JP7034020B2 - Effervescent composition for flame-retardant polyurethane foam - Google Patents

Description

The present invention relates to a foamable composition for flame-retardant polyurethane foam, and more particularly to a foamable composition for forming a polyurethane foam having excellent flame retardancy.

Conventionally, polyurethane foam has been mainly used as a heat insulating material for heat insulating materials such as interior and exterior wall materials for buildings, heat insulation of panels, metal siding, electric refrigerators, etc. by utilizing its excellent heat insulating properties, adhesiveness, and light weight. It is used for heat insulation, heat insulation of building walls, ceilings, roofs, etc. of buildings, apartments, frozen warehouses, etc. and prevention of dew condensation, heat insulation of infusion pipes, etc. It is also practically used as a reinforcing material and the like. Further, such a polyurethane foam is generally composed of a polyol compounding solution (premixed solution) in which a polyol is mixed with a foaming agent and, if necessary, various auxiliaries such as a catalyst, a foam stabilizer and a flame retardant. A and composition B containing polyisocyanate as a main component are continuously or intermittently mixed by a mixing device to obtain a foamable composition for polyurethane foam, which is obtained by a slab foaming method, an injection foaming method, or a spray. It is manufactured by foaming and curing by a method such as a foaming method, a laminated continuous foaming method, a lightweight filling method, and an injection backfilling method.

By the way, the polyurethane foam formed as described above is required to have flame retardancy due to its use, and therefore, in Japanese Patent Application Laid-Open No. 2014-524954 (Patent Document 1), improved flame retardancy characteristics are required. Polyisocyanate components, including isocyanate prepolymers and any flame retardant compounds, as well as aromatic polyester polyols, red phosphorus and catalysts, and additional Reactive formulations consisting of polyol components containing components such as flame retardants have been proposed, which have been shown to be able to form elastic polyurethane coatings with improved flammability properties. In addition, as flame-retardant additives further added and contained, halogen-containing compounds, phosphates, inorganic fillers, antimony oxide, zinc tinate and the like are exemplified therein.

Further, in Japanese Patent Application Laid-Open No. 2014-532098 (Patent Document 2), it is proposed to use trialkyl phosphate as a smoke suppressant for polyurethane foam, whereby smoke is remarkably generated when burned. That is, it has been clarified that a polyurethane foam having improved smoke suppression properties can be obtained. Then, a urethane catalyst or a triglyceride catalyst of isocyanate is used for forming the polyurethane foam, and a metal-based inorganic filler for ease of processing, for example, metal hydrate or zinc borate, is used. It has been clarified that it can contain zinc salts such as zinc tinate.

However, the flame-retardant polyurethane coatings and polyurethane foams with improved smoke emission suppression performance obtained in these patent documents cannot sufficiently meet the strict flame-retardant demands of recent years in terms of their flame-retardant characteristics. It was. For example, the flame-retardant polyurethane coating obtained in Patent Document 1 merely clarifies the characteristics of an elastic coating layer, and has severe flame-retardant characteristics required for polyurethane foam (foam). Further, even in the polyurethane foam disclosed in Patent Document 2, the purpose is merely to improve the smoke emission suppressing performance, and the flame retardant performance is stricter. It was not possible to fully respond to the request related to.

Japanese Patent Publication No. 2014-524954 Special Table 2014-532098 Gazette

Here, the present invention has been made in the background of such circumstances, and the problem to be solved thereof is to advantageously form a highly flame-retardant polyurethane foam having synergistically enhanced flame-retardant properties. It is also an object of the present invention to provide an effervescent composition which can be used, and also to provide an effervescent composition which can advantageously form a polyurethane foam having a low calorific value and a high residual carbon content.

The present invention can be suitably carried out in various aspects as listed below in order to solve the above-mentioned problems. It is understood that the aspects or technical features of the present invention are not limited to those described below and can be recognized based on the invention idea that can be grasped from the description of the specification. Should be.

(1) A foamable composition comprising a composition A containing a polyol and a composition B containing a polyisocyanate, which gives a polyurethane foam by foaming with a foaming agent together with the reaction between the polyol and the polyisocyanate. The composition A contains at least a trimerization catalyst as a catalyst, and red phosphorus and a metal tinic acid salt are used in combination, and they are used together or separately of the composition A and the composition B. A foamable composition for flame-retardant polyurethane foam, characterized in that it is contained in at least one of them.
(2) The foamable composition for a flame-retardant polyurethane foam according to the above aspect (1), wherein the tin metal salt is zinc tin sulfate.
(3) The embodiment (1) or the embodiment (1), wherein the red phosphorus is used in a ratio of 5 to 60 parts by mass with respect to 100 parts by mass of the polyol in the composition A.
The effervescent composition for flame-retardant polyurethane foam according to 2).
(4) The embodiments (1) to (3), wherein the tin metal salt is used in a ratio of 5 to 60 parts by mass with respect to 100 parts by mass of the polyol in the composition A. ). The effervescent composition for flame-retardant polyurethane foam according to any one of.
(5) The foamable assembly for flame-retardant polyurethane foam according to any one of the above-mentioned embodiments (1) to (4), wherein the quantification catalyst is a quaternary ammonium salt. thing.
(6) The above-described one of the above-described embodiments (1) to (4), wherein a carboxylic acid alkali metal salt and a quaternary ammonium salt are used in combination as the trimerization catalyst. Foamable composition for flame-retardant polyurethane foam.
(7) The effervescent composition for a flame-retardant polyurethane foam according to any one of the above-described embodiments (1) to (6), wherein the polyol is an aromatic polyester polyol. ..
(8) The foamable composition for flame-retardant polyurethane foam according to the above aspect (7), wherein the aromatic polyester polyol is a phthalic acid polyester polyol.
(9) The flame retardant according to any one of the above aspects (1) to (8), wherein the phosphoric acid ester is further contained in the composition A or the composition B. Foamable composition for sex polyurethane foam.
(10) The difficulty according to any one of the above-described embodiments (1) to (9), wherein the metal hydroxide is further contained in the composition A or the composition B. Foamable composition for flammable polyurethane foam.
(11) The above-mentioned embodiment (1) No. 1-mentioned above-mentioned embodiment, characterized in that a polyurethane foam having a total calorific value of 8 MJ / m ² or less obtained by measurement according to the ISO-5660 test method is provided. The foamable assembly for flame-retardant polyurethane foam according to any one of 10).

As described above, in the effervescent composition for flame-retardant polyurethane foam according to the present invention, at least a trimerization catalyst is used as a reaction catalyst between the polyol and polyisocyanate, and red phosphorus and succinic acid are used as flame retardants. The isocyanurate structure introduced by the trimerization catalyst from the place where it is added and contained in at least one of the composition A containing a polyol and the composition B containing a polyisocyanate in combination with a metal salt. In the presence of, the synergistic flame retardant action of both red phosphorus and the isocyanate metal salt can be effectively exhibited, which further enhances the flame retardancy of the obtained polyurethane foam. It was possible to be.

In particular, in a polyurethane foam formed from such an effervescent composition according to the present invention, the calorific value at the time of combustion can be effectively reduced, and even if ignited, it does not continue to burn and remains high. It is possible to provide a charcoal ratio, which makes it possible to advantageously provide a polyurethane foam that is extremely difficult to burn and has improved self-extinguishing properties.

Hereinafter, the effervescent composition for a flame-retardant polyurethane foam according to the present invention will be described in detail, and a specific configuration thereof will be further clarified.

First, the effervescent composition for flame-retardant polyurethane foam according to the present invention is composed of a composition A containing a polyol as a main component and a composition B containing a polyisocyanate as a main component, and together with the reaction between the polyol and the polyisocyanate. , A foamable composition in which the target polyurethane foam is formed by foaming with a foaming agent. The polyol, which is the main component constituting the composition A used therein, reacts with polyisocyanate. Various known polyol compounds that yield polyurethane are used alone or in combination as appropriate. Then, a polyether polyol, a polyester polyol, or the like is preferably used there. Of course, in addition to these polyols, it goes without saying that various known polyol compounds such as polyolefin-based polyols, acrylic-based polyols, polymer polyols and the like can be used alone or in combination as appropriate. ..

Specifically, among such polyols, the polyether polyol is used as an initiator for at least one of polyhydric alcohols, saccharides, aliphatic amines, aromatic amines, phenols, Mannig condensates and the like, and alkylene oxides. It is obtained by reacting. Therefore, examples of the alkylene oxide include propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, ethylene oxide and the like. In addition, polyhydric alcohols as initiators include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like, and sugars include sucrose, dextrose, sorbitol and the like. Further, as the aliphatic amine, there are alkanolamines such as diethanolamine and triethanolamine, polyamines such as ethylenediamine and the like, and as aromatic amines, various methyl substituents of phenylenediamine collectively referred to as tolylenediamine. Other examples include derivatives in which substituents such as methyl, ethyl, acetyl and benzoyl are introduced into the amino group, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine and the like. Further, examples of the phenols include bisphenol A, novolak type phenol resin and the like. In addition, examples of the Mannich condensation product include a Mannich condensation product obtained by subjecting phenols, aldehydes, and alkanolamines to a Mannich condensation reaction.

Examples of the polyester polyol include a polyhydric alcohol-polyvalent carboxylic acid condensation system polyol, a cyclic ester ring-opening polymerization system polyol, and the like. Here, 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. Further, as the cyclic ester, ε-caprolactone or the like will be used.

Among them, as the polyester polyol, it is preferable to use an aromatic polyester polyol from the viewpoint of flame retardancy and compatibility, and specifically, it is preferable to use a phthalic acid polyester polyol, and further, such a polyester. It is also effective to combine two or more types of polyols. The phthalic acid-based polyester polyol is a phthalic acid composed of a condensate of phthalic acid, terephthalic acid, isophthalic acid and their anhydrides and dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol. A polyester polyol is preferably used. When such a phthalic acid-based polyester polyol is used, even when on-site foaming is performed at a low temperature (about -10 ° C to 5 ° C), the generated foam is less likely to be peeled off from the building frame or the like, and further on-site. There is an advantage that it is possible to obtain a rigid polyurethane foam having flexibility to a extent that the treatment of the foam end portion after foaming is relatively easy. In particular, when a hydrofluoroolefin-based foaming agent or a hydrochlorofluoroolefin-based foaming agent is contained, the composition is characterized by 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), and two in the molecule. Organic isocyanate compounds having the above isocyanate groups (NCO groups), for example, aromatic polyisocyanates such as diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, polytolylene triisocyanate, xylylene diisocyanate, naphthalene diisocyanate, etc. In addition to aliphatic polyisocyanates such as hexamethylene diisocyanate and alicyclic polyisocyanates such as isophorone diisocyanate, urethane prepolymers having an isocyanate group at the molecular terminal, isocyanurate-modified polyisocyanates, carbodiimide-modified products and the like can be mentioned. I can. 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 viewpoint of reactivity, economy, handleability and the like.

The ratio of the polyisocyanate in the composition B to the polyol in the composition A described above will be appropriately determined depending on the type of foam to be formed (for example, polyurethane or polyisocyanurate). However, 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 decided appropriately.

Then, in the present invention, the composition A and the composition B as described above are mixed and reacted in the presence of a catalyst, and are foamed by a foaming agent and cured to be a hard polyurethane. Foam will be formed, and as the catalyst used there, at least a trimerization catalyst, in other words, a catalyst that reacts with the isocyanate group of polyisocyanate to tritrate it and promotes the formation of an isocyanurate ring. (Isocyanurate-forming catalyst) will be contained in the composition A. As the trimerization catalyst, various known catalysts can be appropriately selected and used, but a quaternary ammonium salt, potassium octylate, potassium 2-ethylhexanoate, sodium acetate are preferable. Carboxylic acid alkali metal salts such as; nitrogen-containing aromatic compounds such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, tris (dimethylaminopropyl) hexahydrotriazine; trimethylammonium salt, triethyl Examples thereof include tertiary ammonium salts such as ammonium salts and triphenylammonium salts. Of these, it is preferable to use a quaternary ammonium salt from the viewpoint of improving flame retardancy, and above all, it is preferable to use a quaternary ammonium salt and a carboxylic acid alkali metal salt in combination to improve the flame retardancy. It is particularly preferable from the viewpoint of improvement.

Examples of the quaternary ammonium salt advantageously used here include tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, heptyltrimethylammonium, and octyltrimethylammonium. Aliphatic ammonium such as nonyltrimethylammonium, decyltrimethylammonium, undecyltrimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, tetradecyltrimethylammonium, heptadecyltrimethylammonium, hexadecyltrimethylammonium, heptadecyltrimethylammonium, octadecyltrimethylammonium, etc. Compounds, hydroxyammonium compounds such as (2-hydroxypropyl) trimethylammonium, hydroxyethyltrimethylammonium, trimethylaminoethoxyethanol, hydroxyethyl-2-hydroxypropyldimethylammonium, 1-methyl-1-azania-4-azabicyclo [2, 2,2] Examples thereof include alicyclic ammonium compounds such as octanium, 1,1-dimethyl-4-methylpiperidinium, 1-methylmorpholinium, and 1-methylpiperidinium. Among these, tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, butyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium, because of their excellent catalytic activity and industrial availability, 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-methylpiperidinium will be preferably used.

Examples of the organic acid group or inorganic acid group constituting such a quaternary ammonium salt include formic acid group, acetic acid group, octyl acid group, oxalic acid group, malonic acid group, succinic acid group and glutaric acid group. Organic acid groups such as adipic acid group, benzoic acid group, toluic acid group, ethyl benzoic acid group, methyl carbonate group, phenol group, alkylbenzene sulfonic acid group, toluene sulfonic acid group, benzene sulfonic acid group, phosphoric acid ester group, etc. Examples thereof include inorganic acid groups such as halogen groups, hydroxyl groups, hydrogen carbonate groups and carbon dioxide groups. Among these, a formic acid group, an acetic acid group, an octylate group, a methyl carbonate group, a halogen group, a hydroxyl group, a hydrogen carbonate group and a carbonic acid group are preferable because they have excellent catalytic activity and are industrially available.

Further, as a catalyst composed of such a quaternary ammonium salt, various catalysts are commercially available. For example, U-CAT 18X, U-CAT 2313 (manufactured by Sun Appro Co., Ltd.), Kaorizer No. 410, Kao Riser No. 420 (manufactured by Kao Corporation) and the like can be mentioned.

As described above, the amount of the trimerization catalyst used as one of the catalysts is 0 with respect to 100 parts by mass of the entire polyol in the composition A in order to effectively exert the function as the catalyst. It will be selected within the range of 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 polyisocyanate cannot be sufficiently realized, and therefore it becomes difficult to sufficiently achieve the effect of improving flame retardancy. On the other hand, if the amount exceeds 8 parts by mass, the reaction proceeds too much and the solidification becomes faster, which makes spraying work difficult.

Further, in the present invention, it is also possible to use a urethanization catalyst, which is a resinification catalyst, in combination with such a quantification catalyst. Examples of the urethanization catalyst include known fatty acid bismuth salts such as dibutyltin dilaurate, bismuth octylate (bismuth 2-ethylhexylate), bismuth neodecanoate, bismuth neododecanoate, and bismuth naphthenate, and lead naphthenate. I can.

The amount of the resinification catalyst used is 0.1 to 5 parts by mass, preferably 0 with respect to 100 parts by mass of the entire polyol in the composition A in order to effectively exert its function as a catalyst. It will be selected within the range of .5 to 3 parts by mass. If the amount of this resinification catalyst used is less than 0.1 parts by mass, the obtained foam may become sticky, dust or the like may adhere to the resin, resulting in a poor appearance. In the spray foaming operation, the floor or the like may be used. Since the droplets adhering to the salt become sticky, there is a problem that workability deteriorates. On the other hand, if the amount exceeds 5 parts by mass, heat generation increases during the resinification reaction, and the appearance is abnormal such as yellowing of the foam. The catalyst containing the quaternary ammonium salt contained in the droplets generated during foaming may worsen the work environment at the work site where the spraying work is performed.

Further, in addition to the above-mentioned quantification catalyst and resinification catalyst, if necessary, a known catalyst conventionally used in the production of polyurethane foam is appropriately selected to have a composition containing a polyol as a main component. It will be contained in the thing A. For example, an amine-based catalyst can advantageously improve the initial foamability of polyurethane, and also has the effect of reducing the overall density of the foam without changing the density difference between the skin layer and the core layer, and further. The stickiness of the foam can be improved to advantageously prevent the deterioration of the appearance due to the adhesion of dust, etc., and in the spray foaming method, the feature of improving the deterioration of workability due to the stickiness of the droplets adhering to the floor, etc. is exhibited. It is something to do. As such an amine-based 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. Among them, the reactive amine compound is recommended. By using it as a catalyst, the odor can be further reduced.

The reactive amine compound or cyclic amine compound used as such an amine-based catalyst can be appropriately selected from known urethanization catalysts. For example, the reactive amine compound includes 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'-hydroxyethylpiperazine 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'-oxydiethylenedimorpholin, N, N'-diethylpiperazine, N, N'-dimethylpiperazine, N- Methyl-N'-dimethylaminoethylpiperazine, 1,8-diazobicyclo (5,4,0) -undecene-7 and the like can be mentioned.

As for the amount of the amine-based catalyst used as one of the catalysts, the function as the catalyst is effectively exhibited, the problems such as odor and deterioration of the working environment are reduced, and the effective foam characteristics are obtained. In order to obtain it, in the range of 0.1 to 7 parts by mass, preferably 0.2 to 3 parts by mass, and more preferably 0.3 to 1 part by mass with respect to 100 parts by mass of the entire polyol in the polyol composition. , Will be selected. If the amount of this amine-based catalyst used is less than 0.1 parts by mass, it becomes difficult to fully exert the function as a catalyst, and the obtained foam becomes sticky, dust, etc. adheres, and the appearance deteriorates. In addition, in the spray foaming operation, the droplets adhering to the floor or the like become sticky, which causes problems such as poor workability. Further, when the amount of the amine-based catalyst used is more than 7 parts by mass, the odor of the obtained polyurethane foam becomes remarkable, and the amine-based catalyst volatilized during foaming causes a problem that the spraying work environment is deteriorated. It will be like. Therefore, from the viewpoint of odor, it is preferable that the amount of the amine-based catalyst added is small.

Moreover, in the present invention, the above-mentioned trimerization catalyst is contained in the composition A as at least one of the catalysts, and the polyol in the composition A is reacted with the polyisocyanate in the composition B. In addition to producing polyurethane, red phosphorus and a metal tinic acid salt are used in combination as flame retardants, and these two flame retardants are used together or separately at least one of Composition A and Composition B. By containing the polyurethane foam in the above, the flame retardancy of the produced polyurethane foam could be synergistically enhanced, whereby the polyurethane foam having a high degree of flame retardancy could be advantageously provided.

As the red phosphorus used here, any known one is targeted, and usually, it is appropriately selected from commercially available products and used. The amount of this red phosphorus used is generally determined in the range of 5 to 60 parts by mass, preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyol in the composition A. This is because if the amount of red phosphorus added is too small, it becomes difficult to sufficiently exert the flame-retardant synergistic effect, and if the amount of red phosphorus added is too large, the viscosity of the composition to which the red phosphorus is added increases. However, in addition to causing problems such as poor stirring, problems such as deterioration of workability will also occur.

Examples of the tin metal salt include zinc tin, barium tin, sodium tin, potassium tin, cobalt tint, magnesium tin, and the like, and among them, zinc tin is preferable. Will be used. The amount of the tinous acid metal salt added is appropriately determined within the range of generally 5 to 60 parts by mass, preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyol in the composition A. Will be done. This is because if the amount of the tin acid metal salt added is too small, it becomes difficult to sufficiently exert the synergistic effect related to the improvement of flame retardancy, and if the amount of the tin acid metal salt added is too large, the above-mentioned red phosphorus is described. As in the case of the above, the viscosity of the composition to which the composition is added is increased, which causes problems such as deterioration of workability.

Further, in the present invention, in addition to the combined use of red phosphorus and a tin acid metal salt as described above, the composition further comprises at least one of a phosphoric acid ester and a metal hydroxide as a flame retardant. It is advantageously adopted to be blended and contained in A or composition B, whereby the flame retardancy of the formed polyurethane foam can be further advantageously improved.

The phosphoric acid ester used here is not particularly limited, and known ones such as monophosphoric acid ester and condensed phosphoric acid ester can be used alone or in combination. This phosphoric acid ester also acts as a thickener that can effectively reduce the viscosity of the chemical solution (composition A or composition B) and improve workability such as spraying.

Specifically, among these phosphate esters, the monophosphate ester is not particularly limited, but for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, tri. Phenylphosphine, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyldiphenyl 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, diphenyl methanephosphonate, diethyl phenylphosphonate, resilcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, tris (1-Chloro-2-propyl) phosphate and the like can be mentioned.

The condensed phosphoric acid ester is not particularly limited, but for example, trialkylpolyphosphate, resorcinolpolyphenyl phosphate, resorcinolpoly (di-2,6-xylyl) phosphate (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.). ), Hydroquinonepoly (2,6-xylyl) phosphate, and condensed phosphoric acid esters such as condensates thereof.

Further, as commercially available condensed phosphoric acid ester, for example, resorcinol polyphenyl phosphate (CR-733S), bisphenol A polycredyl phosphate (CR-741), aromatic condensed phosphoric acid ester (CR747), resorcinol polyphenyl phosphate (resolsinol polyphenyl phosphate). Adecastab PFR manufactured by ADEKA Co., Ltd.), bisphenol A polycresyl phosphate (FP-600, FP-700) and the like can be mentioned.

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

The amount of such a phosphoric acid ester used is in the range of 5 to 160 parts by mass, preferably about 20 to 140 parts by mass with respect to 100 parts by mass of the polyol in the composition A. preferable. This is because if the amount of the phosphoric acid ester used is too small, it becomes difficult to sufficiently exert the effect of adding the phosphoric acid ester, and if the amount of the phosphoric acid ester added is too large, the catalytic effect for forming the polyurethane foam is lowered. This causes problems such as inhibition of foaming.

Examples of the metal hydroxide include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, and 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 a combination of two or more kinds. Among them, aluminum hydroxide is particularly preferably used. The amount of the metal hydroxide added is generally in the range of about 5 to 50 parts by mass, preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyol in the composition A. preferable. This is because if the amount of the metal hydroxide added is too small, the effect of the addition cannot be sufficiently exerted, and if the amount of the metal hydroxide added is too large, the isocyanurate-forming reaction of the polyisocyanate is difficult to proceed. As a result, problems such as deformation of the formed foam and deterioration of flame retardancy will be caused.

By the way, in the composition A or the composition B constituting the effervescent composition for flame-retardant polyurethane foam according to the present invention, in addition to the above-mentioned compounding components or contained components, the polyurethane to be produced is further foamed. A foaming agent is blended, and if necessary, various conventionally known auxiliary agents such as a known foam stabilizer and other flame retardants are appropriately selected and blended. Is also possible.

As the foaming agent used here, various known foaming agents can be appropriately selected. In particular, in the present invention, a non-fluorocarbon foaming agent (and / or a source thereof) is used. ) Is advantageously used, and specifically, an organic foaming agent such as hydrofluorocarbon (HFC), hydrocarbon (HC), hydrofluoroolefin (HFO), or hydrochlorofluoroolefin (HCFO) is contained. The organic foaming agent is appropriately selected from various known foaming agents and used. For example, as the hydrocarbon (HFC), 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-pentafluoroethane (HFC365mfc), 1,1,1,2,2,3,4,5,5-decafluoropentane (HFC4310mee) and the like can be mentioned, and further. Examples of the hydrocarbon (HC) include normal pentane, isopentane, cyclopentane, isobutane and the like.

Examples of the hydrofluoroolefin (HFO) include pentafluoropropenes such as 1,2,3,3,3-pentafluoropropene (HFO1225ye), 1,3,3,3-tetrafluoropropene (HFO1234ze), and the like. Tris such as tetrafluoropropenes such as 2,3,3,3-tetrafluoropropene (HFO1234yf) and 1,2,3,3-tetrafluoropropene (HFO1234ye), and trifluoropropenes such as 3,3,3-trifluoropropene (HFO1243zf). Hexafluorobutene isomers such as fluoropropene, tetrafluorobutene (HFO1345), pentafluorobutene isomers (HFO1354), 1,1,1,4,4,4-hexafluoro-2-butene (HFO1336mzz). HFO1336), heptafluorobutene isomer (HFO1327), heptafluoropentene isomer (HFO1447), octafluoropentene isomer (HFO1438), nonafluoropentene isomer (HFO1429) and the like can be mentioned. Further, as hydrochlorofluoroolefin (HCFO), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), dichloro Trifluoropropene (HCFO1223) and the like can be mentioned. In particular, these hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) have a low global warming potential due to their chemical instability, and are therefore suitably used as environmentally friendly foaming agents. Get it. Then, along with these hydrofluoroolefins (HFOs) or hydrochlorofluoroolefins (HCFOs), water described later will be advantageously used as a foaming agent.

Further, in the present invention, water as a foaming agent is advantageously used together with or in place of the above-mentioned organic foaming agent. The presence of such water in the composition A containing the polyol causes the water and the polyisocyanate to react when the composition A and the polyisocyanate in the composition B are mixed and reacted. When the reaction produces carbon dioxide, heat of reaction is generated. Therefore, the heat can effectively promote the urethanization reaction and the isocyanurate-forming reaction, and the resulting polyurethane foam can be compressed. The strength can be further increased. Then, due to the presence of water in such composition A, the composition A and the polyisocyanate in the composition B are mixed and reacted, and carbon dioxide is generated by the reaction between the water and the polyisocyanate. This carbon dioxide is also generated and contributes to the foaming of polyurethane. The amount of such water used is generally 0.5 to 5 parts by mass, preferably 1 to 3 parts by mass with respect to 100 parts by mass of the entire polyol in the composition A. It is contained in A. If the amount of water used is more than 5 parts by mass, the strength of the produced polyurethane foam will be lowered. The reason is that the urea bond generated by the reaction between water and polyisocyanate increases in the resin, and the polyisocyanate used for the isocyanurate-forming reaction is consumed in the reaction with water, so that the polyisocyanate in the reaction system decreases. Because. Further, when the amount used is less than 0.5 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 to uniformly arrange the cell structure of the polyurethane foam, and here, a silicone-based surfactant or a nonionic surfactant is preferably adopted. 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 may be used alone, or two or more types may be used in combination. The blending amount of this defoaming agent is appropriately determined according to the desired foam characteristics, the type of the defoaming agent to be used, and the like, but it is included in 100 parts by mass of the entire 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 to be foamed and cured, they are known. Various methods for producing polyurethane foams can be appropriately adopted. For example, a laminate obtained by applying a mixture of the composition A and the composition B onto a face material and foaming / curing it in a plate shape. Continuous foaming method, injection foaming method that injects and fills in spaces where heat insulation is required such as electric refrigerators, in honeycomb structures of lightweight and high-strength boards, in voids generated in civil engineering work, etc., and foams and cures. The effervescent composition according to the present invention is foamed and cured by a spray foaming method in which the foaming composition according to the present invention is foamed and cured by spraying from the spray gun head of the on-site foaming machine onto a predetermined adherend (structure) to foam and cure the desired, highly advanced composition. A flame-retardant polyurethane foam will be formed.

Hereinafter, the features of the present invention will be clarified more specifically by showing some examples of the present invention and comparing them with the comparative examples. Needless to say, it is not subject to any restrictions. Further, in addition to the following examples, the present invention is further modified in various ways based on the knowledge of those skilled in the art, as long as it does not deviate from the gist of the present invention, in addition to the above-mentioned specific description. It should be understood that modifications, improvements, etc. can be made. Unless otherwise specified, the percentages (%) and parts shown below are all shown on a mass basis.

In addition, the density, maximum heat generation rate, total heat generation amount, residual carbon ratio, and residual state of the polyurethane foams obtained in the following Examples and Comparative Examples were evaluated or measured as follows, respectively.

(1) Measurement of maximum heat generation rate and total heat generation amount A sample for a cone calorimeter test having a size of 100 mm × 100 mm × 50 mm was cut out from the heating element to be measured, and conformed to the combustion test method specified in ISO-5660. The maximum heat generation rate and total heat generation amount when heated for 10 minutes at a radiant heat intensity of 50 kW / m ² and the total heat generation amount when heated for 20 minutes (the maximum heat generation amount is the same value as when heating for 10 minutes). , Each was measured. Then, the case where the maximum heat generation rate was 80 kW / m ² or less and the case where the total heat generation amount was 8 MJ / m ² or less were regarded as acceptable. In this test, when the foam sample expands and the tip of the spark plug, which is the ignition source, comes into contact with the expanded foam sample, sparks do not occur and normal measurement cannot be performed. The measurement was discontinued.

(2) Density measurement The dimensions of the cone calorimeter test sample cut out from the foam are measured using a caliper, while the mass is measured using an electronic balance to obtain them. The density of the sample (foam) was calculated from the measured values.

(3) Measurement of residual coal rate The mass of the sample after heating for 20 minutes when the combustion test conforming to ISO-5660 was carried out was measured, and the residual carbon rate was calculated according to the following formula. The case where the residual coal ratio was 60% or more was regarded as acceptable.
Residual coal rate (%) = (mass of sample remaining after heating for 20 minutes / mass of previous sample) × 100

(4) Evaluation of residue state-Judgment of expansion state-
When the combustion test conforming to the ISO-5660 is carried out, if the heated test sample comes into contact with the igniter (spark plug), it is marked with "x", and if it does not come into contact with it, it is marked with "○". I evaluated it as.

-Judgment of deformation state-
When the combustion test conforming to the ISO-5660 is carried out, if deformation or cracks reaching the back surface of the test sample are observed, it is marked with "x", and if no deformation reaching the back surface is observed. Was evaluated as "○".

-Judgment of contraction state-
When a combustion test conforming to the ISO-5660 is carried out, if deformation of 10 mm or more in the lateral direction and 5 mm or more in the thickness direction is observed in the test sample, it is marked as "x" and such deformation is observed. If it was not recognized, it was evaluated as "○".

First, the following various raw materials were prepared as the components used in the following examples and comparative examples.
Polyester compound: Phthalic acid polyester polyol (RF K505 manufactured by Kawasaki Kasei Chemicals Co., Ltd.)
Triquantization catalyst: Potassium octylate (Dabco K-15 manufactured by Evonik Japan Co., Ltd.)
: Quaternary ammonium salt (Kao Corporation Kaorizer No.420)
Resinification catalyst: Bismuth octylate (Pucat 25 manufactured by Nihon Kagaku Sangyo Co., Ltd.)
: N, N-dicyclohexylmethylamine (Polycat 12 manufactured by Evonik Japan Co., Ltd.)
Flame Retardant: Red Phosphorus (Nova Excel 140 manufactured by Rinkagaku Kogyo Co., Ltd.)
: Metal salt of tin (Zinc tin): Fram Tard S manufactured by Nippon Light Metal Co., Ltd.)
: Metal tintate salt (calcium tintinate: calcium metastinate manufactured by Mitsuwa Chemical Co., Ltd.)
: Metal sulphate salt (magnesium succinate: Magnesium metastinate manufactured by Mitsuwa Chemical Co., Ltd.)
: Phosphate ester [TCPP: Tris (1-chloro-2-propyl) phosphate]
: Phosphoric acid ester (Polyphosphoric acid ester: Adeka Stub P FR manufactured by ADEKA Corporation)
: Metal hydroxide (aluminum hydroxide: B-1403 manufactured by Nippon Light Metal Co., Ltd.)
: Metal hydroxide (magnesium hydroxide: Kisma-5 manufactured by Kyowa Chemical Industry Co., Ltd.)
Foaming agent: HCFO-1233zd (Honeywell 1-chloro-3,3,3-trifluoropropene)
: HFO-1336mzz (Chemours 1,1,1,4,4,4-hexafluoro-2-butene)
: HFC245fa (1,1,1,3,3-pentafuuropropane manufactured by Central Glass Co., Ltd.)
:water

-Preparation of polyol composition (Composition A)-
The various raw materials prepared above, that is, the polyol, the quantification catalyst, the resinification catalyst, the flame retardant and the foaming agent, are uniformly mixed in the various combinations and blending ratios shown in Tables 1 and 2 below. Various polyol compositions according to Examples 1 to 14 and Comparative Examples 1 to 6 were prepared, respectively.

-Preparation of polyisocyanate composition (composition B)-
Polymeric MDI (Wannate PM-200 manufactured by Manka Chemical Japan Co., Ltd.) was prepared as a polyisocyanate, and the composition B was composed only of this polyisocyanate.

-Manufacturing 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. After that, it was housed in a polypropylene container having a capacity of 300 parts, and mixed for 10 seconds using a stirrer: TK Homo Disper (manufactured by Primix Corporation). Then, the mixed liquid was poured into a polypropylene container of 2000 parts by volume and foamed and cured to obtain a desired foam. In the case of Comparative Example 6, since the reaction at room temperature causes poor curing as in Comparative Example 5, the container into which the mixed liquid was poured was placed in a constant temperature bath at 50 ° C. for 24 hours. The one that was hardened by holding was used.

Then, using the various polyurethane foams thus obtained, the density, the maximum heat generation rate, the total calorific value, the residual carbon content and the state of the residue are measured or evaluated, respectively, and the obtained results are obtained. , Are summarized in Tables 1 to 3 below.

As is clear from the results of Tables 1 and 2, the foamability of the combination of the polyol composition (composition A) and the polyisocyanate (composition B) adopted in Examples 1 to 14 according to the present invention. Regarding the composition, in a combustion test method compliant with ISO-5660, a polyurethane foam having a high degree of flame retardancy, which exhibits excellent total calorific value and residual carbon content and has a good residual state, is obtained. It is recognized that it can be done.

On the other hand, as is clear from the results shown in Table 3, in Comparative Example 1 using the polyol composition containing only red phosphorus as a flame retardant, the foam sample expanded at the time of measurement. In Comparative Example 2 in which the amount of red phosphorus used as a flame retardant was increased, the maximum calorific value was extremely high, the total calorific value was increased, and the residual coal rate was reduced. As a result, it became clear that there was a problem with flame retardancy. Further, in Comparative Examples 3 and 4 in which only the tin acid metal salt was used as the flame retardant and the polyol composition containing no red phosphorus was used, the total calorific value was high and the residue remained. It is understood that the flame retardancy is not sufficient due to the foam having a low carbon content. In addition, in the case of Comparative Example 5 in which only the resinification catalyst is used without using the trimerization catalyst in forming the polyurethane foam, the curing of the foam does not proceed sufficiently, and therefore ISO The result was that it was not possible to obtain a sample that could be used for testing in accordance with -5660. Furthermore, in the case of Comparative Example 6, it became clear that there are inherent problems in all of the maximum heat generation rate, the total heat generation amount, and the residual coal rate. Therefore, from the results of Comparative Examples 1 to 6, it can be understood that excellent flame retardancy can be imparted only by using a trimerization catalyst and two specific flame retardants.

Claims (11)

A foamable composition composed of a composition A containing a polyol and a composition B containing a polyisocyanate, which gives a polyurethane foam by foaming with a foaming agent together with the reaction between the polyol and the polyisocyanate.
The composition A contains at least a trimerization catalyst as a catalyst, and red phosphorus and a tinous acid metal salt are used in combination, and they are used together or separately at least one of the above composition A and the above composition B. A foamable composition for flame-retardant polyurethane foam, characterized in that it is contained in one of them. The foamable composition for a flame-retardant polyurethane foam according to claim 1, wherein the tin metal salt is zinc tin. The flame-retardant polyurethane foam according to claim 1 or 2, wherein the red phosphorus is used in a ratio of 5 to 60 parts by mass with respect to 100 parts by mass of the polyol in the composition A. Effervescent composition for. The invention according to any one of claims 1 to 3, wherein the tin metal salt is used in a ratio of 5 to 60 parts by mass with respect to 100 parts by mass of the polyol in the composition A. The effervescent composition for the flame-retardant polyurethane foams described. The effervescent composition for a flame-retardant polyurethane foam according to any one of claims 1 to 4, wherein the trimerization catalyst is a quaternary ammonium salt. The foamability for flame-retardant polyurethane foam according to any one of claims 1 to 4, wherein a carboxylic acid alkali metal salt and a quaternary ammonium salt are used in combination as the trimerization catalyst. Composition. The effervescent composition for a flame-retardant polyurethane foam according to any one of claims 1 to 6, wherein the polyol is an aromatic polyester polyol. The effervescent composition for a flame-retardant polyurethane foam according to claim 7, wherein the aromatic polyester polyol is a phthalic acid-based polyester polyol. The effervescent composition for a flame-retardant polyurethane foam according to any one of claims 1 to 8, wherein the phosphoric acid ester is further contained in the composition A or the composition B. .. The foamable composition for a flame-retardant polyurethane foam according to any one of claims 1 to 9, wherein the metal hydroxide is further contained in the composition A or the composition B. thing. ⁶ . The foamable composition for the flame-retardant polyurethane foams described.