foamed foam having a weight average molecular weight in the range of 5 mole fraction, 0.51 mole fraction as ethylene oxide and 0.34 mole fraction as propylene oxide in the range of about 21,000. Agent Urethane catalyst Xl; Active ingredient concentration 70% obtained by mixing triethylenediamine, dimethylaminoethanol and N, N-dimethylbenzylamine in a weight ratio of 1: 1: 1.
Dioctylphthalate solution of urethane catalyst X2; dibutyltin dilaurate urethane catalyst X3; 2,4,6-tri (dimethylaminomethyl) phenol urethane catalyst X4; 1,8-diazobicyclo (5
4,0) -Undecene-7CR-200; Crude diphenylmethane diisocyanate type polyisocyanate [Mitsui Toatsu Chemicals] 20 ° C. viscosity 180 Cp CR-300; Crude diphenylmethane diisocyanate type polyisocyanate [Mitsui Toatsu Chemicals] 20 ° C.
Viscosity 245 cp β hemi-water / anhydrous gypsum; composite type calcined gypsum powder obtained by continuously calcining natural gypsum at 175 ° C., average particle diameter 12 μm, hemihydrate stone growth content: 78 wt%, 22 Wt as type III anhydrous gypsum
% Content αTCP powder; Meaning of α-type tricalcium phosphate powder Cream time; Foaming start time, and'is minutes, 'represents seconds Rise time; Foaming end time, and'is minutes,' is seconds Time; curing time until touch dry,
In addition, 'is minutes, second is 20 ℃ compressive fracture strength ・ x direction; applied stress value per unit area when compressive stress is applied in the vertical elongating direction, 20 ℃ compressive fracture Strength / y direction: Applied stress value per unit area at the time when fracture is observed when compressive stress is applied in the direction directly lateral to the embracing direction

[0328]

EFFECTS OF THE INVENTION In Comparative Example 1, the melamine-modified hard urethane foam modified with 1.5 mol of formaldehyde-added monomer to 1 mol of melamine obtained in Production Example 15 has a strong flammability and is a building product. It is clear that it does not pass the non-combustible characteristics of the flame retardant class 3 or higher.

Similarly, in Comparative Example 2 and Comparative Example 3, the composition of Comparative Example 1 contains 40% by weight of natural gypsum powder or aluminum hydroxide powder before curing. The foam of the mixed product with the non-hydrated inorganic aggregate showed a remarkable foam breaking phenomenon and hardening shrinkage in the hardening and foaming process, and had a high bulk specific gravity and did not form a lightweight foam.

Although the cause thereof is not clear, a thermosetting reaction produced by the action effect with polyisocyanate which is the other main curing agent due to the low introduction amount of the methylol group into the molecule of the melamine-based aminoplast resin. It is presumed that the initial structural viscosity of the composition is insufficiently increased and the inorganic aggregate is adversely affected,
In any case, even in a compounding example of adding 45% by weight of a known non-hydrating flame-retardant inorganic filler aid to the cured body composition,
It is clear that the product is heavy and does not satisfy the non-combustible property of building materials of Class 3 or higher.

Further, as is apparent from Comparative Example 4, in the organic-inorganic hybrid composite outside the scope of the present invention, even if a hydrated inorganic aggregate and an aminoplast resin-modified hard urethane resin obtained by adding high formaldehyde are added, Even if a multi-phase structure is formed, for example, the result of Experiment No. Y1 of Comparative Example 4 does not show the satisfactory non-combustible property of the present invention in the low inorganic aggregate phase region, and the result of Experiment No. Y2 of Comparative Example 4 is obtained. As is clear from the above, it is clear that the water resistance property and the weight saving property are not satisfied, and that it lacks elasticity because it cannot withstand 10% compression.

Comparative Example 5 is an example of a melamine resin precursor containing no norbornanediguanmine, but it was confirmed that a lightweight foam having good flame retardancy and water resistance, which is suitable for building materials, is produced. However, it lacked elasticity, and compression failure within 10% was recognized, and the problem of lack of elasticity was found.

The effects of the present invention are, as shown in Examples 1 to 3, 39.98 to 80% by weight of the effective resin component of the diguanamine-based polyvalent aminoplast resin precursor aqueous solution containing CTU guanamine as an essential raw material. %, 19.98 to 60% by weight of an organic polyisocyanate containing at least two or more isocyanate groups in one molecule, 0.01 to 3% by weight of a tertiary amine-based urethane-forming catalyst, and a silicon-based foam stabilizer. Agent and / or anionic surfactant foam stabilizer from 0.01 to
70 parts by weight of a rehydration-curable inorganic aggregate composed of one or a mixture of anhydrous gypsum, hemihydrate gypsum and α-tricalcium phosphate based on 100 parts by weight of an organic component consisting of 5% by weight. And 850 parts by weight, in the presence of water corresponding to 50 to 200 mol% of theoretical water necessary for rehydrating and hardening the inorganic aggregate, a thermosetting organic-inorganic obtained by mixing and reacting together By using a hybrid type flame-retardant foam composition, the single product (member) has excellent non-combustibility characteristics of class 3 or higher for flame-retardant building materials, and has a bulk specific gravity of 0.6.
It was confirmed that it was as light as 5 or less and had excellent compressive strength characteristics, elasticity and water resistance.

In particular, it is clear that the values of high compressibility up to the point of compressive failure in Table 2 are both hard and have excellent elasticity. In addition, from Table 3 of Example 3, a high elastic recovery property was observed in the result of measuring the permanent strain rate at the time of 10% compression, and it was revealed that the cured foam was obviously rich in elasticity. Furthermore, it is clear that the composite of the present invention can be basically obtained without going through a process such as forced drying, and it was also clarified that it can be easily shaped and used as a core member of a metal siding product.

Further, it has been clarified that the foam composition of the present invention has excellent adhesion to various inorganic surface plates, and that laminate building material products and sandwich type building material products for decorative steel plate surface materials can be manufactured easily and inexpensively. .

That is, in the foam composition of the present invention, a hydratable inorganic bone agent is obtained, which undergoes foam hardening at a low temperature in a short time, and basically does not require a dehydration step by forced drying after foam consolidation. It can be said that one of the advantages and characteristics of the present invention is that it can be handled in a closed system when hydrated, and as a result, it exhibits sufficient strength.

In particular, the diguanamine-based polyvalent aminoplast resin precursor substance constituting one component of the present invention can be preliminarily made into a solution, and the water component which is the medium thereof is almost 1: 1.
It can be said to be an extremely resource-saving foaming composition that can be effectively reflected in the cured composition by 00%. Also, as its effect,
As is clear from Examples 4 to 10, a building material product in which the organic-inorganic hybrid thermosetting foamed cured composition of the present invention is used as a backup core material or a sandwich core material sufficiently satisfies the object of the present invention. It was a core material. As an industrially rational manufacturing method, in Example 4, the organic polyisocyanate of the present invention is used as the liquid B, and the other batch components are used as the liquid A, which is easy and reproducible. It has been suggested that it is possible to continuously produce a flame-retardant foamed cured product, and it is widely proposed that it is a method that is industrially sufficiently compatible.

As described above, the present invention has been judged to be a material that has a high industrial value and can contribute to society as various members of a novel flame-retardant lightweight foam building material.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 25, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0110

[Correction method] Change

[Correction content]

[0110] Formula 2: -CH ₂ OR type _{3 :-( CH 2 CH 2 O)} n-R Formula _{4: - [CH 2 CH (} CH 3) O] n-R Formula 5: - CH ₂ SO ₃ M Formula 6: —CH ₂ —NH— Formula 7: —CH ₂ 0CH ₂ —NH— Formula 8: —CH ₂ —N (CH ₂ OR) — Formula 9: —CH ₂ 0CH ₂ —N (CH ₂ OR) — However, R in the formulas 2 to 9 is methyl, ethyl, butyl,
M represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, or an amine group or an ammonium group, respectively.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0131

[Correction method] Change

[Correction content]

By the way, the modification with the aliphatic alkyl ether having 1 to 4 carbon atoms means that a part of the methylol group of the precursor substance in the diguanamine-based aminoplast solution is
Methanol, ethanol, isopropyl alcohol, n
It is represented by the introduction of a so-called alkoxymethylol group obtained by reacting lower alcohols such as -butanol, n-propyl alcohol and t-butanol.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0132

[Correction method] Change

[Correction content]

The aliphatic alkyl ether having 1 to 4 carbon atoms is a group formed by adding ethylene oxide and / or propylene oxide to a part of the methylol group of diguanamine aminoplast, or polyethylene glycol or polypropylene. A group obtained by dehydration condensation of glycol is included, and a group modified with a so-called polyalkylene glycol ether, and other, ε-
A group formed by ring-opening addition of a cyclic lactam compound typified by caprolactam is also included herein. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 1, 1996

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 4

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 12

[Correction method] Change

[Correction content]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0053

[Correction method] Change

[Correction content]

Typical examples of the above-mentioned mono-ε-triazine compound include the following, for example, melamine, benzocarboguanamine, acetocarboguanamine, cyclohexylcarboguanamine, 1,2- or
Is 1,3- or 1,4-cyanocyclohexylmonog
Anamine or its isomer mixture, 5- or 6-nor
Bornecarboguanamine or a mixture of isomers thereof,
2,5- or 2,6-cyanonorbornene monocarbo
Guanamine or its isomer mixture, 5- or 6-no
Rubornane carboguanamine or its isomer mixture, etc.
And can be used alone or in combination of two or more.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0137

[Correction method] Change

[Correction content]

For example, inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, nitric acid and salts thereof, and organic acids include acetic acid, succinic acid, malic acid, oxalic acid, lactic acid, alkylbenzenesulfonic acid, alkylphosphine. Fonic acid, alkylphosphinic acid, alkali metal salts thereof, alkaline earth metal salts thereof, amine salts thereof, ammonium salt thereof and the like can be used.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0159

[Correction method] Change

[Correction content]

As the tertiary amine-based urethane-forming catalyst, any known one may be used without any particular limitation. Preferably, triethylenediamine, N, N, N ', N',
N'-pentamethyldipropylenetriamine, N, N,
N ', N', N'-pentamethyldiethylenetriamine, N, N, N ', N'-tetramethylhexamethylenediamine, bis (dimethylaminoethyl) ether, 2
-(N, N dimethylamino) -ethyl-3- (N, N dimethylamino) propyl ether, N, N'-dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, methylenebis (dimethylcyclohexyl) amine, triethylamine, N , N-dimethylacetylamine, N, N-dimethyldodecylamine, N, N-dimethylhexadecylamine, N, N, N ′, N′-tetramethyl-1,3-butanediamine, N, N-dimethylbenzyl Amine, morpholine, N-methylmorpholine, N
-Ethylmorpholine, N- (2-dimethylaminoethyl) morpholine, 4,4'-oxydiethylenedimorpholine, N, N'-dimethylpiperazine, N, N'-diethylpiperazine, N, -methyl-N'-dimethyl Amine ethyl piperazine, 2,4,6-tris (dimethylamido)
Nomethyl) phenol, tetramethylguanidine, 3-
Dimethylamino-N, N-dimethylpropionamide,
N, N, N ', N'-tetra (3-dimethylaminopropyl) methanediamine, N, N-dimethylaminoethanol, N, N, N', N'-tetramethyl-1,3-diamino-2- Propanol, N, N, N'-trimethylaminoethylethanolamine, 1,4-bis (2-hydroxypropyl) -2-methylpiperazine, 1- (2
-Hydroxypropyl) imidazole, 3,3-diamino-N-methylpropylamine, 1,8-diazobicyclo (5,4,0) -undecene-7, N-methyl-N-
It is preferable to use one kind or two or more kinds selected from hydroxyethylpiperazine and the like.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0160

[Correction method] Change

[Correction content]

Among them, triethylenediamine, 2,
4,6-tris (dimethylaminomethyl) phenol,
1,8-diazobicyclo (5,4,0) -undecene-
It is preferable to use one kind or two or more kinds selected from No. 7, and the initial curing reaction of the organic-inorganic hybrid flame-retardant foam composition of the present invention is strong and highly tough while carbon dioxide gas foaming in a short time. This is a highly preferable example because it forms a semi-hard urethane cured phase.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0216

[Correction method] Change

[Correction content]

[0216] As a preferable manufacturing method which has particularly good reproducibility and high productivity, rehydratable inorganic aggregate powder 10 is used.
A good method is to make the total amount of the organic component and water for rehydration to be 40 to 100 parts by weight based on 0 parts by weight, and the initial fluidity at the time of mixing the composition is smooth. Because it is secured in.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0233

[Correction method] Change

[Correction content]

In water dilution ratio measurement of DG-1 1: 1.
5 was a CTU guanamine-based aminoplast monomer solution. Production Example 2 3280 parts of a low meta 37% formalin solution containing 6% methanol in a reaction vessel and 4340 CTU guanamine.
And 3330 parts of water were charged, and 28 parts of a 20% aqueous solution of caustic soda was charged and stirred.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0242

[Correction method] Change

[Correction content]

Then, 2000 parts of M-1 and Production Example 2
As a result of simply blending 3000 parts of the DG-2 obtained in 1. at room temperature, the mixed aminoplast resin aqueous solution is a colorless and transparent diguanamine-based polyvalent aminoplast resin precursor to be DG-4 having a viscosity of 83 cps and a pure content of 50%. A solution was obtained.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0244

[Correction method] Change

[Correction content]

2500 parts of M-2 and DG obtained in Production Example 1
DG obtained by simply blending 2500 parts of -1 at room temperature
The diguanamine-based aminoplast resin precursor aqueous solution of No. 5 was colorless and transparent, had a viscosity of 145 cps and a pure content of 65%.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0246

[Correction method] Change

[Correction content]

Obtained from 2000 parts of M-3 and Production Example 1.
3000 parts of DG-1 is simply blended at room temperature to give a viscosity of 1
A diguanamine-based polyvalent fuminoplast resin precursor mixed solution of DG-6 having a pure content of 64% at 55 cps was obtained.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction item name] 0283

[Correction method] Change

[Correction content]

On the other hand, in a 2 liter beaker, the ND obtained in Preparative Example 15 was prepared in the same manner as shown in Experiment No. (F) of Table 2 of Example 2, except that the polyisocyanate component was the same.
To the 200 parts of G-10, 1 of the silicone foam stabilizer L-5305
Parts and urethanization catalyst X3: 2,4,6-tris (dimethy
2 parts of luaminomethyl) phenol , 1 part of X2: dibutyltin dilaurate, 540 parts of β-type hemihydrate gypsum powder (Blaine value is 5,800 cm 2 / g), and an isocyanate group content of 31% which is a polyisodianate component. 265 parts of Mitsui Toatsu Chemicals CR # 300 were collectively added and stirred at 600 rpm for 5 seconds with an agitator having a turbine blade with a diameter of 70 mm.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Name of item to be corrected] 0327

[Correction method] Change

[Correction content]

[0327]

[Table 4] Explanation of symbols and words in Tables 1 to 4 Silicon foam stabilizer L-5302; For urethane foam, which is a product of Nippon Yunika Co., Ltd., in which dimethylpolysiloxane having a hydroxyl value of about 30 and polyalkylene glycol are bonded in a block form. Silicon foam stabilizer. Silicon foam stabilizer L-5305; a silicone foam stabilizer for hard urethane foam manufactured by Nippon Yunika Co., Ltd., which is a continuous propelling foam stabilizer having a hydroxyl value of 375. Silicon foam stabilizer YY; 0.1 as dimethyl siloxane
A dimethylpolysiloxane main chain type foamed foam having a weight average molecular weight in the range of 5 mole fraction, 0.51 mole fraction as ethylene oxide and 0.34 mole fraction as propylene oxide in the range of about 21,000. Agent. Urethane catalyst Xl; active ingredient concentration 70% obtained by mixing triethylenediamine, dimethylaminoethanol and N, N-dimethylbenzylamine in a weight ratio of 1: 1: 1.
Dioctyl phthalate solution. Urethane- forming catalyst X2; dibutyltin dilaurate Urethane-forming catalyst X3; 2,4,6-tris (dimethylacetate)
Minomethyl) phenol urethane formation catalyst X4; 1,8- diazobicyclo (5,5)
4,0) -Undecene-7 CR-200; Crude diphenylmethane diisocyanate type polyisocyanate Mitsui Toatsu Chemical Co., Ltd. product
(Viscosity at 20 ° C. 180 cps) CR-300; crude diphenylmethane diisocyanate type polyisocyanate Mitsui Toatsu Chemical Co., Ltd. product
(Viscosity at 20 ° C. 245 cps) β hemihydrate / anhydrous gypsum; composite type calcined gypsum powder obtained by continuously calcining natural gypsum at 175 ° C., average particle size 12 μm, hemihydrate stone content: 78 wt%, as type III anhydrous gypsum 22 w
Contains t% . αTCP powder; Meaning of α-type tricalcium phosphate powder Cream time; Foaming start time, and'is minutes, ”is seconds rise time; Foaming end time, and'is minutes,” is seconds tack free time; Curing time until touch dry,
In addition, 'is minutes, and is seconds is 20 ℃ compressive fracture strength ・ x direction : vertical
Applied stress value per unit area at the time when fracture is observed when compressive stress is applied from above . 20 ° C compressive fracture strength ・ y direction : True at right angle
The applied stress value per unit area at the time when fracture was observed when compressive stress was applied from the side .

[Procedure Amendment 14]

[Document name to be amended] Statement

[Name of item to be corrected] 0332

[Correction method] Change

[Correction content]

In Comparative Example 5, 3,9-bis (3,5-
Diamino-6-ethyl-1,3,5-triazine)-
2,4,8,10-Tetraoxaspiro [5,5 ']-
It is an example of a melamine resin precursor that does not contain undecane (CTU guanamine), but it was confirmed that it produces a lightweight foam that has good flame retardancy and water resistance that are suitable for building material products, but lacks elasticity, A compressive failure of 10% or less was recognized, and a problem of a little lack of elasticity was found.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08G 18/08 NGN 18/18 NFV 18/22 NFW 18/32 NDR C08L 75/04 NFY // C08G 12/40 NCH (C08G 18/54 101: 00)

Claims (23)

[Claims] 1. An organic component comprising 39.98 to 80% by weight of an effective resin component of a diguanamine-based polyvalent aminoplast resin precursor aqueous solution represented by the following (A), and at least 2 isocyanate groups in one molecule. 19.98 to 60% by weight of an organic polyisocyanate having a ke, 0.01 to 3% by weight of a tertiary amine-based urethane-forming catalyst, and a silicone-based foam stabilizer and / or an anionic surface-active foam stabilizer of 0. 01
To 100 parts by weight of the organic component consisting of
70 to 850 parts by weight of a rehydration-hardenable inorganic aggregate comprising one or a mixture of anhydrous gypsum, hemihydrate gypsum and α-tricalcium phosphate, and the inorganic aggregate is rehydrated and hardened. A thermosetting organic-inorganic hybrid flame-retardant foam composition obtained by mixing and reacting in the presence of water corresponding to 50 to 200 mol% of theoretical water required for the reaction. (A) 3,9-bis (3,5-diamino-6-ethyl-1,3,5-triazine) -2 represented by the following formula 1
Total of polyvalent amino compounds consisting of 100 to 1 mol% of 4,8.10-tetraoxaspiro [5,5] -undecane and 0 to 99 mol% of mono-ε-triazine compound and / or urea or thiourea A diguanamine-based polyvalent aminoplast resin precursor aqueous solution containing 10 to 85% by weight of a monomer obtained by adding 2 to 8 mol of formaldehyde to 1 mol and / or an initial condensation product thereof. Embedded image 2. A diguanamine-based polyvalent aminoplast resin precursor is 3,9-bis (3,5-diamino-6-ethyl-1,3,5-triazine) -2,4,8.10-tetra 10-10 of oxaspiro [5,5] -undecane
0 to 90 mol% of the mono-ε-triazine compound and / or urea or thiourea, and 2 to 6 of formaldehyde based on 1 mol of the polyvalent amino compound.
1 to 50 mol% of a methylol group, which is a monomer and / or an initial condensate thereof obtained by adding moles, and is formed at that time.
The heat-resistant foam composition according to claim 1, wherein is a compound modified with an aliphatic alkyl ether of 1-4. 3. The flame-retardant foam according to claim 2, wherein the initial condensate is further reacted with sodium sulfite to sulfonate 0.6 to 15 mol% of the introduced methylol groups. Composition. 4. The mono-ε-triazine compound is one or more selected from the group consisting of melamine, benzocarboguanamine, acetocarboguanamine, cyclohexylcarboguanamine, norbornene benzoguanamine norbornane benzoguanamine. The flame-retardant foam composition according to claim 1. 5. The diguanamine-based polyvalent aminoplast resin precursor is an initial condensate, and in the water dilutability as a measure of the degree of condensation, the condensation solution: diluting water ratio is 1: 1.
The flame-retardant foam composition according to claim 1 or 4, wherein the flame-retardant foam composition is a product in which the condensation reaction has proceeded to 0.5 to 1: 5. 6. The diguanamine-based polyvalent aminoplast resin precursor aqueous solution (a) comprises an initial condensate aqueous solution at 20 ° C.
The flame-retardant foam composition according to any one of claims 1 to 5, wherein the viscosity of the aqueous solution is 500 cp or less. 7. A diguanamine-based polyvalent aminoplast resin precursor (a) prepared separately from the following (b) and (c):
And / or (d) mixture, or its initial cocondensate, or 0.6 to 15 mol% of its introduced methylol group
A flame-retardant foam composition according to any one of claims 1 to 6, which is a modified product obtained by further sulfonating. (B) 3,9-bis (3,5-diamino-6-ethyl-
1,3,5-triazine) -2,4,8.10-tetraoxaspiro [5,5] -undecane added to 1 mol of formaldehyde in an amount of 4 to 8 mol, resulting in a methylol group 1 to 50 mol% of the above is a monomer modified with an aliphatic alkyl ether having 1 to 5 carbon atoms and / or an initial condensate thereof. (C) 1.1 mol of formaldehyde to 1 mol of melamine
A monomer and / or an initial condensate thereof in which 1 to 50 mol% of the methylol group formed at that time is modified with an aliphatic alkyl ether having 1 to 5 carbon atoms. (D) 1.1 to 1% of formaldehyde to 1 mol of urea
A monomer obtained by adding 2.5 mol, wherein 1 to 35 mol% of the methylol group produced at that time is modified with an aliphatic alkyl ether having 1 to 5 carbon atoms, and / or an initial condensation product thereof. 8. A diguanamine-based polyvalent aminoplast resin precursor solution (a) having 1 free carbon atoms.
The flame-retardant foam composition according to any one of claims 1 to 7, wherein the amount of the aliphatic alkoxylating agent of to 5 is 5% by weight or less. 9. A diguanamine-based polyvalent aminoplast resin precursor aqueous solution (a), wherein the amount of the free aliphatic C 1-5 aliphatic alkoxylating agent is 1% by weight or less, and its 20 ° C. aqueous solution viscosity is The flame-retardant foam composition according to any one of claims 1 to 8, which is a transparent or semi-suspended aqueous solution of 300 cp or less. 10. As the organic polyisocyanate, one or more selected from the group consisting of diphenylmethane diisocyanate, tolylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, tetramethylene diisocyanate and norbornane diisocyanate are used. A flame-retardant foam composition according to any one of claims 1 to 9. 11. The flame-retardant foam composition according to any one of claims 1 to 10, wherein diphenylmethane diisocyanate and / or its polynuclear body or its polymer is used as the organic polyisocyanate. 12. A tertiary amine-based urethane-forming catalyst,
One or more selected from the group consisting of triethylenediamine, 2,4,6-tri (dimethylaminomethyl) phenol, and 1,8-diazobicyclo (5,4,0) -undecene-7. Claim 1 characterized by the above
No. 11, a flame-retardant foam composition. 13. The foam stabilizer is a silicon-based foam stabilizer, and the silicone-based foam stabilizer finally reacts with propylene oxide and / or ethylene oxide on active hydrogen in the molecule to finally form a polyalkylene glycol pendant group. It is a modified silicon compound having, and is 0.05 to 0.2 mole fraction as dimethyl siloxane, 0.3 to 0.8 mole fraction as ethylene oxide, and 0.3 to 0.8 mole fraction as propylene oxide. The flame-retardant foam composition according to any one of claims 1 to 12, characterized in that the weight average molecular weight thereof is in the range of 5,000 to 25,000. 14. The foam stabilizer is an alkali metal salt of an aliphatic monoalkyl polyalkylene glycol ether sulfonic acid having an alkyl group having 10 to 12 carbon atoms, and 8 carbon atoms.
The flame-retardant foam composition according to any one of claims 1 to 12, which is an anionic surfactant of any one of alkali metal salts of alkyl sulfonic acids of Nos. 15. The Blaine value of the inorganic aggregate is 2,000 to
The flame-retardant foam composition according to claim 1, which is β-type hemihydrate gypsum powder and / or α-type hemihydrate gypsum powder in a range of 7,000 cm ² / g. 16. The flame-retardant foam composition according to claim 1, having a bulk density in the range of 0.01 to 0.65. 17. The content ratio of dihydrate gypsum obtained by rehydrating hemihydrate gypsum in the foamed cured product composition is finally 60 to 85.
The content is in the range of wt%.
16. The flame-retardant foam composition according to any of 16. 18. One part selected from an organic tin compound, an organic lead compound and an organic cobalt compound as a urethanization promoter is added in an amount of 0.01 to 1 part by weight to 100 parts by weight of an organic component. The flame-retardant foam composition according to any one of claims 1 to 17. 19. During the urethane curing foaming reaction and the hydration curing reaction of the inorganic aggregate component, the diguanamine-based polyvalent aminoplast resin precursor aqueous solution and / or the entire mixed system is acidified to have a PH value of 3 or more and 6.9 or less. The thermosetting flame-retardant foam composition according to claim 1 or 18, characterized in that: 20. In the urethane curing foaming reaction and the hydration curing reaction of the inorganic aggregate component, the diguanamine-based polyvalent aminoplast resin precursor aqueous solution and / or the entire mixed system is made alkaline with a PH value of 8 or more and 12 or less. The flame-retardant foam composition according to claim 1 or 18. 21. 3,9-bis (3,5-diamino-6-ethyl-1,3,5-triazine) -2,4,8,10-tetraoxaspiro [5 represented by the following formula 1 ，
5] -Undecane in an amount of 100 to 1 mol% and a mono-ε-triazine compound and / or urea or thiourea in an amount of 0 to 9
10 to 85% by weight of a monomer obtained by adding 2 to 8 mol of formaldehyde and / or an initial condensate thereof to 1 mol in total of 9 mol% of a polyvalent amino compound. Embedded image Diguanamine-based polyvalent aminoplast resin precursor aqueous solution, tertiary amine urethanization catalyst and, if necessary, organometallic urethanization co-catalyst, silicon-based foam stabilizer and / or anionic surface-active foam stabilizer, and further inorganic From at least one or two or more selected from anhydrous gypsum, hemihydrate gypsum and α-tricalcium phosphate in the presence of water corresponding to 50 to 200 mol% of theoretical water necessary for rehydrating the aggregate. At the same time, a liquid A containing the rehydration-curable inorganic aggregate and a liquid B containing an organic polyisocyanate containing at least two isocyanate groups in one molecule are quantitatively supplied to the mixing tank. 21. High-speed stirring, mixing at room temperature to 40 [deg.] C. for 1 to 40 seconds, and then discharging the mixture to the outside of the mixing tank to cause a foaming and curing reaction into a certain shape. Method for producing Re or organic-inorganic hybrid fire 燃発 foam composition. 22. The surface material comprises any one of an inorganic fiber board, a steel plate, a cement board, and a gypsum board, and the organic-inorganic hybrid flame-retardant foam composition according to claim 1 is used as a backup core material. A composite building material panel characterized by doing. 23. The surface material is a steel plate, the back material is paper or aluminum foil laminated paper, and the organic-inorganic hybrid flame-retardant foam composition according to claim 1 is used as a core material. And sandwich building material panel.