JP6621571B1 - Foamable composition for nonflammable polyurethane foam - Google Patents

Abstract

Provide a foamable composition that can advantageously form a non-combustible polyurethane foam that synergistically enhances flame retardancy, and increases the degree of freedom in coloring without losing the color of the polyurethane resin itself. The present invention provides a foamable composition that can advantageously form a non-combustible polyurethane foam. In a foamable polyurethane foam composition comprising a composition A containing a polyol, a composition B containing a polyisocyanate, and a foaming agent, at least a trimerization catalyst is contained as a catalyst, and the organic metal salt of an organic phosphinic acid is as described above. At least one of the composition A and the composition B was allowed to be contained in a proportion of 30 parts by mass or more with respect to 50 parts by mass of the polyol.

Description

  The present invention relates to a foamable composition for a nonflammable polyurethane foam, and more particularly to a foamable composition for forming a polyurethane foam that advantageously satisfies the nonflammable characteristics defined in Japan's Building Standard Law.

  Conventionally, polyurethane foam has been used mainly as a heat insulating material by utilizing its excellent heat insulating properties, adhesive properties, lightness and other properties, such as heat insulating materials for interior and exterior walls and panels for construction, metal siding, electric refrigerators, etc. It is used for heat insulation, insulation of building walls, condominiums, refrigerated warehouses, etc., ceilings, roofs, etc., prevention of condensation, infusion pipes, etc. It is also practically used as a reinforcing material. Such polyurethane foam is generally a composition comprising a polyol compounded liquid (premixed liquid) in which a polyol is blended with a foaming agent and, if necessary, various auxiliary agents such as a catalyst, a foam stabilizer, and a flame retardant. A and a composition B containing polyisocyanate as a main component are mixed continuously or intermittently by a mixing device to obtain a foamable composition for polyurethane foam, which is a slab foaming method, an injection foaming method, a spray. It is manufactured by foaming and curing by a method such as a foaming method, a laminate continuous foaming method, a lightweight embankment method, and an injection backfilling method.

  By the way, the polyurethane foam formed as described above is required to have flame retardancy in view of its use. For this reason, a foamable composition for flame retardant polyurethane foam is proposed in which various flame retardants are blended. For example, in Japanese Patent Application Publication No. 2014-524955 (Patent Document 1), as a reactive formulation for producing a sprayable elastic polyurethane coating having improved flame retardant properties, isocyanate prepolymers are used. A reactive formulation comprising a polyisocyanate component comprising a polymer and any flame retardant compound and a polyol component comprising components such as aromatic polyester polyol, red phosphorus and catalyst, and further flame retardant is proposed, thereby It is clear that elastic polyurethane coatings with improved flammability properties can be formed. It has been in either. In addition, halogen-containing compounds, phosphates, inorganic fillers, antimony oxides, zinc, and the like are exemplified as flame retardant additives that can be further added and contained therein.

  Moreover, in Japanese translations of PCT publication No. 2014-532098 gazette (patent document 2), it is proposed to use a trialkyl phosphate as a smoke suppressant for polyurethane foam. That is, it has been clarified that a polyurethane foam having improved smoke suppression properties can be obtained. And, there is used a urethane catalyst or an isocyanate trimerization catalyst for the formation of polyurethane foam, and a metal inorganic filler for ease of processing, such as metal hydrate and zinc borate, It is clarified that zinc salts such as zinc stannate can be contained.

  Furthermore, in JP-A-2015-193839 (Patent Document 3), a predetermined amount of red phosphorus is blended as one of additives together with a polyol compound, a polyisocyanate compound, a trimerization catalyst, a foaming agent and a foam stabilizer. A flame retardant urethane resin composition has been clarified, and with the addition of a small amount of a flame retardant (red phosphorus), excellent flame retardancy can be expressed and handling is difficult. It has been shown that a flammable urethane resin composition can be provided. In addition, as one of the additives, the addition of a water-releasing substance such as metal hydroxide, crystal water-containing inorganic compound, clay mineral, etc. is essential, phosphate ester, phosphate-containing flame retardant It has been clarified that bromine-containing flame retardants and the like can be further blended as additives.

  However, among those patent documents, the flame retardant polyurethane coating obtained in Patent Document 1 and Patent Document 2 and the polyurethane foam with improved smoke suppression performance have severe flame retardance in recent years due to their flame retardant properties. It was not able to fully respond to the request for conversion. For example, the flame retardant polyurethane coating obtained in Patent Document 1 only reveals the characteristics of the coating layer having elasticity, and is a severe flame retardant characteristic required for polyurethane foam (foam). Furthermore, the polyurethane foam disclosed in Patent Document 2 is merely intended to improve smoke suppression performance, and has a more severe flame retardant performance. It was not possible to fully respond to the request concerning.

  In addition, red phosphorus used in Patent Document 1 and Patent Document 3 is an excellent flame retardant, but the amount used thereof is increased in order to increase the flame retardancy of the formed polyurethane foam. Then, there is a problem that the foam tends to burn easily, and since there is a risk of ignition in the red phosphorus itself, there is a problem that an accident is easily caused during the production of polyurethane foam, and its use At this time, there are problems such as poor handling. In addition, red phosphorus, as its name suggests, is purple-red. Therefore, when the entire resin (foam) is dyed red and colored with a colorant, the purpose is Therefore, there is a demand for avoiding the use of red phosphorus as much as possible.

By the way, in Japan's Building Standard Law, regarding fire resistance and fire prevention performance of materials, it is divided into flame retardant materials, quasi-incombustible materials and non-flammable materials, from flame retardant materials to quasi-incombustible materials, and further to incombustible materials, Although more severe fire-proof performance is required, the above-mentioned in order to give a high degree of flame retardancy to the foam material made of polyurethane foam obtained by reacting polyol and polyisocyanate and foaming. When a conventional flame retardant as disclosed in the publication is used, it has been difficult to satisfy the non-flammability performance of a non-flammable material that requires the most stringent fireproof performance. In particular, when it is heated at the characteristics required for the non-combustible material specified by the Building Standard Law, that is, radiant heat intensity: 50 kW / m ² , the total calorific value for 20 minutes after the start of heating is 8.0 MJ / In order to obtain non-flammable properties of m ² or less, when the blending amount of the above-mentioned known flame retardant is increased with respect to the foamable composition for polyurethane foam, the reaction between the polyol and the polyisocyanate is inhibited, Problems such as the inability to obtain the desired foam, deterioration of the physical or mechanical properties of the resulting foam, and limitations on the color of the foam are caused. It becomes like this.

According to the provisions of the Building Standards Act (Enforcement Ordinance, Article 1, Item 5), the incombustible material satisfies the total calorific value described above, and the maximum heat generation rate continues for more than 10 seconds. The polyurethane foam material formed by blending a conventional flame retardant is not to exceed 200 kW / m ² and has no cracks and holes penetrating to the back side, which are harmful to flameproofing. However, while ensuring the useful physical or mechanical properties as a polyurethane resin, it has not been able to sufficiently meet the demand for such incombustibility.

Special table 2014-524554 gazette Special table 2014-532098 gazette Japanese Patent Laid-Open No. 2015-193839

  Here, the present invention has been made in the background of such circumstances, and the problem to be solved is to advantageously form a non-flammable polyurethane foam having a synergistic increase in flame retardancy. The present invention provides a foamable composition that can advantageously form a non-combustible polyurethane foam with an increased degree of freedom in coloring without losing the color of the polyurethane resin itself. There is also.

  And in order to solve the above-mentioned subject, this invention can be favorably implemented in various modes as listed below. It should be understood that the aspects and technical features of the present invention are not limited to those described below, and can be recognized based on the inventive concept that can be grasped from the description of the specification. Should be.

(1) A composition A comprising a polyol and a composition B comprising a polyisocyanate, and a reaction between the polyol and the polyisocyanate,
A foamable composition in which a polyurethane foam is formed by foaming with a foaming agent, and the composition A contains at least a trimerization catalyst as a catalyst, and an organic phosphinic acid metal salt contains the polyol. The foamable composition for non-combustible polyurethane foam, which is contained in at least one of the composition A and the composition B in a ratio of 30 parts by mass or more with respect to 50 parts by mass of object.
(2) A composition A containing a polyol and a composition B containing a polyisocyanate, and a reaction between the polyol and the polyisocyanate,
A foamable composition in which a polyurethane foam is formed by foaming with a foaming agent, and the composition A contains at least a trimerization catalyst as a catalyst, and is also composed of an organic phosphinic acid metal salt and an organic phosphate ester. Are separately or together contained in at least one of the composition A and the composition B, and the organic phosphinic acid metal salt and the organic phosphate ester are added in the total amount to the polyol. The organic phosphinic acid metal salt is contained in a proportion of 30 parts by mass or more with respect to 50 parts by mass of the above, and the content of the organic phosphinic acid metal salt is 5 parts by mass or more with respect to 50 parts by mass of the polyol. A foamable composition for nonflammable polyurethane foams.
(3) The foamable composition for incombustible polyurethane foam according to the aspect (2), wherein the organic phosphate ester is selected from the group consisting of a monophosphate ester and a condensed phosphate ester.
(4) The organophosphate is tris (1-chloro-2-propyl)
Said aspect (2) or said aspect (characterized by being a phosphate)
The foamable composition for noncombustible polyurethane foams as described in 3).
(5) The organic phosphinic acid metal salt is composed of an organic phosphinic acid having a structure in which a methyl group, an ethyl group or a phenyl group is bonded to a phosphorus atom, and Mg, A
The salt for a nonflammable polyurethane foam according to any one of the above aspects (1) to (4), which is a salt with a metal selected from the group consisting of l, Ca, Ti and Zn Effervescent composition.
(6) The metal hydroxide is based on the composition A and / or the composition B.
The foamable composition for noncombustible polyurethane foam according to any one of the above aspects (1) to (5), further comprising:
(7) The trimerization catalyst is a quaternary ammonium salt, The foamable composition for nonflammable polyurethane foam according to any one of the above aspects (1) to (6) .
(8) The aspect (1) to the aspect (6), wherein a carboxylic acid alkali metal salt and a quaternary ammonium salt are used in combination as the trimerization catalyst. Foamable composition for non-combustible polyurethane foam.
(9) The foamable composition for incombustible polyurethane foam according to any one of the above aspects (1) to (8), wherein the polyol is an aromatic polyester polyol.
(10) The foamable composition for nonflammable polyurethane foam according to the aspect (9), wherein the aromatic polyester polyol is a phthalic polyester polyol.
(11) The aspect (1) to the aspect (10), wherein the foaming agent is an organic foaming agent selected from the group consisting of hydrocarbon, hydrofluoroolefin, and hydrochlorofluoroolefin.
The foamable composition for nonflammable polyurethane foams according to any one of (1).
(12) As the foaming agent, water is used together with hydrofluoroolefin or hydrofluorofluoroolefin, The nonflammable polymer according to any one of the above aspects (1) to (11), A foamable composition for urethane foam.
(13) When the polyurethane foam is heated at a radiant heat intensity of 50 kW / m ² in accordance with the heat generation test method specified in ISO-5660, the total calorific value for 20 minutes from the start of heating is 8 The foamable composition for a nonflammable polyurethane foam according to any one of the above embodiments (1) to (12), which has a nonflammable property of 0.0 MJ / m ² or less.

  Thus, in the foamable composition for nonflammable polyurethane foam according to the present invention, at least a trimerization catalyst is used as a reaction catalyst between a polyol and a polyisocyanate, and an organic phosphinic acid metal salt is used as a flame retardant. A single or a combination of an organic phosphinic acid metal salt and an organic phosphoric acid ester is added to and contained in at least one of the composition A containing a polyol and the composition B containing a polyisocyanate in a predetermined ratio. Therefore, in the presence of the isocyanurate structure introduced by such a trimerization catalyst, the synergistic flame retarding action by the organic phosphinic acid metal salt or both of the organic phosphinic acid metal salt and the organic phosphate ester is exhibited. The resulting polyurethane can be effectively expressed. Flame retardancy of Omu is obtained more are further enhanced, is the so that the non-combustibility of interest may be advantageously applied.

  In particular, in the polyurethane foam formed from such a foamable composition according to the present invention, the calorific value at the time of combustion can be effectively reduced, and it does not continue to burn even when ignited. This makes it possible to provide a polyurethane foam that is extremely incombustible and has high self-extinguishing properties.

  Moreover, in the foamable composition for incombustible polyurethane foam according to the present invention, the hue of polyurethane foam formed from such a foamable composition is not used as a flame retardant, since red phosphorus is not used. In addition to being able to be completely avoided from the influence of purple red inherent to red phosphorus, the organic phosphinic acid metal salt and organic phosphate ester used have no effect on the hue of the polyurethane foam formed. Therefore, the formed polyurethane foam can be advantageously colored in a desired hue by the colorant, and the degree of freedom in coloring the polyurethane foam can be effectively increased.

  Hereinafter, the foamable composition for nonflammable polyurethane foam according to the present invention will be described in detail, and the specific configuration thereof will be further clarified.

  First, the foamable composition for non-combustible polyurethane foam according to the present invention is composed of a composition A mainly containing a polyol and a composition B mainly containing a polyisocyanate, and with the reaction of these polyol and polyisocyanate, The foaming composition in which the desired polyurethane foam is formed by foaming with the foaming agent, but the polyol, which is the main component constituting the composition A used there, reacts with the polyisocyanate. Various known polyol compounds that produce polyurethane are used alone or in appropriate combination. In this case, polyether polyol, polyester polyol, or the like is preferably used as the polyol. Of course, in addition to these polyols, it is needless to say that various known polyol compounds such as polyolefin polyols, acrylic polyols, polymer polyols and the like can be used alone or in appropriate combination.

  Specifically, among such polyols, the polyether polyol is an alkylene for at least one initiator such as a polyhydric alcohol, a saccharide, an aliphatic amine, an aromatic amine, a phenol, and a Mannich condensation product. It is obtained by reacting an oxide. Here, examples of the alkylene oxide include propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and ethylene oxide. In addition, polyhydric alcohols as initiators include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc., and saccharides include sucrose, dextrose, sorbitol, etc. Furthermore, as aliphatic amines, there are alkanolamines such as diethanolamine and triethanolamine, polyamines such as ethylenediamine, etc., and aromatic amines include various methyl-substituted phenylenediamines collectively called tolylenediamine. In addition, derivatives in which a substituent such as methyl, ethyl, acetyl, benzoyl or the like is introduced into the amino group, 4,4′-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, Lid diamine and the like, as still yet phenols, bisphenol A, can be mentioned a novolak type phenolic resin. Examples of Mannich condensation products include Mannich condensation products obtained by subjecting phenols, aldehydes, and alkanolamines to a Mannich condensation reaction.

  Examples of polyester polyols include polyols of polyhydric alcohol-polycarboxylic acid condensation, and cyclic ester ring-opening polymerization. In this case, as the polyhydric alcohol, those described above can be used, and in particular, dihydric alcohols are preferably used. Examples of the polyvalent carboxylic acid include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, isophthalic acid, and anhydrides thereof. In addition, ε-caprolactone or the like is used as the cyclic ester.

  Among these, as the polyester polyol, it is preferable to use an aromatic polyester polyol from the viewpoint of flame retardancy and compatibility. Specifically, it is preferable to use a phthalic acid-based polyester polyol. It is also effective to combine two or more types of polyols. The phthalic polyester polyol includes phthalic acid, which is a condensate of phthalic acid, terephthalic acid, isophthalic acid and their anhydrides, and a dihydric alcohol such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol. A polyester polyol is preferably used. When such a phthalic polyester polyol is used, even when in-situ foaming is performed at a low temperature (about −10 ° C. to 5 ° C.), it is difficult for the foam to be peeled off from the building frame and the like. There exists an advantage which can obtain the rigid polyurethane foam which has a softness | flexibility of the grade which the process of the foam edge part after foaming is comparatively easy. In particular, when a hydrofluoroolefin-based foaming agent or a hydrochlorofluoroolefin-based foaming agent is contained, there is a feature that gives a composition having excellent storage stability.

  On the other hand, the polyisocyanate in the composition B is blended with the composition A and reacts with the polyol in the composition A to form a polyurethane (resin). It is an organic isocyanate compound having the above isocyanate group (NCO group), for example, aromatic polyisocyanate such as diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, polytolylene triisocyanate, xylylene diisocyanate, naphthalene diisocyanate, In addition to aliphatic polyisocyanates such as hexamethylene diisocyanate and cycloaliphatic polyisocyanates such as isophorone diisocyanate, urethane prepolymers having isocyanate groups at the molecular ends, polyisocyanates Isocyanurate modified product of over bets, it may be mentioned carbodiimide modified product or the like. These polyisocyanate compounds may be used alone or in combination of two or more. In general, polymethylene polyphenylene polyisocyanate (polymeric MDI) is preferably used from the viewpoints of reactivity, economy, and handling properties.

  In addition, the use ratio of the polyisocyanate in the composition B and the polyol in the composition A described above is appropriately determined depending on the type of foam to be formed (for example, polyurethane, polyisocyanurate). In general, the NCO / OH index (equivalent ratio) indicating the ratio of the isocyanate group (NCO) of the polyisocyanate to the hydroxyl group (OH) of the polyol is in the range of about 0.9 to 2.5. It will be determined appropriately.

  In the present invention, the composition A and the composition B as described above are mixed, reacted in the presence of the catalyst, foamed with a foaming agent, and hardened, thereby being hardened. A polyurethane foam will be formed, but as a catalyst used there, at least a trimerization catalyst, in other words, an isocyanate group possessed by polyisocyanate is reacted and trimerized to promote formation of an isocyanurate ring. The catalyst (isocyanurate-forming catalyst) is contained in the composition A. As the trimerization catalyst, various known catalysts can be appropriately selected and used. Preferably, quaternary ammonium salts, potassium octylate, potassium 2-ethylhexanoate, sodium acetate are used. Carboxylic acid alkali metal salts such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, nitrogen-containing aromatic compounds such as tris (dimethylaminopropyl) hexahydrotriazine; trimethylammonium salt, triethyl Examples thereof include tertiary ammonium salts such as ammonium salts and triphenylammonium salts. Of these, the use of a quaternary ammonium salt is preferable from the viewpoint of improving the flame retardancy, and among them, the combined use of a quaternary ammonium salt and a carboxylic acid alkali metal salt is more suitable for flame retardancy. This is particularly preferable from the viewpoint of improvement.

  Examples of quaternary ammonium groups (monovalent cations in which four organic groups are covalently bonded to a nitrogen atom) in the quaternary ammonium salt advantageously used here include tetramethylammonium, methyltriethylammonium, and ethyltrimethyl. Ammonium, propyltrimethylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, heptyltrimethylammonium, octyltrimethylammonium, nonyltrimethylammonium, decyltrimethylammonium, undecyltrimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, tetradecyl Trimethylammonium, heptadecyltrimethylammonium, hexadecyltrimethyl Aliphatic ammonium groups such as ruammonium, heptadecyltrimethylammonium and octadecyltrimethylammonium, hydroxyammonium such as (2-hydroxypropyl) trimethylammonium, hydroxyethyltrimethylammonium, trimethylaminoethoxyethanol and hydroxyethyl-2-hydroxypropyldimethylammonium Groups such as 1-methyl-1-azania-4-azabicyclo [2,2,2] octanium, 1,1-dimethyl-4-methylpiperidinium, 1-methylmorpholinium, 1-methylpiperidinium, etc. An alicyclic ammonium group etc. are mentioned. Among these, tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, butyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium are excellent in catalytic activity and are industrially available , Tetradecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, (2-hydroxypropyl) trimethylammonium, hydroxyethyltrimethylammonium, hydroxyethyl-2-hydroxypropyldimethylammonium, 1-methyl-1-azania-4-azabicyclo [2,2,2] octanium and 1,1-dimethyl-4-mes Quaternary ammonium groups such Rupiperijiniumu becomes possible and is preferably employed.

  Examples of the organic acid group or inorganic acid group that is a monovalent anion that forms an ion with a quaternary ammonium group and forms a quaternary ammonium salt include, for example, a formic acid group, an acetic acid group, and octylic acid. Group, oxalic acid group, malonic acid group, succinic acid group, glutaric acid group, adipic acid group, benzoic acid group, toluic acid group, ethylbenzoic acid group, methyl carbonate group, phenol group, alkylbenzenesulfonic acid group, toluenesulfonic acid group And organic acid groups such as benzenesulfonic acid group and phosphate ester group, and inorganic acid groups such as halogen group, hydroxyl group, hydrogen carbonate group, and carbonate group. Among these, formic acid groups, acetic acid groups, octylic acid groups, methyl carbonate groups, halogen groups, hydroxyl groups, hydrogen carbonate groups, and carbonate groups are preferably employed because of their excellent catalytic activity and industrial availability. .

  And as a catalyst which consists of a quaternary ammonium salt of the above structures, various things are marketed, for example, U-CAT 18X, U-CAT 2313 (made by San Apro Co., Ltd.), Kao Raiser No., etc. 410, Kao Riser No. 420 (manufactured by Kao Corporation).

  As described above, the amount of the trimerization catalyst used as one of the catalysts is 0 with respect to 50 parts by mass of the whole polyol in the composition A in order to effectively exhibit the function as the catalyst. .1 to 8 parts by mass, preferably 1 to 6 parts by mass. If the amount of the trimerization catalyst used is less than 0.1 parts by mass, the trimerization of the polyisocyanate cannot be realized sufficiently, and therefore it becomes difficult to sufficiently achieve the effect of improving flame retardancy. On the other hand, if the amount is more than 8 parts by mass, the reaction proceeds excessively and the solidification becomes faster, so that the spraying construction becomes difficult.

  And in this invention, it is also possible to use together the urethanization catalyst which is a resinification catalyst with this trimerization catalyst. Examples of the urethanization catalyst include dibutyltin dilaurate, bismuth octylate (bismuth 2-ethylhexylate), bismuth neodecanoate, bismuth neododecanoate, bismuth naphthenate and the like, and known ones such as lead naphthenate. I can do it.

  Further, the amount of the resinification catalyst used is preferably 0.1 to 5 parts by mass, preferably 50 to 5 parts by mass with respect to 50 parts by mass of the total polyol in the composition A, in order to effectively exhibit the function as the catalyst. Is selected within the range of 0.5 to 3 parts by mass. When the amount of the resinification catalyst used is less than 0.1 parts by mass, there is a problem that the resulting foam becomes sticky, dust or the like adheres to it, and the appearance deteriorates. There are problems such as poor workability due to stickiness of the droplets adhering to the surface. On the other hand, if the amount exceeds 5 parts by mass, heat generation becomes high during the resinification reaction, and yellowing of the foam causes abnormal appearance. The catalyst containing the quaternary ammonium salt contained in the droplets generated during foaming may deteriorate the working environment of the work site where spraying is being performed.

  Furthermore, in addition to the trimerization catalyst and resinification catalyst as described above, a known catalyst conventionally used in the production of polyurethane foam is appropriately selected as necessary, and a composition mainly comprising a polyol. It will be contained in the product A. For example, an amine-based catalyst can advantageously improve the initial foamability of polyurethane, and has the effect of lowering the overall density of the foam without changing the density difference between the skin layer and the core layer. The stickiness of the foam can be improved to prevent the deterioration of the appearance due to the adhesion of dust, etc., and the spray foaming method exhibits the characteristics that improve the deterioration of workability due to the stickiness of the droplets adhering to the floor etc. To do. And as such an amine catalyst, it is recommended to use a reactive amine compound having an OH group or an NH group in the chemical structure or a cyclic amine compound having a cyclic structure. By using it as a catalyst, odor can be further reduced.

  In addition, the reactive amine compound and cyclic amine compound used as such an amine catalyst can be appropriately selected from known urethanization catalysts. For example, as the reactive amine compound, 2, 4,6-tri (dimethylaminomethyl) phenol, tetramethylguanidine, N, N-dimethylaminoethanol, N, N-dimethylaminoethoxyethanol, ethoxylated hydroxylamine, 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-methyldipropylamine, N-methyl-N′-hydroxy It can be mentioned ethyl piperazine and the like. Examples of the cyclic amine compound include triethylenediamine, N, N′-dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, methylenebis (dimethylcyclohexyl) amine, N, N-dimethylbenzylamine, morpholine, and N-methyl. Morpholine, N-ethylmorpholine, N- (2-dimethylaminoethyl) morpholine, 4,4'-oxydiethylenedimorpholine, N, N'-diethylpiperazine, N, N'-dimethylpiperazine, N- And methyl-N′-dimethylaminoethylpiperazine, 1,8-diazobicyclo (5,4,0) -undecene-7, and the like.

  And the amount of the amine catalyst used as one of such catalysts is to effectively demonstrate its function as a catalyst, while reducing problems such as odor and deterioration of working environment, and effective foam characteristics. In order to obtain, in 50 mass parts of the whole polyol in a polyol composition, 0.1-7 mass parts, Preferably it is 0.2-3 mass parts, More preferably, in the range of 0.3-1 mass part. Will be selected. If the amount of the amine catalyst used is less than 0.1 parts by mass, it will be difficult to fully function as a catalyst, and the resulting foam will be sticky and dust will adhere, resulting in poor appearance. In addition, the spray foaming operation causes problems such as poor workability because the spray adhering to the floor or the like becomes sticky. Further, when the amount of the amine catalyst used is more than 7 parts by mass, the odor of the resulting polyurethane foam becomes remarkable, and the amine catalyst that volatilizes during foaming causes a problem that the spraying work environment deteriorates. It becomes like this. For this reason, it is preferable that the amount of the amine catalyst used is small in terms of odor.

  Moreover, in the present invention, the trimerization catalyst as described above is included in the composition A as at least one of the catalysts, and the polyol in the composition A and the polyisocyanate in the composition B are reacted. In addition to forming polyurethane, a flame retardant of a polyurethane foam to be formed by using an organic phosphinic acid metal salt as a flame retardant and containing it in at least one of composition A and composition B The properties can be increased synergistically, which can advantageously provide a polyurethane foam with a high degree of flame retardancy.

  By the way, in the organic phosphinic acid metal salt used here, one or two organic groups such as a linear alkyl group having 1 to 6 carbon atoms and a phenyl group are covalently bonded to the phosphorus atom constituting the phosphinic acid. Various types of known metals are ionically bonded to the organic phosphinic acid having the structure thus formed to form a salt form. In general, a phosphorus atom is bonded to a methyl group, an ethyl group or a phenyl group. The metal is preferably Mg, Al, Ca, Ti or Zn, and particularly preferably Al or Zn. Specifically, (mono or di) zinc methylphosphinate, (mono or di) zinc ethylphosphinate, (mono or di) zinc phenylphosphinate, (mono or di) aluminum methylphosphinate, (mono or di) Examples include aluminum ethylphosphinate and aluminum (mono or di) phenylphosphinate. Since these phosphinic acid metal salts are usually colorless or white powders, they can be advantageously used without impairing the colorability of the polyurethane foam.

  In addition, such an organic phosphinic acid metal salt needs to be used in a ratio of 30 parts by mass or more with respect to 50 parts by mass of the polyol in the composition A, and more preferably 35 parts by mass or more. Is preferably used at a ratio of 40 parts by mass or more. This is because if the amount of the organic phosphinic acid metal salt used is too small, it is difficult to sufficiently achieve the synergistic effect of flame retardancy. In addition, if the amount used is too large, the viscosity of the composition to which it is added increases, causing problems such as poor stirring, and also causes problems such as reduced workability. Generally, as the upper limit of the amount of the organic phosphinic acid metal salt, a proportion of 100 parts by mass or less, preferably 75 parts by mass or less, more preferably 50 parts by mass or less is generally employed with respect to 50 parts by mass of the polyol. It will be.

  Further, in the present invention, it is desirable that an organic phosphate ester is used in combination with the organic phosphinic acid metal salt as described above, and they are present in the foamable composition according to the present invention. The flame retardant properties of polyurethane foams formed from such foamable compositions can be further advantageously improved, and non-flammable polyurethane foams conforming to the non-flammable materials defined in the previous building code It will be formed advantageously. The organic phosphinic acid metal salt and the organic phosphate ester are contained separately or together in at least one of the composition A and the composition B described above.

  In addition, it does not specifically limit as organic phosphate ester used here, Well-known things, such as a monophosphate ester and condensed phosphate ester, can be used individually or in combination. This organophosphate ester acts as a viscosity reducing agent that can effectively lower the viscosity of a chemical solution (Composition A or Composition B) and can improve workability such as spraying.

  Specifically, among these organic phosphate esters, the monophosphate ester is not particularly limited. For example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, Triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate , Di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, methane Examples thereof include diphenyl phosphonate, diethyl phenylphosphonate, regilucinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, tris (1-chloro-2-propyl) phosphate, and the like.

  The condensed phosphate ester is not particularly limited. For example, trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.) ), Hydroquinone poly (2,6-xylyl) phosphate, and condensed phosphates such as condensates thereof. Furthermore, examples of commercially available condensed phosphate esters include resorcinol polyphenyl phosphate (CR-733S), bisphenol A polycresyl phosphate (CR-741), aromatic condensed phosphate ester (CR747), and resorcinol polyphenyl phosphate ( ADEKA Corporation ADK STAB PFR), bisphenol A polycresyl phosphate (FP-600, FP-700) and the like.

  Among the above, it is preferable to use a monophosphate ester because the effect of reducing the viscosity in the composition before curing and the effect of reducing the initial calorific value are high, and tris (1-chloro-2-propyl) is particularly preferable. More preferably, phosphate is used.

  And as the usage-amount of such an organic phosphate ester, in the total amount with the usage-amount of the organic phosphinic acid metal salt used simultaneously, it is 30 mass with respect to 50 mass parts of the polyol in the above-mentioned composition A. It is necessary to employ a ratio of at least 35 parts, and among them, it is desirable that a ratio of at least 35 parts by mass, more preferably at least 40 parts by mass be employed. Moreover, in the total amount of such an organic phosphinic acid metal salt and an organic phosphoric acid ester, the organic phosphinic acid metal salt needs to be configured to have a ratio of 5 parts by mass or more with respect to 50 parts by mass of the polyol. Yes, preferably 7 parts by mass or more, more preferably 10 parts by mass or more. In addition, if the total amount of the organic phosphinic acid metal salt and the organic phosphoric acid ester becomes too small or the amount of the organic phosphinic acid metal salt used becomes too small, the organic phosphinic acid metal salt and the organic phosphoric acid ester The flame retardancy improving effect due to the synergistic effect is not sufficiently achieved. On the other hand, if the amount of use is excessive, the catalytic effect for forming polyurethane foam is lowered, and problems such as foaming inhibition are caused. From these organic phosphinic acid metal salts and organic phosphoric acids. As the upper limit of the total amount of esters, a proportion of generally 180 parts by mass or less, preferably 150 parts by mass or less, more preferably 120 parts by mass or less, with respect to 50 parts by mass of the polyol is advantageously employed. Become.

  Furthermore, in the present invention, in addition to the use of the organic phosphinic acid metal salt as described above alone or in combination of the organic phosphinic acid metal salt and the organic phosphate ester, as one of the additives, a metal hydroxide is further provided. Can be incorporated into the composition A and / or the composition B described above, thereby further increasing the nonflammability of the polyurethane foam. Examples of such a metal hydroxide include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, Vanadium hydroxide, tin hydroxide and the like can be mentioned, and these can be blended into the composition A and / or the composition B alone or in combination of two or more. The amount of the metal hydroxide used is generally about 5 to 50 parts by mass, preferably 10 to 40 parts by mass with respect to 50 parts by mass of the polyol in the composition A. preferable.

  By the way, the composition A or the composition B constituting the foamable composition for incombustible polyurethane foam according to the present invention is foamed for foaming the polyurethane to be produced, in addition to the above-described blending components or components. Additives are added, and in addition, if necessary, various conventionally known auxiliaries such as known foam stabilizers and other flame retardants may be appropriately selected and added. Is possible.

  And as a foaming agent used here, well-known various non-fluorocarbon-type / fluorocarbon-type foaming agents can be appropriately selected. In particular, in the present invention, a non-fluorocarbon-based foaming agent ( And / or its source), and specifically, an organic foaming agent such as hydrocarbon (HC), hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO) or the like is contained.

  For example, among the blowing agents that can be used in the present invention, the hydrofluorocarbon (HFC) of the fluorocarbon blowing agent includes difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125). 1,1,1-trifluoroethane (HFC143a), 1,1,2,2-tetrafluoroethane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane ( HFC152a), 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3 Pentafluorobutane (HFC365mfc) and 1,1,1,2,2,3,4,5,5,5-decafluorope Tan (HFC4310mee), etc. can be mentioned.

  On the other hand, normal pentane, isopentane, cyclopentane, isobutane, etc. can be mentioned as hydrocarbon (HC) which is one of the non-fluorocarbon blowing agents preferably used in the present invention. Examples of the hydrofluoroolefin (HFO) include pentafluoropropene such as 1,2,3,3,3-pentafluoropropene (HFO1225ye), 1,3,3,3-tetrafluoropropene (HFO1234ze), Tetrafluoropropenes such as 2,3,3,3-tetrafluoropropene (HFO1234yf) and 1,2,3,3-tetrafluoropropene (HFO1234ye), and tris such as 3,3,3-trifluoropropene (HFO1243zf) Hexafluorobutene isomers such as fluoropropene, tetrafluorobutene (HFO1345), pentafluorobutene isomer (HFO1354), 1,1,1,4,4,4-hexafluoro-2-butene (HFO1336mzz) HFO1336), hepta Examples include fluorbutene isomers (HFO1327), heptafluoropentene isomers (HFO1447), octafluoropentene isomers (HFO1438), nonafluoropentene isomers (HFO1429), and the like. As HCFO), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), dichlorotrifluoropropene (HCFO1223) Etc. can be mentioned. In particular, these hydrofluoroolefins (HFO) and hydrochlorofluoroolefins (HCFO) are chemically unstable and therefore have a low global warming potential. Therefore, they are suitably used as environmentally friendly blowing agents. To get. And the water mentioned later will be advantageously used as a foaming agent with these hydrofluoro olefins (HFO) or hydrochlorofluoro olefins (HCFO).

  Furthermore, in the present invention, water as a foaming agent is advantageously used together with or in place of the above organic foaming agent. When such water is present in the composition A containing a polyol, when such composition A and the polyisocyanate-containing composition B are mixed and reacted, the water and the polyisocyanate are mixed. Since it reacts to generate carbon dioxide, the carbon dioxide can effectively contribute to foaming of the polyurethane formed by the reaction between the polyol and the polyisocyanate. Moreover, since the heat of reaction is generated during the generation of such carbon dioxide, the urethane foam can be obtained by effectively allowing the urethanization reaction and the isocyanuration reaction to proceed with the heat. The compressive strength of can be further increased. In addition, as usage-amount of this water, it is generally 0.1-5 mass parts with respect to 50 mass parts of the whole polyol in the composition A, Preferably it is a ratio of 0.5-3 mass parts. It is contained in the composition A. If the amount of water used is greater than 5 parts by mass, the strength of the polyurethane foam that is produced is reduced. This is because the urea bond produced by the reaction between water and polyisocyanate increases in the resin, and the polyisocyanate used for the isocyanuration reaction is consumed in the reaction with water, reducing the polyisocyanate in the reaction system. Because. On the other hand, when the amount used is less than 0.1 parts by mass, the effect as a foaming agent due to the use of water cannot be sufficiently obtained.

  Further, the foam stabilizer is used for uniformly adjusting the cell structure of the polyurethane foam, and here, a silicone-based one or a nonionic surfactant is suitably employed. Specific examples include polyoxyalkylene-modified dimethylpolysiloxane, polysiloxaneoxyalkylene copolymer, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, lauryl fatty acid ethylene oxide adduct, and the like. One type is used alone, or two or more types are used in combination. The blending amount of the foam stabilizer is appropriately determined according to the desired foam properties, the type of foam stabilizer to be used, etc., but it is 50 parts by mass of the total polyol in the composition A. On the other hand, it is selected in the range of 0.1 to 10 parts by mass, preferably 1 to 8 parts by mass.

  Then, when the composition A containing a polyol and the composition B containing a polyisocyanate obtained as described above are reacted in the presence of at least a trimerization catalyst and foamed and cured, it is known. The various polyurethane foam manufacturing methods can be appropriately employed. For example, a laminate in which a mixture of the composition A and the composition B is applied onto a face material and foamed and cured in a plate shape. Continuous foaming method, injection foaming method in which foaming and hardening is performed by filling and filling the space required for heat insulation such as electric refrigerators, the honeycomb structure of lightweight / high-strength boards, and voids generated during civil engineering work. Alternatively, the foamable composition according to the present invention is foamed and sprayed by a spray foaming method in which foam is sprayed and cured from a spray gun head of an in-situ foaming machine to a predetermined adherend (structure). Was allowed reduction aims at a polyurethane foam comprising high flame retardancy is imparted, it is to be the noncombustible defined by the previous building codes are advantageously formed.

  Hereinafter, some examples of the present invention will be shown, and the features of the present invention will be more specifically clarified by comparing with comparative examples. However, the present invention will be described by describing such examples. It goes without saying that it is not subject to any restrictions. In addition to the following examples, the present invention includes various modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the specific description described above. It should be understood that modifications, improvements, etc. can be made. Note that the percentages (%) and parts shown below are all expressed on a mass basis unless otherwise specified.

  Further, the density, maximum heat generation rate, total heat generation amount, residue state, and colorability of the polyurethane foam obtained in the following Examples and Comparative Examples were evaluated or measured as follows.

(1) Measurement of maximum heat generation rate and total calorific value A sample of a 100 mm × 100 mm × 50 mm corn calorimeter test was cut out from the heating element to be measured and conformed to the combustion test method specified in ISO-5660. Then, the maximum heat generation rate and the total heat generation amount when heated for 20 minutes at a radiant heat intensity of 50 kW / m ² are respectively measured. A case where the maximum heat generation rate is 200 kW / m ² or less and a case where the total heat generation amount is 8 MJ / m ² or less are regarded as acceptable.

(2) Measurement of density About the sample for the corn calorimeter test cut out from the foam, the dimensions thereof are measured using a caliper, while the mass is measured using an electronic balance. The density of the sample (foam) is calculated from the measured values.

(3) Evaluation of residue state When deformation or cracks reaching the back surface are observed in the test sample after completion of the test, which is obtained when a combustion test based on ISO-5660 is performed, “ If the deformation reaching the back surface is not recognized, it is evaluated as “◯”.

(4) Colorability evaluation 0.016 parts by mass of a predetermined coloring dye is added to each of the polyol compositions in each Example and each Comparative Example, and a colored foam (foamed foam) is produced according to the polyurethane foam production method described later. Body). Then, the hue of the obtained colored foam is compared with the hue of the colored foam obtained from the polyol composition containing no flame retardant (Comparative Example 8). On the other hand, when a difference is recognized, it is evaluated as “X”.

First, the following various raw materials were prepared as components used in the following Examples and Comparative Examples.
Polyol compound: Phthalic acid-based polyester polyol (Kawasaki Chemical Industry Co., Ltd.)
RFK505 manufactured by a formula company)
: Mannich polyether polyol (Daiichi Kogyo Seiyaku)
DK polyol 3776 manufactured by Corporation; hydroxyl value: 35
0 mgKOH / g, viscosity: 500 mPa · s / 25 ° C
)
Trimerization catalyst: Potassium octylate (Evonik Japan Co., Ltd. Da
bco K-15)
: Quaternary ammonium salt (Kao Riser No. manufactured by Kao Corporation
. 420)
Resinization catalyst: Bismuth octylate (Nippon Chemical Industry Co., Ltd.
5)
Flame retardant: Aluminum diethylphosphinate (Client Chemicals Co., Ltd.)
EXOLIT OP930, EXOLIT OP935 made by a type company
)
: Phosphate ester [TCPP: Tris (1-chloro-2-propyl
) Phosphate]
: Phosphate ester (polyphosphate ester: ADEKA Corporation
Decastab PFR)
: Red phosphorus (Nova Excel 140 manufactured by Rin Chemical Industry Co., Ltd.)
: Aluminum hydroxide (Nippon Light Metal Co., Ltd. B1403, average grain
(Diameter: 2μm)
Foaming agent: HCFO-1233zd (Honeywell 1-chloro-
3,3,3-trifluoropropene)
: HFC365mfc (SOLVAY 1,1,1,3,3-pe
Ntafluorobutane)
: HFC245fa (Central Glass Co., Ltd. 1,1,1,3
3-pentafluoropropane)
: Water Foam stabilizer: Silicone foam stabilizer (SH-1 manufactured by Toray Dow Corning Co., Ltd.)
93)
Dye: Red dye (OIL RED RR manufactured by Orient Chemical Co., Ltd.
)
: Blue dye (OIL BLUE 2 manufactured by Orient Chemical Co., Ltd.
N)
: Green dye (OIL GREEN manufactured by Orient Chemical Co., Ltd.)
502)

-Preparation of polyol composition (Composition A)-
Various raw materials prepared above, that is, polyol, trimerization catalyst, resinification catalyst, flame retardant, foaming agent, foam stabilizer and dye, in various combinations and blending ratios shown in Tables 1 to 3 below, Various polyol compositions according to Examples 1 to 12 and Comparative Examples 1 to 8 were prepared by mixing uniformly.

-Preparation of polyisocyanate composition (Composition B)-
Polymeric MDI (Wannate PM-130 manufactured by Wanhua Chemicals Japan Co., Ltd.) was prepared as a polyisocyanate, and composition B was composed only of this polyisocyanate.

-Production of polyurethane foam-
80 parts of the various polyol compositions (composition A) obtained above and 120 parts (mass ratio 1: 1.5) of the composition B consisting only of polyisocyanate were adjusted to a liquid temperature of 20 ° C., respectively. Then, it accommodated in the container made from a polypropylene of 300 capacity parts, and mixed for 10 seconds using the stirrer: TK homodisper (made by Primix Co., Ltd.). Thereafter, the mixed liquid was poured into a 2000 volume part polypropylene container and foamed and cured to obtain a desired foam.

  Then, using the various polyurethane foams thus obtained, the density, the maximum heat generation rate, the total heat generation amount, the state of the residue and the colorability were measured or evaluated, respectively, and the obtained results were respectively The results are summarized in Tables 1 to 3 below.

As is clear from the results of Tables 1 and 2, the foamable composition comprising a combination of the polyol composition (Composition A) and the polyisocyanate (Composition B) employed in Examples 1 to 12 according to the present invention. If it is a thing, in the combustion test method based on ISO-5660, while being able to obtain the polyurethane foam which has high flame retardance in which total calorific value (20 minutes) will be 8 MJ / m < ² > or less, a flame retardant It is recognized that the hue does not change depending on the color, and that a colored foam having the desired hue can be easily obtained by using a predetermined colored dye.

On the other hand, as is apparent from the results shown in Table 3, the amount of the organic phosphinic acid metal salt used as the flame retardant and the organic phosphinic acid as well as the case of Comparative Example 8 in which the flame retardant is not used. In the case of Comparative Examples 1 and 2 where the total amount of the metal salt and the organic phosphate ester is small, the total calorific value (20 minutes) is a value much larger than 8 MJ / m ² , and the polyurethane is a nonflammable material. It is recognized that foam formation is difficult. Further, even when the total amount of the organic phosphinic acid metal salt and the organic phosphoric acid ester is larger than the numerical value defined in the present invention, Comparative Example 3 in which the amount of the organic phosphinic acid metal salt is small is used. In the case of Comparative Example 4, the effect of improving flame retardancy is not sufficient, and even in the case of Comparative Example 5 in which only an organic phosphate ester is blended as a flame retardant, as a non-flammable material It is clear that the total calorific value (20 minutes) that satisfies the above criteria cannot be satisfied. In addition, when forming polyurethane foam, in the case of Comparative Example 6 using only the resinification catalyst without using the trimerization catalyst, the curing of the foam does not proceed sufficiently. As a result, it was impossible to obtain a sample that could be subjected to a test based on ISO-5660. Furthermore, in the case of Comparative Example 7 in which red phosphorus is used as a flame retardant and an organic phosphate is used in combination therewith, although the total calorific value (20 minutes) is satisfied, a coloring test is performed. It was clarified that the colored foam obtained by using the blue dye or the green dye cannot achieve the original blue or green hue and is limited in the degree of freedom of coloring. .

Claims (11)

It is composed of a composition A containing a polyol and a composition B containing a polyisocyanate, and a polyurethane foam is formed by the reaction between the polyol and the polyisocyanate and foaming with a foaming agent . No foamable composition,
The composition A contains a phthalic polyester polyol as the polyol, and further contains at least a trimerization catalyst as a catalyst, and the organic phosphinic acid metal salt is contained in 50 parts by mass of the polyol. A foamable composition for nonflammable polyurethane foam, which is contained in at least one of the composition A and the composition B in a proportion of 30 parts by mass or more. It is composed of a composition A containing a polyol and a composition B containing a polyisocyanate, and a polyurethane foam is formed by the reaction between the polyol and the polyisocyanate and foaming with a foaming agent . No foamable composition,
The composition A contains a phthalic acid-based polyester polyol as the polyol, and further contains at least a trimerization catalyst as a catalyst, and an organic phosphinic acid metal salt and an organic phosphate ester separately or together. The organic phosphinic acid metal salt and the organic phosphoric acid ester are contained in at least one of the composition A and the composition B, and the total amount of the organic phosphinic acid metal salt and the organic phosphoric acid ester is 30 masses with respect to 50 mass parts of the polyol. Foam for nonflammable polyurethane foam, characterized in that it is contained in a proportion of at least parts and the content of the organic phosphinic acid metal salt is 5 parts by mass or more with respect to 50 parts by mass of the polyol Sex composition.   The foamable composition for nonflammable polyurethane foam according to claim 2, wherein the organic phosphate ester is selected from the group consisting of a monophosphate ester and a condensed phosphate ester.   The foamable composition for nonflammable polyurethane foam according to claim 2 or 3, wherein the organic phosphate is tris (1-chloro-2-propyl) phosphate.   An organic phosphinic acid having a structure in which a methyl group, an ethyl group, or a phenyl group is bonded to a phosphorus atom; and a metal selected from the group consisting of Mg, Al, Ca, Ti, and Zn. The foamable composition for noncombustible polyurethane foam according to any one of claims 1 to 4, wherein the foamable composition is a salt of the following.   The metal hydroxide is further contained with respect to the composition A and / or the composition B. 6. The nonflammable polyurethane foam according to any one of claims 1 to 5, Effervescent composition.   The foamable composition for nonflammable polyurethane foam according to any one of claims 1 to 6, wherein the trimerization catalyst is a quaternary ammonium salt.   The foamable composition for nonflammable polyurethane foam according to any one of claims 1 to 6, wherein an alkali metal carboxylate and a quaternary ammonium salt are used in combination as the trimerization catalyst. object. The nonflammability according to any one of claims 1 to 8 , wherein the foaming agent is an organic foaming agent selected from the group consisting of hydrocarbon, hydrofluoroolefin, and hydrochlorofluoroolefin. A foamable composition for polyurethane foam. The foamable composition for nonflammable polyurethane foam according to any one of claims 1 to 9 , wherein water is used as the foaming agent together with hydrofluoroolefin or hydrochlorofluoroolefin. When the polyurethane foam is heated at a radiant heat intensity of 50 kW / m ² in accordance with the exothermic test method specified in ISO-5660, the total calorific value for 20 minutes from the start of heating is 8.0 MJ / incombustible polyurethane foam for foam composition according to any one of claims 1 to 10, characterized in that it has a non-combustible characteristics is m ² or less.