WO2021255958A1 - Foam composition for flame-retardant polyisocyanurate foam and method for producing flame-retardant polyisocyanurate foam using said foam - Google Patents

Abstract

Provided is a foam composition that yields a polyisocyanurate foam having a low calorific value upon combustion and excellent self-extinguishing properties, said composition also being capable of advantageously forming a polyisocyanurate foam having higher flame retardancy even in the presence of a skin layer.　In a foam composition configured from a composition A containing a polyisocyanate and a polyol-free composition B containing at least a trimerization catalyst as a catalyst, said composition being capable of forming a polyisocyanurate foam via an isocyanuration reaction caused by the trimerization catalyst and foaming caused by a foaming agent, the composition B also contains a liquid organic phosphoric acid ester and a powdered phosphorus-containing flame retardant.

Description

Effervescent composition for flame-retardant polyisocyanurate foam and method for producing flame-retardant polyisocyanurate foam using the same.

The present invention relates to an effervescent composition for flame-retardant polyisocyanurate foam and a method for producing a flame-retardant polyisocyanurate foam using the same, and in particular, exhibits nonflammable properties specified by the Building Standards Law of Japan. It relates to an effervescent composition capable of advantageously forming a polyisocyanurate foam having, and a method capable of advantageously forming a nonflammable polyisocyanurate foam from such an effervescent composition.

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., and prevention of dew condensation, heat insulation of infusion pipes, etc. It is also practically used as a reinforcing material for the case. Further, such a polyurethane foam is generally composed of a polyol compounding liquid (premixed liquid) 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. And a composition 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 used as a slab foaming method, an injection foaming method, or a spray foaming method. , Laminate continuous foaming method, lightweight filling method, injection backfilling method, etc., by foaming and curing.

However, since the polyurethane foam formed as described above is flammable when exposed to fire, high flame retardancy is required from the viewpoint of its use. Therefore, a foamable composition for a flame-retardant polyurethane foam containing various flame retardants has been proposed. For example, in Japanese Patent Publication No. 2014-524954 (Patent Document 1), improved flame retardancy has been proposed. Polyisocyanate components, including isocyanate prepolymers and any flame retardant compounds, as well as aromatic polyester polyols, red phosphorus and catalysts, and further 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, halogen-containing compounds, phosphates, inorganic fillers, antimony oxide, zinc and the like are exemplified there as flame-retardant additives to be further added and contained.

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, urethane catalysts and triglycerides of isocyanates are used for the formation of polyurethane foams, and metal-based inorganic fillers for ease of processing, such as metal hydrates and zinc borate, are used. It has been clarified that zinc salts such as zinc succinate can be contained.

Further, in WO2014 / 112394 (Patent Document 3), a flame retardant urethane resin composition containing an additive containing red phosphorus as an essential component together with a polyol compound, a polyisocyanate compound, a trimerization catalyst, a foaming agent and a foam stabilizer. In addition to red phosphorus, such urethane resin compositions include phosphate esters, phosphate-containing flame retardants, brominated flame retardants, and boron-containing flame retardants. , Antimon-containing flame retardant and at least one selected from the group consisting of metal hydroxides are said to be contained in combination, which makes it easy to handle, has excellent flame retardancy, and when heated. It has been clarified that a flame retardant urethane resin composition capable of forming a foam that maintains a constant shape can be provided.

However, among those patent documents, the flame-retardant polyurethane coating obtained in Patent Document 1 and Patent Document 2 and the polyurethane foam having improved smoke emission suppressing performance are severely flame-retardant in recent years in terms of their flame-retardant characteristics. It was not possible to fully respond to the request for conversion. 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.

Further, the red phosphorus used in Patent Document 1 and Patent Document 3 promotes the formation of a surface carbonized layer necessary for increasing the flame retardancy of the polyurethane foam when the polyurethane foam is burned, and suppresses the propagation of flame. However, when the polyurethane foam is ignited, the red phosphorus itself has the property of burning when the amount used is increased in order to enhance the flame-retardant effect. Since the contained red phosphorus is burned, there is a problem that the initial calorific value of the polyurethane foam becomes high, and there is an inherent problem that the time to self-extinguishing becomes long.

On the other hand, in JP-A-2010-195920 (Patent Document 4) and JP-A-2012-236874 (Patent Document 5), organic as a filler (flame retardant) for imparting flame retardancy to polyurethane resin. Although it has been clarified that a phosphinate compound is used, a polyurethane foam formed by using only such an organic phosphinate compound has good self-extinguishing property at the time of ignition. However, there is an inherent problem that the formation of the carbonized layer on the surface of the polyurethane foam, which is necessary for enhancing the flame retardancy, is insufficient, and the carbonized layer is liable to crack due to the heat of combustion. Then, when cracks occur in the carbonized layer, further combustion is caused from the cracks, and there is a possibility that the calorific value increases.

By the way, the polyurethane foam formed by the reaction of the polyol and the polyisocyanate and the foaming by the foaming agent is generally formed on the core layer (main body portion) having a laminated structure of a large number of foam cells and the surface of the core layer. It is composed of a dense skin layer (skin part) that is substantially free of foam cells, but the material (resin) of such polyurethane foam is a flammable substance, in particular. The skin layer formed on the foam surface is dense and flammable. Therefore, when the obtained polyurethane foam is made flame-retardant by using various flame retardants proposed in the above-mentioned publication, the core layer portion, which is the main body of the foam, has excellent flame retardancy. Even if it is non-flammable, it will burn in the skin layer, which is the skin of the foam, which will increase the calorific value and worsen the self-extinguishing property. It was not able to fully exhibit flame retardancy and nonflammability.

In Japan's Building Standards Law, the fire resistance and fire protection performance of materials are classified into flame retardant materials, semi-incombustible materials, and non-combustible materials. Although stricter fire protection performance is required, the above is to give a high degree of flame retardancy to the foam material made of polyurethane foam obtained by reacting the polyol and polyisocyanate and foaming. It has been difficult to satisfy the non-combustible performance of the non-combustible material that requires the strictest fire protection performance even when the conventional flame retardant as disclosed in the published publication is used. In particular, when heated at the characteristics required for non-combustible materials specified by the Building Standards 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 /. If the amount of the above-mentioned known flame-retardant agent is increased with respect to the effervescent composition for polyurethane foam in order to obtain nonflammable properties of ^{m 2 or less, the reaction between the polyol and the polyisocyanate is inhibited.} Problems such as the inability to obtain the desired foam and the deterioration of physical or mechanical properties such as the thermal conductivity of the obtained foam will be caused.

In addition, according to the provisions of the Building Standards Act (Article 1, Item 5 of the Enforcement Ordinance), the non-combustible material satisfies the total calorific value described above, and the maximum calorific value continuously exceeds 10 seconds. It is said that it does not exceed 200 kW / m ² and that there are no cracks or holes that penetrate to the back surface, which is harmful in terms of flame resistance. While ensuring useful physical or mechanical properties as a polyurethane resin, it was not possible to sufficiently meet the demand for such nonflammable performance.

Japanese Patent Publication No. 2014-524954 Special Table 2014-532098 Gazette WO2014 / 112394 JP-A-2010-195920 Japanese Unexamined Patent Publication No. 2012-236874

Here, the present invention has been made in the background of such circumstances, and the solution thereof is a polyisocyanurate foam that further enhances flame retardancy even in the presence of a skin layer. It is an object of the present invention to provide an effervescent composition which can advantageously form a polyisocyanurate foam which has a low calorific value at the time of combustion and has excellent self-extinguishing property, and also provides such a polyisocyanurate foam. It is an object of the present invention to provide a method capable of advantageously producing a polyisocyanurate foam having such excellent flame retardancy by using an effervescent composition for use.

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) The polyisocyanate is composed of a composition A containing a polyisocyanate and a polyol-free composition B containing at least a trimerization catalyst as a catalyst, and the trimericization of the polyisocyanate in the absence of polyol. A foamable composition capable of forming a polyisocyanurate foam by a catalytic isocyanurate-forming reaction and foaming with a foaming agent is obtained, and the composition B is further prepared into a powdery state with a liquid organic phosphate ester. A foaming composition for a flame-retardant polyisocyanurate foam containing a phosphorus-containing flame retardant.
(2) The phosphorus concentration in the composition B is set to 10 to 30% by mass.
The effervescent composition for flame-retardant polyisocyanurate foam according to the above aspect (1), which is prepared.
(3) The difficulty according to the above aspect (1) or the above aspect (2), wherein the liquid organic phosphoric acid ester is contained in the composition B in a proportion of 25 to 60% by quantity. Foamable composition for flammable polyisocyanurate foam.
(4) The embodiment (4), wherein the liquid organic phosphate ester is selected from the group consisting of a monophosphate ester and a condensed phosphate ester.
The effervescent composition for flame-retardant polyisocyanurate foam according to any one of 1) to (3) above.
(5) Any one of the above-described embodiments (1) to (4), wherein the powdered phosphorus-containing flame retardant has an average particle size of 50 μm or less.
The effervescent composition for flame-retardant polyisocyanurate foam according to one.
(6) Described in any one of the above-described embodiments (1) to (5), wherein the powdered phosphorus-containing flame retardant is selected from the group consisting of red phosphorus and phosphate. Effervescent composition for flame retardant polyisocyanurate foam.
(7) The flame retardant according to the above-mentioned embodiment (6), wherein the phosphate is selected from the group consisting of monophosphate, pyrophosphate, polyphosphate, and organic phosphinate. Effervescent composition for sex polyisosocyanurate foam.
(8) The difficulty according to any one of the above-described embodiments (1) to (7), wherein red phosphorus and an organic phosphinate are used in combination as the powdered phosphorus-containing flame retardant. Foamable composition for flammable polyisocyanurate foam.
(9) The powdered phosphorus-containing flame retardant is one of the liquid organic phosphoric acid esters.
The flame-retardant polyisocyanurate foam according to any one of the above aspects (1) to (8), which is contained in a proportion of 40 to 100 parts by mass with respect to 00 parts by mass. Effervescent composition.
(10) The embodiments (1) to (9), wherein the trimerization catalyst is a quaternary ammonium salt or a carboxylic acid alkali metal salt.
The effervescent composition for flame-retardant polyisocyanurate foam according to any one of the above.
(11) The aspect (1) to the above aspect (10), wherein the foaming agent is an organic foaming agent selected from the group consisting of hydrocarbons, hydrofluoroolefins and hydrochlorofluoroolefins.
). The effervescent composition for flame-retardant polyisocyanurate foam according to any one of.
(12) Foaming for flame-retardant polyisocyanurate foam according to any one of the above-described embodiments (1) to (11), wherein the foaming agent is contained in the composition B. Sex composition.
(13) The foaming agent according to any one of the above embodiments (1) to (12), wherein the foaming agent is used in a ratio of 40 to 100 parts by mass with respect to 100 parts by mass of the liquid organic phosphoric acid ester. The foaming composition for flame-retardant polyisocyanurate foam according to any one of them.
(14) Using the effervescent composition for flame-retardant polyisocyanurate foam according to any one of the above-mentioned aspects (1) to (13), the foamable composition can be obtained into a predetermined structure. A method for producing a flame-retardant polyisocyanurate foam, which comprises forming a polyisocyanurate foam layer having a predetermined thickness on the surface of the structure by spraying on the surface of the structure to foam and cure the foam.
^{(15) When the polyisocyanurate foam layer is heated to a radiant heat intensity of 50 kW / m 2} in accordance with the heat generation test method specified in ISO-5660, the total for 20 minutes from the start of heating. The calorific value is 8.0MJ /
The above-mentioned aspect (1) characterized by having a non-combustible property of ^{m 2 or less.}
4) The method for producing a flame-retardant polyisocyanurate foam according to 4).

As described above, in the effervescent composition for flame retardant polyisocyanurate foam according to the present invention, the polyol is not used to further promote the nulation of the polyisocyanate, and at least triglyceride as a reaction catalyst. Since a catalyst is used and, further, a liquid organic phosphate ester and a powdered phosphorus-containing flame retardant are used in combination as a flame retardant, in the presence of the isocyanurate structure introduced by such a trimerization catalyst, The organic phosphate ester and the phosphorus-containing flame retardant can effectively exhibit the flame retardant action of each, and thus the skin layer can be obtained even if the skin layer is present on the foam surface. The flame retardancy of the polyisocyanurate foam can be further enhanced, the total calorific value can be effectively reduced, and thus the realization of nonflammable performance can be advantageously achieved.

In particular, in the polyisocyanurate foam formed from such an effervescent composition according to the present invention, the combustible content in the formed foam is reduced to the limit by the absence of the polyol as a combustible resin component. This also contributes to the fact that the initial calorific value at the time of combustion can be advantageously reduced, the effect of enhancing self-extinguishing property can be effectively exerted, and therefore the flame retardancy can be advantageously enhanced. In addition to this, it effectively promotes the formation of a carbonized layer on the surface of the polyisocyanurate foam at the time of ignition and suppresses the formation of cracks on the surface, thereby preventing the formation of cracks on the surface. It will have the effect of blocking the combustion of polyisocyanurate and preventing the increase in calorific value.

Thus, according to the present invention, with the effective introduction of the isocyanurate structure, by the combined use of the organic phosphate ester and the phosphorus-containing flame retardant, due to the synergistic effect of the flame retardant action as described above, the surface of the polyisocyanurate foam upon combustion. The polyisocyanurate foam has a better balance between the carbonized layer and the self-extinguishing property, does not continue to burn even when ignited, and has high heat-resistant decomposition resistance, whereby a skin layer exists. Even so, polyisocyanurate foam, which is extremely difficult to burn and has improved self-extinguishing properties, could be provided advantageously.

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

First, the effervescent composition for flame-retardant polyisocyanurate foam according to the present invention is composed of a composition A containing a polyisocyanate and a polyol-free composition B containing at least a trimerization catalyst as a catalyst. It is an effervescent composition in which the desired polyisocyanurate foam is formed by foaming with a foaming agent together with an isocyanurate-forming reaction with a triisocyanate catalyst in the absence of a polyol. Polyisocyanate, which is a main component constituting the composition A used, forms an isocyanurate structure by a trimerization catalyst, and further gives polyisocyanurate (resin) by a high molecular weight, various known polyisocyanates. The compounds will be used alone or in combination as appropriate.

Specifically, the polyisocyanate is an organic isocyanate compound having two or more isocyanate groups (NCO groups) in the molecule, and is, for example, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, polytolylene triisocyanate. , Aromatic polyisocyanates such as xylylene diisocyanate and naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, urethane prepolymers having an isocyanate group at the molecular terminal, and polyisocyanates. Examples thereof include isocyanurate modified products and carbodiimide modified products. 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.

On the other hand, in the composition B, the polyisocyanate contained in the above-mentioned composition A is made into a nurate to form a hard foam of polyisocyanurate (resin). A catalyst (isocyanurate-forming catalyst) that promotes the formation of an isocyanurate ring by reacting the isocyanate group contained in the isocyanurate is contained. As the trimerization catalyst, various known ones can be appropriately selected and used, but quaternary ammonium salt or carboxylic acid alkali metal salt; tris (dimethylaminomethyl) phenol is preferable. , 2,4-Bis (dimethylaminomethyl) phenol, tris (dimethylaminopropyl) hexahydrotriazine and other nitrogen-containing aromatic compounds; trimethylammonium salt, triethylammonium salt, triphenylammonium salt and other tertiary ammonium salts, etc. Can be mentioned. Of these, it is preferable to use a quaternary ammonium salt or a carboxylic acid alkali metal salt from the viewpoint of improving flame retardancy, and above all, it is further preferable to use two or more kinds of quaternary ammonium salts in combination. It is particularly preferable from the viewpoint of improving flame retardancy and improving workability by reducing the density of polyisocyanurate foam.

The quaternary ammonium groups (monovalent cations in which four organic groups are covalently bonded to the 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 Adipose ammonium groups such as trimethylammonium, heptadecyltrimethylammonium, hexadecyltrimethylammonium, heptadecyltrimethylammonium, octadecyltrimethylammonium, (2-hydroxypropyl) trimethylammonium, hydroxyethyltrimethylammonium, trimethylaminoethoxyethanol, hydroxyethyl- Hydroxyammonium groups such as 2-hydroxypropyldimethylammonium, 1-methyl-1-azania-4-azabicyclo [2,2,2] octanium, 1,1-dimethyl-4-methylpiperidinium, 1-methylmorpholi Examples thereof include alicyclic ammonium groups such as nium and 1-methylpiperidinium. Among these, tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, butyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, decyltrimethylammonium, and 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 quaternary ammonium groups such as 1,1-dimethyl-4-methylpiperidinium will be preferably adopted.

Further, examples of the organic acid group or inorganic acid group which are monovalent anions which are ionically bonded to such a quaternary ammonium group to form a quaternary ammonium salt include formic acid group, acetic acid group and octyl acid. Group, oxalic acid group, malonic acid group, succinic acid group, glutarate group, adipic acid group, benzoic acid group, toluyl acid group, ethyl benzoic acid group, methyl carbonate group, phenol group, alkylbenzene sulfonic acid group, toluene sulfonic acid group. , Organic acid groups such as benzenesulfonic acid group and phosphoric acid ester group, and inorganic acid groups such as halogen group, hydroxyl group, hydrogencarbonate group and carbonic acid group can be mentioned. Among these, a formic acid group, an acetate group, an octylate group, a methylcarbonic acid group, a halogen group, a hydroxyl group, a hydrogencarbonate group, and a carbonic acid group are preferably used because they have excellent catalytic activity and are industrially available. ..

By the way, as a catalyst composed of a quaternary ammonium salt having the above-mentioned structure, 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 the carboxylic acid alkali metal salt, an alkali metal salt of an aliphatic carboxylic acid having 1 to 8 carbon atoms is preferably used. Here, examples of the aliphatic carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanic acid, octylic acid and the like, and among them, formic acid, acetic acid, hexanic acid, octylic acid and the like are preferable. Carboxylic acid is used. Examples of the alkali metal include lithium, potassium, sodium and the like, and potassium and sodium are preferably used. The aliphatic carboxylic acid alkali metal salt targeted in the present invention may be any compound in the above-mentioned combination of the aliphatic carboxylic acid and the alkali metal, but preferred examples thereof are potassium octylate and potassium 2-ethylhexanoate. , Sodium acetate, potassium acetate, potassium formate and the like.

As described above, the amount of the trimerization catalyst used as one of the catalysts is such that 100 parts by mass of the entire polyisocyanate in the composition A is used in order to effectively exert the function as the catalyst. It will be selected within the range of 3 to 10 parts by mass, preferably 4 to 9 parts by mass. If the amount of the trimerization catalyst used is less than 3 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 is more than 10 parts by mass, the reaction proceeds too much and the solidification becomes faster, which causes a problem in the spray foaming operation and the like, which makes the construction difficult.

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

The amount of such a resinification catalyst used is 0.1 to 5 parts by mass with respect to 100 parts by mass of the entire polyisocyanate in the composition A in order to effectively exert its function as a catalyst. It will be preferably selected within the range of 0.5 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 or the carboxylic acid alkali metal 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 also appropriately selected to include the quantification catalyst and the like. It can be contained in the composition B. 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 is tetramethyl. Guanidin, 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, Examples thereof include N-methyl-N'-hydroxyethyl piperazine. Examples of the cyclic amine compound include 1,2-dimethylimidazole, 1-isopropyl-2-methylimidazole, 2,4,6-tri (dimethylaminomethyl) phenol, triethylenediamine, and N, N'-dimethylcyclohexylamine. , N, N-dicyclohexylmethylamine, methylenebis (dimethylcyclohexyl) amine, N, N-dimethylbenzylamine, morpholine, N-methylmorpholine, N-ethylmorpholin, N- (2-dimethylaminoethyl) morpholine , 4,4'-Oxydiethylenedimorpholine, N, N'-diethylpiperazine, N, N'-dimethylpiperazine, N-methyl-N'-dimethylaminoethylpiperazine, 1,8-diazobicyclo (5,4) , 0) -Undesen-7, etc. 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, it is within 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 polyisocyanate in the composition A. Will be selected in. 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 and the like adhere to it, 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 polyisocyanurate foam becomes remarkable, and the amine-based catalyst volatilized during foaming causes a problem that the spraying work environment is deteriorated. It will be evoked. Therefore, from the viewpoint of odor, it is preferable that the amount of the amine-based catalyst used is small.

Moreover, in the present invention, the polyisocyanurate is carried out by using the composition B containing the above-mentioned trimerization catalyst as at least one of the catalysts to promote the nurateization reaction of the polyisocyanate in the composition A. In addition to producing (resin), the flame retardancy of the produced polyisocyanurate foam is synergistically produced by using a liquid organic phosphate ester and a powdered phosphorus-containing flame retardant in combination as a flame retardant. This allows for higher flame retardancy than when these flame retardants are used alone, and even when the polyol is reacted with polyisocyanates to form polyurethane foam. It was possible to advantageously provide the polyisocyanurate foam having.

By the way, the liquid organic phosphoric acid ester used in the present invention has an effect of reducing the calorific value at the time of burning of the foam, so that the polyisocyanurate foam formed from the effervescent composition according to the present invention is flame-retardant. The properties can be synergistically and further improved, and the composition B can be made into a liquid chemical solution to effectively reduce its viscosity and improve the workability of spraying and the like. It also acts as a thickener. The liquid organic phosphate ester used here is not particularly limited as long as it is liquid, and known ones such as monophosphate ester and condensed phosphate ester may be used alone or in combination. Can be done.

Specifically, among these organic phosphate esters, the monophosphate ester is not particularly limited, but for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxy. Ethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyldiphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2- Ethylhexyl) Phosphonate, Di (Isopropyl) Phenylphosphine, Monoisodecyl Phosphonate, 2-Acryloyloxyethyl Acid Phosphonate, 2-methacryloyloxyethyl Acid Phosphonate, Diphenyl-2-Acryloyloxyethyl Phosphonate, Diphenyl-2-methacryloyloxyethyl Phosphonate , Melamine phosphate, Dimelamine phosphate, Melaminepyrophosphate, Triphenylphosphine oxide, Tricresylphosphine oxide, Diphenyl methanephosphonate, Diethyl phenylphosphonate, Regylsinol bis (diphenyl phosphate), Bisphenol A bis (diphenyl phosphate), Phosphine Phenylphosphine, tris (1-chloro-2-propyl) phosphate and the like can be mentioned.

The condensed phosphoric acid ester is also not particularly limited, and is, for example, trialkylpolyphosphate, resorcinolpolyphenyl phosphate, resorcinolpoly (di-2,6-xylyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd.). PX-200), hydroquinone poly (2,6-xylyl) phosphate, and condensed phosphate esters of these condensates can be mentioned. Further, as commercially available condensed phosphoric acid ester, for example, resorcinol polyphenyl phosphate (CR-733S), bisphenol A polycresyl phosphate (CR-741), aromatic condensed phosphoric acid ester (CR747), resorcinol polyphenyl phosphate (CR-747). 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 an organic phosphoric acid ester used is generally 25 to 60% by mass, preferably about 30 to 50% by mass in the composition B. If the amount of this organic phosphate ester used is too small, there is a problem that it is difficult to fully exert the effect of addition thereof, while if the amount used is too large, a polyisocyanurate foam is formed. Therefore, problems such as a decrease in catalytic effect and inhibition of foaming will be caused. Further, this organic phosphoric acid ester is generally used in a ratio of about 10 to 70 parts by mass, preferably about 30 to 50 parts by mass, with respect to 100 parts by mass of the polyisocyanate in the composition A.

Further, a powdery phosphorus-containing flame retardant that is used together with such an organic phosphoric acid ester to impart effective flame retardancy to the polyisocyanurate foam formed thereof is advantageous in that the average particle size is 50 μm or less. Among them, it has an average particle size of preferably 0.1 to 50 μm, more preferably 0.5 to 40 μm, and even more preferably 1 to 36 μm. If the average particle size of this phosphorus-containing flame retardant becomes too large, it is difficult to obtain a uniform dispersion effect in the effervescent composition, which causes a problem that the object of the present invention cannot be sufficiently achieved. Is. If the particle size of the phosphorus-containing flame retardant becomes too small, problems such as difficulty in handling the phosphorus-containing flame retardant and uniform dispersion in the effervescent composition will occur. Therefore, the lower limit thereof is set as the lower limit. It is desirable that the thickness is about 0.1 μm. The powdery phosphorus-containing flame retardant is generally at a ratio of about 40 to 100 parts by mass, preferably about 50 to 80 parts by mass, based on 100 parts by mass of the liquid organic phosphoric acid ester. , Will be used. If the amount of the phosphorus-containing flame retardant added is too small, there is a problem that it is difficult to fully exert the effect of the addition, while if the amount of the phosphorus-containing flame retardant is added too much, the liquefaction of the composition B is hindered. As a result, problems such as deterioration of spraying workability will be caused.

By the way, as such a powdery phosphorus-containing flame retardant, various known powdery ones can be used, but in particular, in the present invention, a group consisting of red phosphorus and phosphate. It is desirable to be selected more. In the present invention, red phosphorus is treated as a phosphorus-containing flame retardant. The combination of the liquid organic phosphoric acid ester and the powdery phosphorus-containing flame retardant may be a combination of the organic phosphoric acid ester and red phosphorus, a combination of the organic phosphoric acid ester and the phosphate, and further. The organic phosphate ester and the phosphorus-containing flame retardant may be in any combination even if a plurality of them are used.

As one of such phosphorus-containing flame retardants, known red phosphorus is preferably used, and usually, it is appropriately selected from commercially available products and used. It becomes. (For example, those sold under the names of "NOVARED" and "NOVAEXCEL" manufactured by Rinkagaku Kogyo Co., Ltd., "HISHIGUARD" manufactured by Nippon Chemical Industrial Co., Ltd., and "EXOLIT RP" manufactured by Clariant Chemicals Co., Ltd. Among them, such powdered red phosphorus has improved handleability or workability, as well as improved dispersibility in the resin composition and advantageously improved the effect of addition thereof. It is desirable that a coating layer is formed on the surface, specifically, hydroxides of metals such as aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide, aluminum oxide, and oxidation. A coating layer made of an inorganic compound made of an oxide of a metal such as magnesium, zinc oxide, or titanium oxide, and / or a thermosetting resin such as a phenol resin, a furan resin, or a xylene / formaldehyde resin is formed on the particle surface. The red phosphorus powder will be advantageously used. The coating layer is generally formed at a ratio of about 1 to 30 parts by mass with respect to 100 parts by mass of red phosphorus.

In addition, examples of the phosphate pointed out as another suitablely used powdery phosphorus-containing flame retardant include monophosphate, pyrophosphate, polyphosphate, organic phosphinate and the like. One or more selected from them will be contained in the composition B.

The monophosphate, which is one of the specific examples of such a phosphate-containing flame retardant, is not particularly limited, but for example, ammonium such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate. Salts; sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, dissodium phosphite, sodium hypophosphite; monopotassium phosphate, dipotassium phosphate, phosphorus Potassium salts such as tripotassium acid, monopotassium phosphite, dipotassium phosphite, potassium hypophosphite; monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, phosphite Lithium salts such as dilithium and lithium hypophosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate and barium hypophosphite; magnesium monohydrogen phosphate, magnesium hydrogen phosphate, etc. Magnesium salts such as trimagnesium phosphate and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate and calcium hypophosphite; zinc phosphate, zinc phosphite, hypophosphite Zinc salts such as zinc phosphate and the like can be mentioned.

Further, the pyrophosphate is not particularly limited, and for example, ammonium pyrophosphate, melamine pyrophosphate, acetguanamine pyrophosphate, benzoguanamine pyrophosphate, acrylic guanamine pyrophosphate, 2,4-diamino-6 pyrophosphate. -Nonyl-1,3,5-triazine, pyrophosphate 2,4-diamino-6-hydroxy-1,3,5-triazine, pyrrophosphate 2-amino-4,6-dihydroxy-1,3,5- Triazine, pyrophosphate 2,4-diamino-6-methoxy-1,3,5-triazine, pyrophosphate 2,4-diamino-6-ethoxy-1,3,5-triazine, pyrophosphate 2,4-diamino- 6-propoxy-1,3,5-triazine, pyrophosphate 2,4-diamino-6-isopropoxy-1,3,5-triazine, pyrophosphate 2,4-diamino-6-mercapto-1,3,5 -Triazine, 2-amino-4,6-dimercapto-1,3,5-triazine pyrophosphate and the like can be mentioned.

Further, the polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate, aluminum polyphosphate, and the like.

In addition, the organic phosphinate, which is one of the phosphorus-containing flame retardants, is one of the organic groups such as a linear alkyl group and a phenyl group having 1 to 6 carbon atoms in the phosphorus atom constituting the phosphinic acid. Alternatively, various known metals are ionically bonded to the organic phosphinic acid having a structure in which the two are covalently bonded to exhibit a salt form. Generally, the phosphorus atom has a methyl group, an ethyl group or a phenyl group. Is preferable, and the metal is preferably Mg, Al, Ca, Ti or Zn, and particularly preferably Al or Zn. Specifically, (mono or di) zinc phosphinate, (mono or di) zinc phosphinate, (mono or di) zinc phenylphosphinate, (mono or di) aluminum phosphinate, (mono or di). Examples thereof include aluminum ethylphosphinate, (mono or di) aluminum phenylphosphinate, and the like.

In particular, in the present invention, it is desirable to use red phosphorus and an organic phosphinate in combination as a phosphorus-containing flame retardant, and the combined use has sufficient strength on the foam surface when the polyisocyanurate foam is burned. It has the effect of promoting the formation of a carbonized layer, effectively preventing the increase in the total calorific value of the polyisocyanurate foam without causing cracks in the carbonized layer, and the initial calorific value during combustion of the polyisocyanurate foam. It is more difficult than the case where either organic phosphinate or red phosphorus is contained alone in the polyisocyanurate foam by allowing the effect of reducing the amount of fire and increasing the self-extinguishing property to be exerted advantageously. By making it possible to synergistically exert the flame retardant characteristics of the flame retardant, it is possible to advantageously form a polyisocyanurate foam that is extremely difficult to burn and has improved self-extinguishing properties.

Then, the composition B, which is one of the constituents of the effervescent composition according to the present invention, contains the above-mentioned organic phosphoric acid ester or phosphorus-containing flame retardant, so that the composition B is generally 10 to 30% by mass. It will be adjusted to have a phosphorus concentration of preferably 12 to 25% by mass. If the phosphorus concentration in the composition B is too low, there is a problem that it is difficult to sufficiently increase the flame retardancy of the foam, while if the phosphorus concentration is too high, the flame retardancy is improved. However, it causes a problem that adversely affects the nucleolation reaction of polyisocyanate and the spray foaming operation. By the way, the phosphorus concentration in the composition B can be determined as follows. First, the content of P (phosphorus atom) in each compound of the added flame retardant (organic phosphate ester or phosphorus-containing flame retardant) is measured or calculated as the phosphorus concentration (% by mass). In the case of this calculation, the phosphorus concentration of each flame retardant is calculated according to the formula [total atomic weight of P in the compound] ÷ [molecular weight of the compound] × 100 (%). Next, the phosphorus concentration in each composition B is calculated from the amount of each flame retardant added, and the total phosphorus concentration of each flame retardant is calculated to obtain the phosphorus concentration in composition B. Of course, it is also possible to directly measure the phosphorus concentration (total amount) from the composition B containing the flame retardant by quantitative analysis. Then, ICP emission spectroscopic analysis, fluorescent X-ray analysis, Auger electron spectroscopy and the like are used for such quantitative analysis.

Further, in the composition A or the composition B constituting the effervescent composition for the flame retardant polyisocyanurate foam according to the present invention, in addition to the above-mentioned compounding components or contained components, the polyisocyanurate (resin) produced is further added. ) Is compounded, and in addition, various conventionally known auxiliary agents such as known foam stabilizers and other flame retardants are appropriately selected as necessary. It is also possible to mix them.

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

For example, as the hydrofluorocarbon (HFC) of the fluorocarbon-based foaming agent, which is one of the foaming agents that can be used in the present invention, difluoromethane (HFC32) and 1,1,1,2,2-pentafluoroethane (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), 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC4310mee) and the like.

Further, examples of the hydrocarbon (HC), which is one of the non-CFC foaming agents preferably used in the present invention, include normal pentane, isopentane, cyclopentane, isobutane and the like. Further, as the hydrofluoroolefin (HFO), for example, pentafluoropropene such as 1,2,3,3,3-pentafluoropropene (HFO1225ye), 1,3,3,3-tetrafluoropropene (HFO1234ze), and the like. Tetrafluoropropene such as 2,3,3,3-tetrafluoropropene (HFO1234yf), 1,2,3,3-tetrafluoropropene (HFO1234ye), and birds 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. In addition, examples of the hydrochlorofluoroolefin (HCFO) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) and 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). , Dichlorotrifluoropropene (HCFO1223) and the like. 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.

In the present invention, water can be used as the foaming agent in addition to the above-mentioned ones. However, since water reacts with polyisocyanates, such water cannot be present in composition A, and when it becomes present in composition B, such composition B becomes present. When it is mixed with the composition A containing polyisocyanate and reacted, the water reacts with the polyisocyanate, the polyisocyanate is consumed, and the polyisocyanate in the reaction system is reduced. The total amount of isocyanurate rings may be reduced, leading to a decrease in the flame retardancy of the polyisocyanurate foam produced. For this reason, it is desirable that the effervescent composition according to the present invention contains substantially no water. Here, the term "substantially free of water" means that the content of water in each composition is less than 0.1% by mass. Even if a trace amount of water of less than 0.1% by mass is detected in each composition, it is considered as an error and it is judged that water is not contained. In addition, when water is contained, it is permissible within the range where the flame retardancy does not decrease, and the content of water in the composition B is generally 1% by mass or less, preferably 0.5% by mass or less. , Will be adjusted.

By the way, the above-mentioned foaming agent contained in the effervescent composition for flame retardant polyisocyanurate foam according to the present invention is generally about 40 to 100 parts by mass with respect to 100 parts by mass of the above-mentioned liquid organic phosphoric acid ester. It is desirable that it is used in a proportion of about 50 to 90 parts by mass. If the content of the foaming agent is too small, the foaming characteristics deteriorate, for example, there is a problem that sufficient foaming cannot be obtained by spray foaming, and if it is too large, the foam shrinks or the like. It will cause problems.

Further, the foam stabilizer is used to uniformly arrange the cell structure of the polyisocyanurate 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 is 0.5 to 5% by mass in the composition B. It is selected in the range of about 1 to 3% by mass, preferably about 1 to 3% by mass.

A composition containing the polyisocyanate-containing composition A obtained as described above, a composition containing at least a trimerization catalyst as a catalyst, and further containing a liquid organic phosphoric acid ester and a powdery phosphorus-containing flame retardant. By mixing them with B in volume ratio, generally at a ratio of composition A: composition B = 2: 1 to 1: 1 in the absence of the polyol, by a trimerization catalyst. The desired polyisocyanurate foam is formed by the isocyanurate-forming reaction of the polyisocyanate and the foaming by the foaming agent.

In forming such polyisocyanurate foam, various known methods for producing polyurethane foam can be adopted as they are, and for example, a mixture of these compositions A and composition B is applied onto the face material. Then, it is injected into a laminated continuous foaming method that foams and cures in a plate shape, in a space where heat insulation is required such as an electric refrigerator, in a honeycomb structure of a lightweight and high-strength board, in a void generated in civil engineering work, etc. A foamable composition according to the present invention by an injection foaming method of filling and foaming / curing, or a spray foaming method of spraying from a spray gun head of an on-site foaming machine onto a predetermined adherend (structure) to foam / cure. Is foamed and cured to form the desired polyisocyanurate foam.

In this way, the polyisocyanurate foam (foam) formed by mixing the composition A and the composition B according to the present invention, foaming and curing them is a resin. Based on the isocyanurate structure and the synergistic action of the organic phosphate ester as a flame retardant and the phosphorus-containing flame retardant, while reducing the combustibles constituting the foam to the limit by not using the polyol as a component. Since it is effectively realized as a foam capable of exhibiting a high degree of flame retardancy even in the presence of a skin layer, a non-combustible material specified by Japan's Building Standards Law is advantageously provided. I got it.

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, self-fire extinguishing time, and the state of surface cracks after the combustion test obtained in the following examples and comparative examples are as follows. Evaluation or measurement.

(1) Measurement of maximum heat generation rate and total heat generation amount From the polyisocyanurate foam layer (thickness: about 60 mm) obtained by spray foaming in Examples and Comparative Examples, the skin layer on the foam surface remains. , Cut out so as to be a test piece having a wall thickness of 50 mm, and collect a polyisocyanurate foam test piece having a size of 100 mm × 100 mm × 50 mm.

Next, the maximum heat generation rate and total heat generation amount when the ^{collected test piece was heated for 20 minutes at a radiant heat intensity of 50 kW / m 2} in accordance with the combustion test method specified in ISO-5660. , Each measure. Then, the case where the maximum heat generation rate is 200 kW / m ² or less and the case where the total heat generation amount is 8 MJ / m ² or less are accepted.

(2) Density measurement The dimensions of the test pieces cut out from the polyisocyanurate foam layer are accurately measured using a caliper, while the mass is measured using an electronic balance to obtain them. From the measured values obtained, the density of the sample (foam) is calculated according to JIS K7222.

(3) Measurement of self-extinguishing time The time from ignition by heating to extinguishing the fire when the combustion test conforming to the ISO-5660 was carried out was measured.

(4) Evaluation of the state of cracks (residues) If no cracks are found on the surface of the test piece after the test, which is obtained when the combustion test conforming to the ISO-5660 is performed, "○" is displayed. If cracks are observed on the surface thereof, it is evaluated as "x", and if the cracks reach the back surface of the test piece, it is evaluated as "XX".

First, the following various raw materials were prepared as the components used in the following examples and comparative examples.
Polyol compound: Phthalic acid-based polyester polyol (RDK133 manufactured by Kawasaki Kasei Chemicals, Inc., hydroxyl value: 315 mgKOH
/ G)
Triquantization catalyst: quaternary ammonium salt (U-CAT18X manufactured by San Apro)
: Quaternary ammonium salt (Kao Corporation Kaorizer No.
.. 420)
Resinification catalyst: Bismuth octylate (Pucat 2 manufactured by Nihon Kagaku Sangyo Co., Ltd.)
5)
Flame Retardant: Organic Phosphate Ester: TCPP (Wanshan Tris (1-chloro-2-propyl) Phosphate: Liquid, Phosphorus Concentration: 9.5% Content)
: Organic Phosphate Ester: Polyphosphoric Acid Ester (ADEKA Corporation)
Made by Adecaster PFR: Liquid, Phosphorus concentration: 10.9% by mass)
: Organic Phosphate Ester: Tris (Tribromoneopentyl) phosphate (CR-900 manufactured by Daihachi Chemical Industry Co., Ltd .: Powder, Phosphorus concentration: 3.0% by mass)
: Red phosphorus (Nova Excel 140 manufactured by Rin Kagaku Kogyo Co., Ltd., phosphorus concentration: 94% by mass, average particle size: 24-36 μm)
: Red phosphorus (Nova Red 120 manufactured by Rin Kagaku Kogyo Co., Ltd., phosphorus concentration:
85% by mass, average particle size: 20 to 30 μm)
: Ammonium dihydrogen phosphate (Wako Pure Chemical Industries, Ltd., average particle size: 5 μm, phosphorus concentration: 27% by mass)
: Ammonium polyphosphate (E, manufactured by Clariant Chemicals, Inc.)
XOLITAP422, average particle size: 15 μm, phosphorus concentration: 31
mass%)
: Aluminum diethyl phosphinate (EXOLIT OP930 manufactured by Clariant Chemicals Co., Ltd., average particle size (D ₅₀ ): 3 ~
5 μm, phosphorus concentration: 23% by mass)
: Aluminum diethyl phosphinate (EXOLIT OP935 manufactured by Clariant Chemicals Co., Ltd., average particle size (D ₅₀ ): 2 to
3 μm, phosphorus concentration: 23% by mass)
Foaming agent: HCFO-1233zd (Honeywell 1-chloro-
3,3,3-trifluoropropene)
: HFO-1336mzz (Chemours 1,1,1,4)
, 4,4-Hexafluoro-2-butene)
: HFC365mfc (1,1,1,3,3-pentafluorobutane manufactured by SOLVAY)
: HFC245fa (manufactured by Central Glass Co., Ltd. 1,1,1,3)
3-Pentafluoropropane)
: Water defoaming agent: Silicone-based defoaming agent (Momentive Performance Materials Japan GK Niax Silicone L-6
100)

-Preparation of polyisocyanate composition (composition A)-
Polymeric MDI (Wannate PM-130 manufactured by Manka Kagaku Japan Co., Ltd.) was prepared as a polyisocyanate, and the composition A was composed only of this polyisocyanate.

-Preparation of catalyst composition (composition B)-
The various raw materials prepared above, that is, the trimerization catalyst, the resinification catalyst, the flame retardant (organic phosphate ester, red phosphorus, organic phosphinate), the foaming agent and the foam stabilizer are shown in Tables 1 to 3 below. Various catalyst compositions according to Examples 1 to 16 and Comparative Examples 1 to 9 were prepared as Composition B, respectively, by uniformly mixing them in the various combinations and blending ratios shown.

-Manufacturing of polyisocyanurate foam-
The various catalyst compositions obtained above and the polyisocyanate composition are used at a volume ratio of 1: 1 and mixed by an in-situ spray foaming machine (trade name: A-25, manufactured by Graco) to prepare an effervescent stock solution. Then, under the condition of atmospheric temperature: 15 ° C., the surface of the inorganic flexible board (910 mm × 910 mm) as an adherend was sprayed once with a bottom blow and once with a top blow, and foamed. -Various foam layers (thickness) according to Examples 1 to 16 and Comparative Examples 1 to 9, which are made of a hard isocyanate foam having a bottom blown layer of about 5 mm and a top blown layer of 50 to 60 mm by curing. : Approximately 60 mm) were prepared respectively.

Then, using the various polyisocyanurate foams thus obtained, the density, maximum heat generation rate, total heat generation amount, self-fire extinguishing time and state of cracks (residues) are measured or evaluated, respectively, and obtained. The results are summarized in Tables 1 to 3 below, respectively.

As is clear from the results of Tables 1 and 2, it comprises a combination of the polyisocyanate composition (composition A) and the catalyst composition (composition B) adopted in Examples 1 to 16 according to the present invention. All of the effervescent compositions have a highly flame-retardant polyisocyanurate foam having a total calorific value (20 minutes) of 8 MJ / m ^{2 or less in the combustion test method based on ISO-5660.} It was confirmed that the time from the onset of fire to the self-extinguishing of the fire was short. Further, it is understood that in each of the test pieces after the combustion test, no cracks are observed on the surface thereof, and high flame retardancy can be realized.

On the other hand, as is clear from the results shown in Table 3, a polyol is added to the catalyst composition (composition B) to be combined with the polyisocyanate composition (composition A), and such a polyol is added. In the foams of Comparative Examples 1 to 4 obtained by reacting with polyisocyanate, the desired high flame retardancy cannot be obtained, and the maximum heat generation rate and the total calorific value (20 minutes) are inferior. It became. Further, in Comparative Examples 5 to 6 in which the liquid organic phosphoric acid ester is not added and blended in the composition B, and Comparative Example 7 in which the powdery organic phosphoric acid ester is blended, the spraying operation can be performed. In addition, the foams obtained in Comparative Examples 8 to 9 in which an effective polyisocyanurate foam could not be obtained and the liquid organic phosphate ester was not combined with a powdery phosphorus-containing flame retardant were used. It was found that the values of the maximum calorific value and the total calorific value (20 minutes) were poor, and the cracks were remarkable, and it was difficult to form a polyisocyanulate foam having a high degree of flame retardancy.

Claims (15)

1. It is composed of a composition A containing a polyisocyanate and a polyol-free composition B containing at least a trimerization catalyst as a catalyst, and isocyanurateization of the polyisocyanate with the trimerization catalyst in the absence of a polyol. A foaming composition capable of forming a polyisocyanurate foam by the reaction and foaming with a foaming agent is obtained.
   A foamable composition for flame-retardant polyisocyanurate foam, wherein the composition B further contains a liquid organic phosphoric acid ester and a powdery phosphorus-containing flame retardant.
2. The effervescent composition for flame-retardant polyisocyanurate foam according to claim 1, wherein the phosphorus concentration in the composition B is adjusted to be 10 to 30% by mass.
3. The foam for flame-retardant polyisocyanurate foam according to claim 1 or 2, wherein the liquid organic phosphoric acid ester is contained in the composition B in a proportion of 25 to 60% by mass. Sex composition.
4. The flame-retardant polyisocyanurate according to any one of claims 1 to 3, wherein the liquid organic phosphoric acid ester is selected from the group consisting of a monophosphate ester and a condensed phosphoric acid ester. Foamable composition.
5. The foam for flame-retardant polyisocyanurate foam according to any one of claims 1 to 4, wherein the powdery phosphorus-containing flame retardant has an average particle size of 50 μm or less. Sex composition.
6. The flame-retardant polyisocyanurate foam according to any one of claims 1 to 5, wherein the powdery phosphorus-containing flame retardant is selected from the group consisting of red phosphorus and phosphate. Effervescent composition for.
7. The foaming for flame-retardant polyisocyanurate foam according to claim 6, wherein the phosphate is selected from the group consisting of monophosphate, pyrophosphate, polyphosphate, and organic phosphinate. Sex composition.
8. The flame-retardant polyisocyanurate foam according to any one of claims 1 to 7, wherein red phosphorus and an organic phosphinate are used in combination as the powdered phosphorus-containing flame retardant. Effervescent composition.
9. Any of claims 1 to 8, wherein the powdered phosphorus-containing flame retardant is contained in a ratio of 40 to 100 parts by mass with respect to 100 parts by mass of the liquid organic phosphoric acid ester. The effervescent composition for flame-retardant polyisocyanurate foam according to item 1.
10. The effervescent composition for flame-retardant polyisocyanurate foam according to any one of claims 1 to 9, wherein the trimerization catalyst is a quaternary ammonium salt or a carboxylic acid alkali metal salt. thing.
11. The flame retardant according to any one of claims 1 to 10, wherein the foaming agent is an organic foaming agent selected from the group consisting of hydrocarbons, hydrofluoroolefins and hydrochlorofluoroolefins. Effervescent composition for sex polyisocyanurate foam.
12. The foamable composition for flame-retardant polyisocyanurate foam according to any one of claims 1 to 11, wherein the foaming agent is contained in the composition B.
13. The invention according to any one of claims 1 to 12, wherein the foaming agent is used in a ratio of 40 to 100 parts by mass with respect to 100 parts by mass of the liquid organic phosphoric acid ester. Effervescent composition for flame-retardant polyisocyanurate foam.
14. Using the foamable composition for flame-retardant polyisocyanurate foam according to any one of claims 1 to 13, the foamable composition is sprayed onto the surface of a predetermined structure to foam. A method for producing a flame-retardant polyisocyanurate foam, which comprises forming a polyisocyanurate foam layer having a predetermined thickness on the surface of the structure by curing.
15. ^{When the polyisocyanurate foam layer 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 The method for producing a flame-retardant polyisocyanurate foam according to claim 14, which has a non-combustible property of .0 MJ / m ^{2 or less.}