JP2022155368A - Composition for flame-retardant foam - Google Patents

Abstract

To provide a composition for flame-retardant foam capable of achieving both high incombustibility and on-site workability while excluding a polyol component.SOLUTION: A composition for flame-retardant foam of the invention forms polyisocyanurate foam without using a polyol. The composition for flame-retardant foam contains a polyisocyanate, a trimerization catalyst for the polyisocyanate, a flame retardant, and a foaming agent and is composed of two or more liquid chemicals, wherein the polyisocyanate is contained in a liquid chemical and the flame retardant and the trimerization catalyst are contained in another liquid chemical. The flame retardant includes a liquid flame retardant and a solid flame retardant. The solid flame retardant includes red phosphorus and a water-releasing material.SELECTED DRAWING: None

Description

The present invention relates to flame retardant foam compositions. More particularly, it relates to flame retardant foam compositions that form polyisocyanurate foams without the use of polyols.

Conventionally, urethane foam is often used as a heat insulating material. However, since urethane, which is a constituent material, is easily flammable, there is a problem in that the conditions of use as foam are limited. Therefore, a method for imparting flame retardancy by adding a flame retardant or the like has been proposed.
On the other hand, Patent Literature 1 below discloses a technique for improving flame retardancy by not using a polyol among polyols and polyisocyanates that are raw materials for urethane.
Furthermore, Patent Document 2 below discloses a technique for improving flame retardancy by forming an isocyanurate ring from a polyisocyanate using a trimerization catalyst while using a polyol.

JP 2009-149760 A International Publication No. 2014-112394 pamphlet

Although the technique of Patent Document 1 achieves higher flame retardancy than urethane foam, it is at a level that clears semi-noncombustibility in ISO5660, and is not at a level that can clear noncombustibility. In addition, there is a problem that the construction situation is limited. That is, the technique of Patent Document 1 is a technique of collectively mixing raw material components for molding, and cannot be carried out on site. In the field of construction, civil engineering, etc., the gaps are filled by forming a heat insulating material by spraying on site, or by foam filling. That is, on-site construction eliminates the need for complicated operations such as gluing pre-measured and cut forms and stuffing them into gaps, and allows the required shape to be completely matched without any gaps. However, a composition that can be applied on site needs to be divided and stored to prevent reactions, but each divided raw material is an appropriate liquid so that each component can be quickly mixed in an appropriate amount during application. There is a need. In this respect, the technique of Patent Document 1 is insufficient.

On the other hand, the technique of Patent Literature 2 is considered to have excellent flame retardancy because of the examples that reach the level of noncombustibility, and is a technique that can be applied on site. However, there is a problem that the polyol component is essential and the polyol component cannot be eliminated. In other words, at least two liquid bases, a polyol component and a polyisocyanate component, are required to ensure on-site workability. Therefore, if the polyol component is excluded, there is a problem that on-site workability cannot be obtained and collective mixing is required as in the technique of Patent Document 1.

In general, a foam material has a core layer (body portion) containing a large number of foam cells and a skin layer (skin layer) formed on the surface of the core layer and substantially free of foam cells. The skin layer of the urethane foam obtained using is easily combustible because the material (resin) itself is combustible. When the skin layer burns, the amount of heat generated increases and the self-extinguishing property decreases. Therefore, there is a problem that it is difficult to achieve sufficient flame retardancy or non-combustibility while providing the skin layer. .

The present invention has been made in view of the above circumstances, and aims to provide a composition for a flame-retardant foam that can achieve both high flame retardancy and on-site workability while eliminating polyol components. aim.

That is, the present invention is as shown below.
[1] The flame-retardant foam composition of the present invention is a flame-retardant foam composition that forms a polyol-free polyisocyanurate foam,
comprising a polyisocyanate, a trimerization catalyst for said polyisocyanate, a flame retardant and a blowing agent;
Consisting of two or more chemical solutions, the polyisocyanate, the flame retardant and the trimerization catalyst are contained in different chemical solutions,
The flame retardant comprises a liquid flame retardant and a solid flame retardant,
The solid flame retardant comprises red phosphorus and a water-releasing material.
[2] In the flame-retardant foam composition of the present invention, the liquid flame retardant is 25 to 60% by mass when the total amount of the chemical containing the flame retardant is 100% by mass. can be done.
[3] In the flame-retardant foam composition of the present invention, the liquid flame retardant can be an organic phosphate ester.
[4] In the flame-retardant foam composition of the present invention, the total solid flame retardant is 100% by mass, the red phosphorus content is M _S1 (mass%), and the water-releasing substance content is When M _S2 (% by mass), M _S1 <M _S2 can be established.
[5] In the flame-retardant foam composition of the present invention, the red phosphorus can be in the form of particles having an average particle diameter of 15 μm or more.
[6] In the flame-retardant foam composition of the present invention, the water-releasing substance may be particulate with an average particle size of 35 μm or less.
[7] In the flame-retardant foam composition of the present invention, the average particle size of the red phosphorus may be larger than the average particle size of the water-releasing substance.
[8] In the flame-retardant foam composition of the present invention, the water-releasing substance can be one or more selected from metal hydroxides, inorganic hydrates and clay minerals.
[9] In the flame-retardant foam composition of the present invention, the liquid flame retardant may have a viscosity of 100 to 1000 mPa·s.
[10] In the flame-retardant foam composition of the present invention, the solid flame retardant may further contain a boron-based flame retardant.
[11] The composition for a flame-retardant foam of the present invention is composed of two types of chemical liquids, liquid A and liquid B,
The A liquid contains the polyisocyanate,
The B liquid contains the flame retardant and the trimerization catalyst,
The foaming agent may be contained in at least one of the A liquid and the B liquid.
[12] The composition for a flame-retardant foam of the present invention is composed of three types of chemical liquids, namely A liquid, B liquid and C liquid,
The A liquid contains the polyisocyanate,
The B liquid contains the flame retardant,
The C solution contains the trimerization catalyst,
The foaming agent may be contained in at least one of the A liquid, the B liquid, and the C liquid.
[13] The composition for a flame-retardant foam of the present invention is composed of three types of chemical liquids, A liquid, B liquid and C liquid,
The A liquid contains the polyisocyanate,
The B liquid contains the flame retardant and the trimerization catalyst,
The C liquid may contain the foaming agent.
[14] The composition for a flame-retardant foam of the present invention is composed of four chemical solutions, A, B, C and D,
The A liquid contains the polyisocyanate,
The B liquid contains the flame retardant,
The C solution contains the trimerization catalyst,
The foaming agent may be contained in the D liquid.

According to the composition for flame-retardant foam of the present invention, the object is to provide a composition for flame-retardant foam that achieves both high flame retardancy and on-site workability while eliminating polyol components. do.

The present invention will be described below. The remarks herein are intended to be illustrative and illustrative of the embodiments of the invention and are believed to be the most effective and readily comprehensible explanations of the principles and conceptual features of the invention. It is described for the purpose of providing what is available. In this regard, it is not intended to present any more than a certain degree of structural detail of the invention, which is necessary for a fundamental understanding of the invention, and that the present description may actually illustrate some aspects of the invention. It will be clear to those skilled in the art how it can be implemented.

The flame-retardant foam composition of the present invention (hereinafter also simply referred to as "this composition") is a flame-retardant foam composition that forms a polyol-free polyisocyanurate foam,
comprising a polyisocyanate, a trimerization catalyst for said polyisocyanate, a flame retardant and a blowing agent;
Consisting of two or more chemical solutions, the polyisocyanate, the flame retardant and the trimerization catalyst are contained in different chemical solutions,
The flame retardant comprises a liquid flame retardant and a solid flame retardant,
The solid flame retardant is characterized by containing red phosphorus and a water-releasing material.

(1) Polyisocyanate Polyisocyanate is an organic compound having two or more isocyanate groups (NCO groups) in the molecule. As the polyisocyanate, a monomer having two or more isocyanate groups (NCO groups) in the molecule may be used, or a polymer may be used. Furthermore, in the case of a multimer, the compound (monomer) constituting the multimer may be of only one type (mononuclear), or may be of two or more types (polynuclear). Furthermore, mixtures of monomers and multimers may be used. Polyisocyanate monomers include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and the like. These may use only 1 type and may use 2 or more types together.

Among the above aromatic polyisocyanates, diphenylmethane diisocyanate [2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate], tolylene diisocyanate [2,4-tri diisocyanate, 2,6-tolylene diisocyanate], phenylene diisocyanate [1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate], xylylene diisocyanate [1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate] , tetramethyl xylylene diisocyanate [1,4-tetramethyl xylylene diisocyanate, 1,3-tetramethyl xylylene diisocyanate], 3,3'-dimethyldiphenyl-4,4'-diisocyanate, naphthalene diisocyanate [1,5- naphthalene diisocyanate, etc.], dianisidine diisocyanate, isopropylidenebis[4-cyclohexylisocyanate], triphenylmethane diisocyanate, triphenylmethane triisocyanate, dimethyltriphenylmethanetetraisocyanate, tris(isocyanatophenyl)-thiophosphoric acid, and the like. These may use only 1 type and may use 2 or more types together.

Among the above, as the aliphatic polyisocyanate, hexamethylene diisocyanate [1,6-hexamethylene diisocyanate], trimethylhexamethylene diisocyanate [2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexa methylene diisocyanate], lysine diisocyanate, lysine triisocyanate, dimer acid diisocyanate, and the like. These may use only 1 type and may use 2 or more types together.
Furthermore, among the above, alicyclic polyisocyanates include 4,4′-dicyclohexylmethane diisocyanate, trans-1,4-cyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, methylcyclohexane diisocyanate [methylcyclohexane-2,4-diisocyanate , methylcyclohexane-2,6-diisocyanate], bis(isocyanatomethyl)cyclohexane [cis-1,3-(diisocyanatomethyl)cyclohexane, trans-1,3-(diisocyanatomethyl)cyclohexane, 1,4-(diisocyanatomethyl ) cyclohexane] and the like. These may use only 1 type and may use 2 or more types together.
Further, the various monomers described above may be modified products thereof (isocyanurate modified products, carbodiimide modified products, etc.), blocked products thereof, hydrogenated products thereof, and the like. Each of these may be used alone or in combination of two or more.

Among the above, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (monomeric MDI, polymeric MDI, crude MDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), bis(isocyanato Methyl)cyclohexane, isophorone diisocyanate (IPDI) and the like are preferred, and diphenylmethane diisocyanate (monomeric MDI, polymeric MDI, crude MDI) is more preferred.
In the polyisocyanate used, the isocyanate content is not limited, but can be, for example, 5 to 60% by mass, 10 to 50% by mass, 15 to 45% by mass, 20 to 40% by mass. % by mass.

(2) Trimerization catalyst The trimerization catalyst is a catalyst (isocyanurate catalyst) that promotes the formation of isocyanurate rings. That is, it is a catalyst (isocyanurate-forming catalyst) that promotes the trimerization of isocyanate groups. The trimerization catalyst is not particularly limited as long as it has the function of the trimerization catalyst. For example, quaternary ammonium salts, tertiary ammonium salts, nitrogen-containing aromatic compounds, carboxylic acid alkali metal salts (alkali metal organic acid salts), alkali metal oxides, alkali metal alkoxides and the like can be mentioned. These may use only 1 type and may use 2 or more types together.

Among the above, quaternary ammonium salts are composed of quaternary ammonium cations and other cations. Among these, the quaternary ammonium cation is not limited, and for example, aliphatic ammonium cations, alicyclic ammonium cations, hydroxylammonium cations, etc. can be used. These may use only 1 type and may use 2 or more types together.
Among these, tetraalkylammonium is mentioned as an aliphatic ammonium cation. That is, an ammonium cation with four alkyl groups. Each alkyl group can be independently a hydrocarbon group having 1 to 20 carbon atoms, but at least two or more alkyl groups among the four alkyl groups can be the same. Two or more alkyl groups can be the same. Examples of aliphatic ammonium cations having the same four alkyl groups include tetramethylammonium and tetraethylammonium. These may use only 1 type and may use 2 or more types together.

Further, examples of aliphatic ammonium cations having the same three alkyl groups include alkyltrimethylammonium and alkyltriethylammonium. These may use only 1 type and may use 2 or more types together.
Among them, alkyltrimethylammonium includes ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, heptyltrimethylammonium, octyltrimethylammonium, nonyltrimethylammonium, decyltrimethylammonium, undecyltrimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, tetradecyltrimethylammonium, heptadecyltrimethylammonium, hexadecyltrimethylammonium, heptadecyltrimethylammonium, octadecyltrimethylammonium and the like. These may use only 1 type and may use 2 or more types together.

Alkyltriethylammonium includes methyltriethylammonium, propyltriethylammonium, butyltriethylammonium, pentyltriethylammonium, hexyltriethylammonium, heptyltriethylammonium, octyltriethylammonium, nonyltriethylammonium, decyltriethylammonium, undecyltriethylammonium and dodecyl. triethylammonium, tridecyltriethylammonium, tetradecyltriethylammonium, heptadecyltriethylammonium, hexadecyltriethylammonium, heptadecyltriethylammonium, octadecyltriethylammonium and the like. These may use only 1 type and may use 2 or more types together. Also

In addition, alicyclic ammonium cations include 1-methyl-1-azania-4-azabicyclo[2,2,2]octanium, 1,1-dimethyl-4-methylpiperidinium, 1-methylmorpholinium, 1-methylpiperidinium and the like. These may use only 1 type and may use 2 or more types together.
Further, hydroxyammonium cations include (2-hydroxypropyl)trimethylammonium, hydroxyethyltrimethylammonium, trimethylaminoethoxyethanol, hydroxyethyl-2-hydroxypropyldimethylammonium and the like. These may use only 1 type and may use 2 or more types together.

On the other hand, the anions that constitute the quaternary ammonium salt are not limited, and organic anions and/or inorganic anions can be used. Among them, organic anions include formate group, acetate group, caproate group (hexanoate group), heptanoate group, octanoate group, octylate group (2-ethylhexanoate group), oleate group, and acrylic acid group. , methacrylic acid group, oxalic acid group, malonic acid group, succinic acid group, glutaric acid group, adipic acid group, benzoic acid group, toluic acid group, ethylbenzoic acid group, phenoxy group, methyl carbonate group, sulfonic acid group (alkylbenzene sulfonic acid group, toluenesulfonic acid group, benzenesulfonic acid group, etc.), phosphate group, and the like. These may use only 1 type and may use 2 or more types together. Examples of inorganic anions include halogen groups, hydroxy groups, hydrogen carbonate groups, carbonate groups, and the like. These may use only 1 type and may use 2 or more types together.

Catalysts containing such quaternary ammonium salts include, for example, the product names "U-CAT 18X" and "U-CAT 2313" (both manufactured by San-Apro Co., Ltd.), the product names "Kaorizer No. 410", "Kao Riser No. 420" (both manufactured by Kao Corporation) and the like. These may use only 1 type and may use 2 or more types together.

Among the above, the tertiary ammonium salts include trimethylammonium salts, triethylammonium salts, triphenylammonium salts and the like. These may use only 1 type and may use 2 or more types together. As the anion constituting the tertiary ammonium salt, the anions exemplified as the anions constituting the quaternary ammonium salt can be similarly used.

Among the above, the carboxylic acid alkali metal salt is a salt of a carboxylic acid and an alkali metal. Among these, the carboxylic acid is preferably an aliphatic carboxylic acid having 1 to 8 carbon atoms. More specific examples include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, and octylic acid. These may use only 1 type and may use 2 or more types together. On the other hand, alkali metals include lithium, potassium, sodium and the like. These may use only 1 type and may use 2 or more types together. More specific examples include potassium acetate, potassium octylate, potassium caprylate and the like. In addition, examples of carboxylic acid metal salts include iron oxalate and the like. These may use only 1 type and may use 2 or more types together.

Among the above, nitrogen-containing aromatic compounds include aromatic compounds having a tertiary amino group as a functional group (aromatic tertiary amines). The tertiary amino group is a group represented by —NR ₂ R ₃ , R ₂ and R ₃ are each a linear, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms, and more preferably, the tertiary amino group is a functional group represented by —R ₁ —NR ₂ R ₃ , where R ₁ is a linear or branched hydrocarbon having 1 to 6 carbon atoms is the base. That is, the tertiary amino group includes dimethylaminomethyl group, dimethylaminoethyl group, dimethylaminopropyl group, diethylaminomethyl group, diethylaminoethyl group, diethylaminopropyl group and the like. These may use only 1 type and may use 2 or more types together. The aromatic ring constituting the nitrogen-containing aromatic compound may be a monocyclic ring (benzene, phenol, toluene, xylene, etc.) or a heterocyclic ring (triazine, etc.). The number of tertiary amino groups substituted on the aromatic ring is not limited, and may be 1-6, preferably 2-4. Specific examples include tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, tris(dimethylaminopropyl)hexahydrotriazine and the like.

Among the trimerization catalysts described above, it is preferable to use at least one of quaternary ammonium salts and alkali metal carboxylates in the present invention. Better flame retardancy can be obtained by using these. Moreover, in the present invention, when a quaternary ammonium salt is used, only one kind may be used, but it is more preferable to use two or more kinds of quaternary ammonium salts in combination. This allows the density of the resulting foam to be reduced while still providing superior flame retardancy. In addition, the workability can be improved by reducing the density.

Although the blending amount of the trimerization catalyst is not limited, when the total polyisocyanate contained in the present composition is 100 parts by mass, the trimerization catalyst can be 0.5 parts by mass or more and 10 parts by mass or less. Within this range, the present composition can effectively promote the trimerization (isocyanurate formation) of isocyanate groups and obtain excellent flame retardancy. In addition, it is possible to obtain a curing speed corresponding to a wide range of construction methods. This amount is preferably 0.7 parts by mass or more and 9.0 parts by mass or less, more preferably 1.0 parts by mass or more and 6.0 parts by mass or less, and 1.2 parts by mass or more and 4.0 parts by mass or less. is more preferable, 1.3 parts by mass or more and less than 3.0 parts by mass is particularly preferable, and 1.4 parts by mass or more and 2.9 parts by mass or less is particularly preferable. Within these preferred ranges, it is possible to obtain a curing rate excellent in on-site workability while achieving a higher degree of flame retardancy due to isocyanuration in the resulting flame-retardant foam.

In the present invention, the above trimerization catalyst may be used alone, but a resinification catalyst may be used in combination. The combined use of a resinification catalyst can reduce or prevent stickiness of the obtained flame-retardant foam. Examples of the resinification catalyst include organometallic compounds of group 14-15 metals. Specific examples include metal organic acid salts and organometallic compounds. Examples of the Group 14-15 metals include bismuth, tin, and lead. On the other hand, an aliphatic carboxylic acid having 5 to 15 carbon atoms can be used as the organic acid constituting the metal organic acid salt. Examples include hexanoic acid, heptanoic acid, octylic acid (2-ethylhexyl acid), decanoic acid, neodecanoic acid, naphthenic acid and the like. Specific examples include bismuth octylate, bismuth neodecanoate (bismuth neododecanoate), bismuth naphthenate, lead naphthenate, tin octylate, and lead octylate. These may use only 1 type and may use 2 or more types together.
Moreover, an organic tin compound is mentioned as an organometallic compound. Specific examples include dibutyltin compounds (dibutyltin dilaurate, etc.), dioctyltin compounds (dioctyltin malate, dibutyltin oxide, etc.). These may use only 1 type and may use 2 or more types together.

When using a resinification catalyst, the amount thereof is not limited, but when the total amount of polyisocyanate contained in the present composition is 100 parts by mass, the resination catalyst should be 0.01 parts by mass or more and 5 parts by mass or less. be able to. Within this range, the composition of the present invention can reduce the stickiness of the obtained flame-retardant foam while achieving both flame retardancy and on-site workability. This amount is preferably 0.02 parts by mass or more and 5.5 parts by mass or less, more preferably 0.06 parts by mass or more and 4.0 parts by mass or less, and 0.10 parts by mass or more and 3.5 parts by mass or less. is more preferable, 0.13 parts by mass or more and less than 3.0 parts by mass is particularly preferable, and 0.16 parts by mass or more and 2.5 parts by mass or less is particularly preferable. Within these preferred ranges, stickiness of the obtained flame-retardant foam can be further reduced or prevented while achieving both flame retardancy and on-site workability.

In the present invention, in addition to the above resinification catalyst, the trimerization catalyst described above and an amine-based catalyst not included in the resinification catalyst can be used in combination with the trimerization catalyst. The combined use of an amine-based catalyst can reduce or prevent stickiness of the resulting flame-retardant foam. In addition, workability can be improved by reducing odor. Examples of amine catalysts include reactive amine compounds having OH groups and/or NH groups, cyclic amine compounds having a cyclic structure, and the like. These may use only 1 type and may use 2 or more types together. Among these, more effective odor reduction can be obtained by using a reactive amine compound.

Examples of reactive amine compounds include 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. These may use only 1 type and may use 2 or more types together.
Cyclic amine compounds include 1,2-dimethylimidazole, 1-isopropyl-2-methylimidazole, triethylenediamine, N,N'-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, methylenebis(dimethylcyclohexyl)amine, N,N-dimethylbenzylamine, morpholine, N-methylmorpholine, N-ethylmorpholine, N-(2-dimethylaminoethyl)morpholine, 4,4'-oxydiethylenedimorpholine, N,N' -diethylpiperazine, N,N'-dimethylpiperazine, N-methyl-N'-dimethylaminoethylpiperazine, 1,8-diazobicyclo(5,4,0)-undecene-7 and the like. These may use only 1 type and may use 2 or more types together.

When using an amine-based catalyst, the amount is not limited, but when the total polyisocyanate contained in the present composition is 100 parts by mass, the amine-based catalyst should be 0.01 parts by mass or more and 7 parts by mass or less. be able to. Within this range, the present composition can obtain the effect of reducing the stickiness of the resulting flame-retardant foam and the effect of improving workability by reducing odor. This amount is preferably 0.02 parts by mass or more and 6.5 parts by mass or less, more preferably 0.06 parts by mass or more and 5.0 parts by mass or less, and 0.10 parts by mass or more and 4.0 parts by mass or less. is more preferable, 0.13 parts by mass or more and less than 3.0 parts by mass is particularly preferable, and 0.16 parts by mass or more and 2.5 parts by mass or less is particularly preferable. Within these preferred ranges, the stickiness reduction effect of the obtained flame-retardant foam and the workability improvement effect due to the odor reduction can be obtained more prominently.

(3) Flame Retardant In the present composition, the flame retardant is a component that imparts flame retardancy to the resulting foam. The flame retardants include liquid flame retardants and solid flame retardants.

(3-1) Liquid flame retardant The liquid flame retardant is a flame retardant that is liquid at a temperature of 0 to 40°C. That is, it is a flame retardant that has fluidity (below the temperature at which it does not decompose) at a temperature of 0 to 40°C. Although the degree of fluidity is not limited, it preferably has a viscosity of 50 mPa·s or more as measured at 25° C. using a Brookfield viscometer according to JIS K7117-1. Although the upper limit of this viscosity is not limited, it can be, for example, 10000 mPa·s or less.

Generally, even a polyisocyanurate foam composition requires a liquid polyol in the same way as a polyurethane foam composition, in order to obtain a composition that can be applied in situ. This is because a liquid-partitioned composition is required for field applicability. That is, in order to perform on-site construction, it is necessary to divide the components so that they do not react with each other. On the other hand, it is preferable that the composition before mixing is divided into 2 to 5 kinds, because even if the number of divisions is large, the preparation on site becomes complicated. Furthermore, in order to ensure that each component is mixed in an appropriate ratio, the divided liquid composition must contain the necessary ingredients in an appropriate amount in advance, and the appropriate fluidity must be maintained in the mixture. There is By dividing the composition in a liquid state in this way, the desired foam can be obtained on site by simply mixing. However, as described above, since liquid division requires various conditions, the degree of freedom of division is narrower than is possible. Therefore, even polyisocyanurate foam compositions currently require a polyol as a liquefied base.
Therefore, if the polyol is not used, the above-mentioned polyol cannot be used as a liquefying base, resulting in a problem that the liquid division that can be applied on site cannot be performed. In this regard, in the present composition, a liquid flame retardant can be used as part of the flame retardant, and this liquid flame retardant can be used as a liquefied base in place of the polyol. This makes it possible to enable field-installable liquid division.

Organic phosphoric acid esters, halogenated paraffins, and the like can be used as such liquid flame retardants. Among these, the organic phosphate includes organic phosphate monoester, organic phosphate diester, and organic phosphate triester. These may use only 1 type and may use 2 or more types together. Furthermore, organic phosphates include monophosphates and condensed phosphates. These may use only 1 type and may use 2 or more types together.

Specific examples of monophosphates include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, and tris(chloropropyl) phosphate. [Tris(1-chloro-2-propyl)phosphate], tributylphosphate, tri(2-ethylhexyl)phosphate, tributoxyethylphosphate, triphenylphosphate, tris(isopropylphenyl)phosphate, tris(phenylphenyl)phosphate, trinaphthyl Phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyl Oxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resylcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), phosphaphenanthrene, and the like. These may use only 1 type and may use 2 or more types together.
Condensed phosphoric acid esters include trialkyl polyphosphate, resorcinol polyphenyl phosphate, hydroquinone poly(2,6-xylyl) phosphate, condensates thereof, and the like. These may use only 1 type and may use 2 or more types together.

Among liquid flame retardants, phosphate-based liquid flame retardants are, for example, product names "ADEKA STAB PFR", "ADEKA STAB FP-900L", "ADEKA STAB FP-600" (all manufactured by ADEKA Corporation), product names "CR- 504L", "CR-570", "CR-733S", "CR-741", "DAIGUARD-540", "DAIGUARD-580", "DAIGUARD-610", "DAIGUARD-880" (all are Daihachi Chemical manufactured by Kogyosha). These may use only 1 type and may use 2 or more types together.

Although the viscosity of the liquid flame retardant is not limited, as described above, it is usually preferable that the viscosity measured at 25° C. using a Brookfield viscometer conforms to JIS K7117-1 and is 50 mPa s or more, Furthermore, it is more preferably 100 mPa·s or more. When the viscosity of the liquid flame retardant is 100 mPa·s or more, the stability over time of the liquid chemical containing the liquid flame retardant can be improved. Although the upper limit of the viscosity of the liquid flame retardant is not limited, it is preferably 5000 mPa·s or less. Within this range, the present composition can achieve both high flame retardancy and on-site workability while excluding polyol components. The viscosity is preferably 100 to 4000 mPa·s, more preferably 100 to 3000 mPa·s, even more preferably 100 to 2000 mPa·s, particularly preferably 120 to 1500 mPa·s, and most preferably 150 to 1000 mPa·s. Within these preferred ranges, it is possible to achieve both high flame retardancy and on-site workability while excluding polyol components.
The viscosity of the liquid flame retardant can be adjusted at the time of blending by mixing a plurality of liquid flame retardants together or by mixing a solvent or the like when preparing the present flame-retardant foam composition.

Although the amount of the liquid flame retardant is not limited, the content of the liquid flame retardant M _L is 20 to 80% by mass when the total amount of the chemical solution containing the flame retardant is 100% by mass. can be Within this range, the present composition can achieve both high flame retardancy and on-site workability while excluding polyol components. This proportion M _L is further preferably 20 to 75% by mass, more preferably 20 to 70% by mass, even more preferably 25 to 65% by mass, particularly preferably 25 to 60% by mass, especially 30 to 60% by mass. preferable. Within these preferred ranges, it is possible to achieve both flame retardancy and on-site workability at a higher level while excluding polyol components, and to carry out favorable spraying work on-site.

(3-2) Solid Flame Retardant The composition contains red phosphorus and a water-releasing substance as a solid flame retardant. A solid flame retardant is a flame retardant that is solid at temperatures between 0 and 40°C. That is, it is a flame retardant with a defined shape and volume that does not have fluidity (below the temperature at which it does not decompose) at temperatures between 0 and 40°C. That is, the solid flame retardant is a flame retardant whose viscosity cannot be measured with a Brookfield viscometer.
The solid flame retardant does not have fluidity and preferably has a property that can be processed as a finely divided solid (granular, flaky, powdery, etc.).

The amount of the solid flame retardant compounded is not limited, but among the chemical solutions constituting the present composition, the total chemical solution containing the flame retardant is 100% by mass, the content of the liquid flame retardant is _ML (% by mass), and the solid flame retardant is When the fuel content is M _S (% by mass), M _L ≦M _S may be satisfied, but M _L >M _S is preferable. That is, it is preferable to contain more liquid flame retardants than solid flame retardants in terms of mass. In the present composition, by using a liquid flame retardant in combination, it is possible to achieve both high flame retardancy and on-site workability while eliminating the polyol component within this range. Furthermore, when this ratio is converted as M _S /M _L , it is more preferable that 0.10 ≤ M _S /M _L ≤ 0.90, and 0.20 ≤ M _S /M _L ≤ 0.75. More preferably, 0.30≦M _S /M _L ≦0.65 is particularly preferred, and 0.35≦M _S /M _L ≦0.55 is particularly preferred. Within these preferred ranges, combined use of a liquid flame retardant makes it possible to achieve both high flame retardancy and on-site workability while eliminating the polyol component.

(3-2-1) Red phosphorus Red phosphorus reacts with water and carbon produced by combustion of combustible gas generated by thermal decomposition of resin to form a carbonized layer on the surface of the resin. Red phosphorus alone may be used, the carbonized layer of which has a digestive effect by blocking oxygen, but red phosphorus having a covering layer (coating layer) may also be used. By having the coating layer, the handleability and workability are improved. Moreover, the dispersibility in the obtained flame-retardant foam can be enhanced, and the addition effect can be improved. The coating layer may be made of any material, but is particularly made of resin, metal hydroxide, metal oxide, or the like. Among these resins, a thermosetting resin can be suitably used. Specific examples include phenol resins, furan resins, xylene-formaldehyde resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, aniline resins, and silicone resins. These may use only 1 type and may use 2 or more types together. Metal hydroxides include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide and the like. These may use only 1 type and may use 2 or more types together. Furthermore, examples of metal oxides include aluminum oxide, magnesium oxide, zinc oxide, and titanium oxide. These may use only 1 type and may use 2 or more types together. In the case of red phosphorus having a coating layer on the particle surface, the ratio of the coating layer to the whole is not limited. be able to.

Such red phosphorus is, for example, the product name “Novared”, the product name “Novaxcel”, the product name “Novaquel” (all manufactured by Rin Kagaku Kogyo Co., Ltd.), the product name “HISHIGUARD” (manufactured by Nippon Kagaku Kogyo Co., Ltd.), the product name It is available as "EXOLIT RP" (manufactured by Clariant Chemicals Co., Ltd.) and the like. These may use only 1 type and may use 2 or more types together.

The average particle size (R _P ) of red phosphorus used in the present composition is not limited, but is usually 1 to 100 μm, preferably 5 to 70 μm, more preferably 10 to 60 μm, but R _P is 10 μm or more, and It is more preferably 15 μm or more. Therefore, 15 to 50 μm is more preferable, 15 to 45 μm is particularly preferable, and 17 to 43 μm is particularly preferable.
Further, when the average particle diameter of red phosphorus is R _P (μm) and the average particle diameter of the water-releasing substance described later is R _W (μm), the size when these are compared is not limited. is preferably larger than the average particle size _RW of the water _- releasing substance. In this case, it is possible to prevent occurrence of reattachment flames more effectively than when R _P and R _W are equal or when R _P is smaller than R _W . More specifically, R _W /R _P is preferably less than 1, more preferably less than 0.9, even more preferably 0.8 or less, particularly preferably 0.7 or less, and particularly preferably 0.6 or less. On the other hand, the lower limit of R _W /R _P is not limited, but is usually 0.01 or more, and can be 0.05 or more.

Incidentally, the average particle size of red phosphorus and the average particle size of the water-releasing substance are usually determined within the composition for flame-retardant foam before blending into the composition for flame-retardant foam, and within the resulting flame-retardant foam. not changed in In addition, in the state before blending into the composition for flame-retardant foam, it is measured by a particle size distribution analyzer. In addition, the average particle size in the flame-retardant foam composition and in the resulting flame-retardant foam can be determined from the particle size distribution measured by a laser diffraction particle size distribution analyzer or the like. Specifically, using a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd. (product name: MT3200II)), the average particle size (D50) was defined as the particle size of 50% of the integrated value from the particle size distribution of the sample.

The amount of red phosphorus to be blended is not limited, but when the total solid flame retardant is 100% by mass, the amount of red phosphorus can be 1 to 90% by mass. Within this range, the present composition can achieve both high flame retardancy and on-site workability while excluding polyol components. This amount is preferably 24 to 80% by mass, more preferably 5 to 60% by mass, even more preferably 6 to 50% by mass, particularly preferably 7 to 45% by mass, and particularly preferably 8 to 40% by mass. . Within these preferred ranges, it is possible to achieve both high flame retardancy and on-site workability while excluding polyol components, and to form a good carbonized layer. In addition, from the viewpoint of suppressing ignition by red phosphorus itself, when the entire chemical solution (usually, liquid B) containing a solid flame retardant is 100% by mass, the content of red phosphorus is preferably 30% by mass or less, and 20% by mass. % or less is more preferable.

(3-2-2) Water Releasing Substance A water releasing substance is a substance that releases water when heated. More specifically, it is a substance that dehydrates when it reaches a predetermined temperature by heating, or that can cause dehydration when it decomposes. In addition, it usually has the property of absorbing heat during dehydration. This release of water and absorption of heat can speed up self-extinguishing, prevent flames from re-igniting after self-extinguishing, and reduce the amount of heat generated.
The temperature at which the water-releasing substance releases water is not limited, but for the purpose of flame retardancy, it is preferably above 100°C (usually 800°C or lower), and more preferably 150°C or higher. , 200° C. or higher is more preferable. The amount of water released is not limited, but the mass reduction rate (mass ratio of released water to the mass before water is released) is preferably 10% by mass or more (usually 50% by mass or less), more preferably 15% by mass or more. This mass reduction rate is measured by thermal mass spectrometry (TG).

The water-releasing substance is not limited as long as it can release water when heated, but inorganic compounds are preferable from the viewpoint of increasing the water-releasing temperature. Examples of inorganic compounds that are water-releasing substances include metal hydroxides, hydrates of metal compounds (excluding metal hydroxides), and clay minerals. These may use only 1 type and may use 2 or more types together.
Among them, metal hydroxides include aluminum hydroxide (aluminum hydroxide), alkaline earth metal hydroxides (magnesium hydroxide, calcium hydroxide, etc.), and metal hydroxides such as these hydrates. and hydrates thereof. These may use only 1 type and may use 2 or more types together. Examples of hydrates of metal compounds include calcium silicate hydrate, aluminum oxide hydrate, aluminum chloride hydrate, aluminum sulfate hydrate, magnesium chloride hydrate, and magnesium sulfate hydrate. . These may use only 1 type and may use 2 or more types together. Furthermore, clay minerals include clay, kaolin, hydrotalcite, and the like. These may use only 1 type and may use 2 or more types together. Among the above, metal hydroxides are preferred.

The average particle size (R _W ) of the water-releasing substance used in the present composition is not limited, but is usually 0.05 to 80 μm, preferably 0.1 to 50 μm, and _more preferably 35 μm or less. . Therefore, 0.1 to 35 μm is preferable, 0.3 to 30 μm is more preferable, 0.5 to 25 μm is still more preferable, and 0.7 to 20 μm is particularly preferable. Incidentally, the measurement of the average particle diameter is as described above.

The content of the water _{- releasing substance} is not _limited . However, it is preferable that M _S1 <M _S2 . That is, it is preferable to contain more water-releasing substances than red phosphorus in terms of mass. In the present composition, by using a liquid flame retardant in combination, it is possible to achieve both high flame retardancy and on-site workability while eliminating the polyol component within this range. Furthermore, when this ratio is converted as M _S2 /M _S1 , 0.6 ≤ M _S2 /M _S1 ≤ 30, and further 0.8 ≤ M _S2 /M _S1 ≤ 20, 1.05≦M _S2 /M _S1 ≦15 is preferred, and 1.5≦M _S2 /M _S1 ≦10 is more preferred. Within these preferred ranges, combined use of a liquid flame retardant makes it possible to achieve a higher degree of both flame retardancy and on-site workability while eliminating the polyol component, prevent reheating flames, and reduce the amount of heat generated. .

(3-2-3) Other Solid Flame Retardants The present composition may contain other solid flame retardants as solid flame retardants in addition to the red phosphorus and water-releasing substance described above. Other solid flame retardants include boron-based flame retardants, phosphate ester-based flame retardants, stannate metal salts, brominated flame retardants, chlorine-based flame retardants, antimony-containing flame retardants, and the like. These may use only 1 type and may use 2 or more types together.
On the other hand, since the present composition contains red phosphorus and a water-releasing substance as solid flame retardants, it can be used as a solid phosphate ester-based flame retardant, a stannate metal salt, among the other solid flame retardants described above. , brominated flame retardants, chlorine flame retardants, antimony-containing flame retardants, and the like. More specifically, for example, the content of other solid flame retardants other than the boron-based flame retardant is, for example, 20% by mass or less when the entire chemical solution containing the flame retardant is 100% by mass. , 10% by mass or less, 5% by mass or less, or 1% by mass or less.

Among the above, the boron-based flame retardant is preferable in the present composition. A boron-based flame retardant is a component containing a boron atom.
Examples include boric acids, borates, boron-based nonmetallic compounds, borate minerals, and organic boron-based compounds. These may use only 1 type and may use 2 or more types together.
Examples of boric acids include boric acid, orthoboric acid, and metaboric acid. Further, borate salts include salts of the above boric acids with metal ions and salts with ammonium ions. Among them, metal species constituting metal ions include sodium, potassium, calcium, magnesium, barium, aluminum, zinc and the like. Moreover, boron oxide, boron nitride, etc. are mentioned as a boron-type nonmetallic compound. Furthermore, borate minerals include borax, colemanite, ulexite, and the like. Examples of organic boron compounds include boric acid esters, boronates, boroxines, and the like. These may use only 1 type and may use 2 or more types together.
Among them, in the present composition, borates are preferable, metal salts of boric acid are more preferable, and zinc borate and alkaline earth metal borate are particularly preferable.

When a boron-based flame _retardant is used, its _blending amount is not limited. _{Although S1} ≥ M _S3 , it is preferable that M _S1 < M _S3 . That is, it is preferable that the amount of the boron-based flame retardant is the same as that of red phosphorus, or that the amount of the boron-based flame retardant is larger than that of red phosphorus in terms of mass. In addition, since the water-releasing substance and the boron-based flame retardant are used together, if the water-releasing substance contains more water-releasing substance than red phosphorus in terms of mass, the boron-based flame retardant is higher than red phosphorus in terms of mass. Less is better. In the present composition, by using a liquid flame retardant in combination, it is possible to achieve both high flame retardancy and on-site workability while eliminating the polyol component within this range. Furthermore, when this ratio is converted as M _S3 /M _S1 , it can be 0.1 ≤ M _S3 /M _S1 ≤ 2.5, and further 0.3 ≤ M _S3 /M _S1 ≤ 2.2. 0.4≦M _S3 /M _S1 ≦2.0, and more preferably 0.5≦M _S3 /M _S1 ≦1.5. Within these preferred ranges, combined use of a liquid flame retardant makes it possible to achieve both high flame retardancy and on-site workability while eliminating the polyol component.

The amount of the flame retardant (total of the liquid flame retardant and the solid flame retardant) is not limited. % by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, particularly preferably 75% by mass or more, particularly preferably 80% by mass or more, and Although the upper limit is not limited, it can be set to 100% by mass (for example, when a catalyst, a foaming agent, etc. are included in other chemicals, etc.). That is, among the chemical solutions constituting the present composition, the chemical solution containing the flame retardant can be composed only of the flame retardant. On the other hand, when the chemical solution contains components other than the flame retardant, it can be, for example, 99% by mass or less. This proportion can even be 95% by weight or less, and can be 90% by weight or less.

In addition, among other solid flame retardants other than boron-based flame retardants, examples of solid phosphate ester-based flame retardants include various monophosphates, pyrophosphates, polyphosphates, organic phosphinates, and the like. can be done.
Among these, monophosphates include phosphates, hydrogen phosphates, phosphites, hypophosphites, and the like. Cations constituting these salts include ammonium ions, alkali metal ions (sodium, potassium, lithium, etc.), alkaline earth metal ions (calcium, magnesium, barium, etc.), zinc ions, and the like.

Pyrophosphates include ammonium pyrophosphate, melamine pyrophosphate, acetoguanamine pyrophosphate, benzoguanamine pyrophosphate, acrylguanamine pyrophosphate, 2,4-diamino-6-nonyl-1,3,5-triazine pyrophosphate, 2,4-diamino-6-hydroxy-1,3,5-triazine pyrophosphate, 2-amino-4,6-dihydroxy-1,3,5-triazine pyrophosphate, 2,4-diamino-6 pyrophosphate -Methoxy-1,3,5-triazine, 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 pyrophosphate, 2-amino-4 pyrophosphate, 6-dimercapto-1,3,5-triazine and the like.
Furthermore, examples of polyphosphates include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate, and aluminum polyphosphate.

In addition, as the organic phosphinate, a structure in which one or two organic groups such as a linear alkyl group having 1 to 6 carbon atoms or a phenyl group are covalently bonded to a phosphorus atom constituting a phosphinic acid. Various known cations are bound to the organic phosphinic acid to form a salt form. Examples thereof include those in which a methyl group, an ethyl group, or a phenyl group is bonded to a phosphorus atom, and examples of metal elements constituting cations include Mg, Al, Ca, Ti, Zn, and the like. Specifically, zinc (mono or di)methylphosphinate, zinc (mono or di)ethylphosphinate, zinc (mono or di)phenylphosphinate, aluminum (mono or di)methylphosphinate, (mono or di) Examples include aluminum ethylphosphinate, aluminum (mono- or di)phenylphosphinate and the like.

The stannate metal salts include zinc stannate, barium stannate, sodium stannate, potassium stannate, cobalt stannate and magnesium stannate.
Further, the brominated flame retardants include brominated organic compounds. Brominated organic compounds include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromphenoxy)ethane, ethylenebis (pentabromophenyl), ethylenebis(tetrabromophthalimide), tetrabromobisphenol A, brominated polycarbonate, brominated epoxy compound (brominated epoxy resin), poly(brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, condensates of cyanuric chloride and brominated phenol, brominated polystyrene, brominated polymethylstyrene and the like.

Solid chlorinated flame retardants include chlorinated polyphenyl, chlorinated polyethylene, diphenyl chloride, triphenyl chloride, chlorinated paraffin, pentachlorinated fatty acid ester, perchloropentacyclodecane, chlorinated naphthalene, tetrachlorophthalic anhydride, and the like. is mentioned.
Furthermore, antimony-containing flame retardants include antimony oxides such as antimony trioxide and antimony pentoxide; antimonates such as sodium antimonate and potassium antimonate; pyroantimonates such as sodium pyroantimonate and potassium pyroantimonate; is mentioned.

(4) Foaming Agent The foaming agent is a component that forms the foamed state of the resulting flame-retardant foam. The type of foaming agent is not limited, and for example, an organic foaming agent, an inorganic foaming agent, or the like can be used. These may use only 1 type and may use 2 or more types together.

Among these, as the organic foaming agent, non-fluorocarbon/fluorocarbon foaming agents and sources of non-fluorocarbon/fluorocarbon foaming agents can be used. Specifically, fluorocarbons are hydrofluorocarbons (HFC), non-fluorocarbons are hydrocarbons (HC), and halogenated olefins (halogenated alkenes) called hydrofluoroolefins (HFO) and hydrochlorofluoroolefins (HCFO) etc. These may use only 1 type and may use 2 or more types together.

Of these, hydrocarbons include propane, normal pentane, isopentane, cyclopentane, butane, isobutane, hexane, isohexane, neohexane, heptane, and isoheptane. Hydrofluorocarbons specifically include difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,1-trifluoroethane (HFC143a), 1, 1,2,2-tetrafluoroethane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), 1,1,1,2,3,3,3 -heptafluoropropane (HFC227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluorobutane (HFC365mfc), and 1,1,1,2 , 2,3,4,5,5,5-decafluoropentane (HFC4310mee), dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like. Further, the halogenated olefins include, for example, unsaturated hydrocarbon derivatives having 2 to 6 carbon atoms having fluorine and/or chlorine halogen substituents, and further fluorine and/or chlorine halogen substituents. Alkenes having 3 or more and 6 or less carbon atoms (propene, butene, pentene, hexene, etc.) can be mentioned. Specific examples include tetrafluoropropene, pentafluoropropene, hexafluorobutene, fluorochloropropene, trifluoromonochloropropene, and fluorochlorobutene.

Examples of hydrofluoroolefins (HFO) include pentafluoropropenes such as 1,2,3,3,3-pentafluoropropene (HFO1225ye); 1,3,3,3-tetrafluoropropene (HFO1234ze), 2, Tetrafluoropropenes such as 3,3,3-tetrafluoropropene (HFO1234yf) and 1,2,3,3-tetrafluoropropene (HFO1234ye); Trifluoropropenes such as 3,3,3-trifluoropropene (HFO1243zf) tetrafluorobutene isomers (HFO1354); pentafluorobutene isomers (HFO1345); hexafluorobutene isomers such as 1,1,1,4,4,4-hexafluoro-2-butene (HFO1336mzz) ( HFO1336) types; heptafluorobutene isomers (HFO1327) types; heptafluoropentene isomers (HFO1447) types; octafluoropentene isomers (HFO1438) types;

Further, hydrochlorofluoroolefins (HCFO) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), Dichlorotrifluoropropene (HCFO1223), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), 1-chloro-1,3,3-trifluoropropene (HCFO-1233zb), 2-chloro- 1,3,3-trifluoropropene (HCFO-1233xe), 2-chloro-2,2,3-trifluoropropene (HCFO-1233xc), 3-chloro-1,2,3-trifluoropropene (HCFO- 1233ye), 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc) and the like.

On the other hand, examples of inorganic foaming agents include water and carbon dioxide. These may use only 1 type and may use 2 or more types together.
Among them, water functions as a foaming agent by generating carbon dioxide in coexistence with polyisocyanate. Therefore, as will be described later, when water is used as a foaming agent, it is preferable that water and polyisocyanate exist as different chemical solutions before foaming the present composition.
Carbon dioxide can also be used as liquefied carbon dioxide. Therefore, as will be described later, it is preferable that the present composition is allowed to exist alone as a chemical solution different from other components before foaming.

The amount of the foaming agent to be blended is not limited, and it can be appropriately blended depending on the density and expansion ratio of the desired flame-retardant foam. , the foaming agent can be 0.1 parts by mass or more and 100 parts by mass or less. The blending amount can further be 0.5 parts by mass or more and 70 parts by mass or less, further be 1 part by mass or more and 50 parts by mass or less, and further be 2 parts by mass or more and 40 parts by mass or less. It can be 3 parts by mass or more and less than 30 parts by mass, and further can be 5 parts by mass or more and 20 parts by mass or less.

The density of the flame-retardant foam is preferably 60 kg/m ³ or less, for example. It is more preferably 58 kg/m ³ or less, more preferably 55 kg/m ³ or less, and even more preferably 53 kg/m ³ or less. Although the lower limit of this density is not limited, it is preferably 45 kg/m ³ or more, more preferably 47 kg/m ³ or more, and even more preferably 48 kg/m ³ or more.

(5) Other Components In addition to the polyisocyanate, catalyst, flame retardant and foaming agent described above, other components may be blended in the present composition, if necessary. Other components include foam stabilizers, viscosity modifiers, fillers, and the like. These may use only 1 type and may use 2 or more types together.

(5-1) Foam Stabilizer A foam stabilizer is a component that improves the uniformity of foam cells that constitute the resulting flame-retardant foam. When using a foam stabilizer, the type of foam stabilizer is not limited, but examples include silicone foam stabilizers (silicone, etc.), nonionic surfactants, polyoxyalkylene-modified dimethylpolysiloxane, polysiloxane oxyalkylene copolymer Coalescence, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, lauryl fatty acid ethylene oxide adduct and the like can be used. These may use only 1 type and may use 2 or more types together. Among the foam stabilizers, for example, silicone-based foam stabilizers are preferred, and polyoxyalkylene-modified dimethylpolysiloxanes, polysiloxaneoxyalkylene copolymers, and the like can be preferably used.
When a foam stabilizer is used, the amount of the foam stabilizer is not limited. 0.5 parts by mass or more and 10 parts by mass or less.

(5-2) Viscosity Adjusting Agent The viscosity adjusting agent is a component that adjusts the viscosity of each chemical liquid constituting the present composition. As the viscosity modifier, for example, a viscosity reducer can be used. That is, viscosity-lowering components can be used. Although the type of viscosity reducing agent is not limited, for example, alcohols, ethers, esters, petroleum hydrocarbons and the like can be used. These may use only 1 type and may use 2 or more types together.
Among these, alcohols include methanol and ethanol. Ethers include ethyl cellosolve, butyl cellosolve, and the like. Examples of esters include cyclic esters such as propylene carbonate; esters (non-cyclic esters) such as dicarboxylic acid methyl ester and ethylene glycol monomethyl ether acetate.

(5-3) Filler A filler is a component that acts to increase the volume of the resulting flame-retardant foam and to improve the strength of the resulting flame-retardant foam. The type of filler is not limited, and inorganic fillers and organic fillers can be used. These may use only 1 type and may use 2 or more types together. Among these, inorganic fillers can be used more preferably from the viewpoint of improving flame retardancy. Although the type of inorganic filler is not limited, examples thereof include calcium carbonate, barium sulfate, silica, clay, talc, white carbon (diatomaceous earth) and the like. These may use only 1 type and may use 2 or more types together.

(6) Composition of chemical solution The present composition is composed of two or more chemical solutions. Further, in the composition, the polyisocyanate, the flame retardant and the trimerization catalyst are contained in different chemical solutions.
The present composition may be composed of two or more types of chemical solutions, usually composed of five types or less of chemical solutions, and preferably composed of four types or less of chemical solutions from the viewpoint of workability. More specifically, for example, it is possible to employ the following chemical liquid configurations <1> to <4>.

<1> Consists of two types of chemicals, liquid A and liquid B, liquid A containing a polyisocyanate, liquid B containing a flame retardant and a trimerization catalyst, and a blowing agent being one of the liquids A and B. It can be a composition contained in at least one. More specifically, <1-1> A composition may contain a polyisocyanate in A and a flame retardant, a trimerization catalyst and a foaming agent in B. Further, <1-2> A composition can be prepared in which the A liquid contains a polyisocyanate and a foaming agent, and the B liquid contains a flame retardant and a trimerization catalyst.

<2> Consists of three chemical solutions, A, B and C, with A containing polyisocyanate, B containing a flame retardant, C containing a trimerization catalyst, and a blowing agent. is contained in at least one of liquid A, liquid B and liquid C. More specifically, <2-1> A composition can be obtained in which a liquid A contains a polyisocyanate, a liquid B contains a flame retardant, and a liquid C contains a trimerization catalyst and a blowing agent. <2-2> A composition can be obtained in which the A liquid contains a polyisocyanate, the B liquid contains a flame retardant and a foaming agent, and the C liquid contains a trimerization catalyst. <2-3> A composition can be prepared in which the A liquid contains a polyisocyanate and a foaming agent, the B liquid contains a flame retardant, and the C liquid contains a trimerization catalyst.

<3> Consists of three chemical solutions, A, B and C, with A containing a polyisocyanate, B containing a flame retardant and a trimerization catalyst, and C containing a blowing agent. It can be a composition with This chemical composition can be said to be a suitable composition when carbon dioxide or the like is used as the foaming agent. In addition, A liquid and B liquid may contain foaming agents other than carbon dioxide as needed.

<4> Consists of four chemical solutions, A, B, C and D, with A containing a polyisocyanate, B containing a flame retardant, and C containing a trimerization catalyst. , a composition in which a foaming agent is contained in the D liquid. This chemical composition can be said to be a suitable composition when carbon dioxide or the like is used as the foaming agent. In addition, A liquid, B liquid, and C liquid may contain foaming agents other than carbon dioxide as needed.

It should be noted that, regardless of which of the chemical liquid compositions <1> to <4> is used, it is preferable that the chemical liquid containing polyisocyanate does not substantially contain water. Specifically, when the entire chemical solution containing polyisocyanate is 100% by mass, the content of water is 1% by mass (may be 0% by mass), or 0.5% by mass (may be 0% by mass) , and particularly preferably 0.1% by mass (may be 0% by mass).

Further, when the A liquid is a chemical solution containing polyisocyanate and the B liquid is a chemical solution containing a flame retardant, the viscosity of each of these A and B liquids is not limited, but conforms to JIS K7117-1, B type The upper limit of the viscosity measured at 25 ° C. using a viscometer can be 100,000 mPa s or less, preferably 50,000 mPa s or less, more preferably 10,000 mPa s or less, and 6,000 mPa ·s or less is more preferable, 5,000 mPa·s or less is particularly preferable, and 3,000 mPa·s or less is particularly preferable. For example, the lower limit can be 20 mPa·s or more, preferably 50 mPa·s or more, more preferably 100 mPa·s or more, and even more preferably 300 mPa·s or more.
Further, although the respective viscosities of liquid A and liquid B may differ, it is preferable that they do not differ excessively. More specifically, when the viscosity of liquid A is _VA (mPa·s) and the viscosity of liquid _B is VB (mPa·s), for example, 0.6 ≤ _VA / _VB ≤ 1 .4.

Furthermore, the reaction time (time from mixing to obtaining a flame-retardant foam) when the chemicals are mixed is preferably 20 minutes or less. When the reaction time is 20 minutes or less, it is possible to obtain a sufficient curing rate and a sufficient mechanical strength in the resulting cured body even at low temperatures such as in winter. Further, the reaction time is more preferably 10 seconds or more and 15 minutes or less, and even more preferably 20 seconds or more and 8 minutes or less. Within the above preferable range, it is possible to more reliably prevent clogging of the injection tube and to provide sufficient permeation time to the injection site after injection.

A flame-retardant foam can also be obtained from the present composition by filling a mold with a mixed liquid obtained by mixing the chemical liquids constituting the present composition and performing molding. On the other hand, as described above, the present composition is excellent in on-site workability. It is particularly preferably used in a mode in which a flame-retardant foam layer made of flame-retardant foam is formed on the surface. In addition, by spraying and filling the gaps formed in structures, etc., with a mixture of chemicals, or by mixing the chemicals in the device and filling the gaps, a filling made of a flame-retardant foam can be filled in the gaps. It is also preferably used in the mode of forming.

(7) Uses of the present composition The present composition may be used for any purpose, but due to its properties, it is particularly suitable for use in the field of construction and civil engineering (construction field and civil engineering field). That is, the present composition can be used, for example, as a composition for flame-retardant foams in the field of construction and civil engineering. Among these, for example, in the construction field, flame-retardant foam for walls, flame-retardant foam for ceilings, flame-retardant foam for floors, wall insulation, ceiling insulation, floor insulation, structures It can be used for on-site spraying during product manufacturing, filling internal gaps, and reinforcing structures that have deteriorated over time. In the field of civil engineering, the present composition is injected into natural ground, underground, soil, ground, bedrock, gaps between these and structures (building structures), further, gaps in structures, etc. to foam. By curing, the injection site can be filled and reinforced.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are merely examples for convenience of explanation, and the present invention is not limited to these examples in any sense. not something.

[1] Preparation of composition Each of the following components is mixed in the combinations and formulations shown in Tables 1 to 4 below, and each of Liquid A and Liquid B of Examples 1 to 13 and Comparative Examples 1 to 8. A composition for a combustible foam was obtained.

(1) Polyisocyanate polymeric MDI (Wannate manufactured by Wanhua Chemical Japan Co., Ltd., product name “PM-130”, viscosity (25 ° C.): 150 mPa s)

(2) Polyol Phthalic acid-based polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name “RDK133”, hydroxyl value 315 mgKOH/g)

(3) trimerization catalyst quaternary ammonium salt (1): quaternary ammonium salt (manufactured by San-Apro, product name “U-CAT 18X”)
Quaternary ammonium salt (2): Quaternary ammonium salt (manufactured by Kao Corporation, product name "Kaorizer No. 420")

(4) Resin catalyst Bismuth octylate (manufactured by Nippon Kagaku Sangyo Co., Ltd., product name “Pcat 25”)

(5) Foam Stabilizer Silicone-based foam stabilizer (manufactured by Momentive Performance Materials Japan LLC, product name “Niax Silicone L-6100”)

(6) Flame retardant - liquid flame retardant Organic phosphate ester (1): Polyphosphate ester (manufactured by ADEKA Co., Ltd., product name "ADEKA STAB PFR", viscosity (25 ° C.): 560 mPa s)
Organic phosphate ester (2): TCPP/tris(1-chloro-2-propyl) phosphate (manufactured by Wan Shan Co., viscosity (25° C.): 70 mPa s)

(7) Flame retardant - solid flame retardant - solid organic phosphate ester Solid organic phosphate ester: tris (tribromoneopentyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name "CR-900", powder)

(8) Flame retardant-solid flame retardant-red phosphorus Red phosphorus: Red phosphorus (manufactured by Rin Kagaku Kogyo Co., Ltd., product name “Nova Excel 140”, phosphorus concentration: 94% by mass, average particle size 30 μm)

(9) Flame retardant-solid flame retardant-water-releasing substance Aluminum hydroxide (2 μm): Aluminum hydroxide powder with an average particle size of 2 μm (manufactured by Nippon Light Metal Co., Ltd., product name “B1403”)
Aluminum hydroxide (12 μm): Aluminum hydroxide powder with an average particle size of 12 μm (manufactured by Nippon Light Metal Co., Ltd., product name “B153”)
Aluminum hydroxide (27 μm): Aluminum hydroxide powder with an average particle size of 27 μm (manufactured by Nippon Light Metal Co., Ltd., product name “SB303”)
Magnesium hydroxide (5 μm): Magnesium hydroxide powder with an average particle size of 5 μm (reagent)
Calcium hydroxide (10 μm): calcium hydroxide powder with an average particle size of 10 μm (reagent)

(10) Flame retardant-solid flame retardant-boron-based flame retardant Zinc borate: (manufactured by Mizusawa Chemical Industry Co., Ltd., product name "Alkanex FRC500", average particle size 4 μm)
Magnesium borate: (manufactured by Wako Pure Chemical Industries, Ltd., reagent)

(11) Foaming agent HCFO-1233zd: 1-chloro-3,3,3-trifluoropropene (manufactured by Honeywell)
HFO-1336mzz: 1,1,1,4,4,4-hexafluoro-2-butene (manufactured by Chemours)
HFC245fa/HFC365mfc (=8/2): HFC245fa, which is 1,1,1,3,3-pentafluoropropane manufactured by Central Glass Co., Ltd., and 1,1,1,3,3-pentafluoro manufactured by SOLVAY Blowing agent mixed with HFC365mfc which is butane at 8:2

[2] Production of foam (flame-retardant foam) Each flame-retardant foam composition of Examples 1 to 13 and Comparative Examples 1 to 8 obtained in the above [1] Used so that the volume ratio is 1: 1, an inorganic flexible board (910 mm × 910 mm), which is an adherend, is applied at an ambient temperature of 15 ° C. via an on-site spray foaming machine (product name: A-25, manufactured by Graco). ) was sprayed once downward and once upwardly. As a result, a foamed layer (thickness: about 60 mm) having a bottom blown layer of about 5 mm and a top blown layer of 50 to 60 mm was obtained. Incidentally, in Comparative Examples 6 and 7, spraying could not be performed.

尚、表中のＭ_Ｌ、Ｍ_Ｓ、Ｍ_Ｓ１及びＭ_Ｓ２は、各々以下の意味を有する。Ｍ_Ｌ＝液体難燃剤／Ｂ液全体（質量％）、Ｍ_Ｓ＝固体難燃剤／Ｂ液全体（質量％）、Ｍ_Ｓ１＝赤リン／固体難燃剤全体（質量％）、Ｍ_Ｓ２＝水放出物質／固体難燃剤全体（質量％）

M _L , M _S , M _S1 and M _S2 in the table respectively have the following meanings. M _L = liquid flame retardant/total B component (mass %), M _S = solid flame retardant/total B component (mass %), M _S1 = red phosphorus/total solid flame retardant (mass %), M _S2 = water release Total substance/solid flame retardant (% by mass)

尚、表中のＭ_Ｌ、Ｍ_Ｓ、Ｍ_Ｓ１及びＭ_Ｓ２は、各々以下の意味を有する。Ｍ_Ｌ＝液体難燃剤／Ｂ液全体（質量％）、Ｍ_Ｓ＝固体難燃剤／Ｂ液全体（質量％）、Ｍ_Ｓ１＝赤リン／固体難燃剤全体（質量％）、Ｍ_Ｓ２＝水放出物質／固体難燃剤全体（質量％）

M _L , M _S , M _S1 and M _S2 in the table respectively have the following meanings. M _L = liquid flame retardant/total B component (mass %), M _S = solid flame retardant/total B component (mass %), M _S1 = red phosphorus/total solid flame retardant (mass %), M _S2 = water release Total substance/solid flame retardant (% by mass)

尚、表中のＭ_Ｌ、Ｍ_Ｓ、Ｍ_Ｓ１及びＭ_Ｓ２は、各々以下の意味を有する。Ｍ_Ｌ＝液体難燃剤／Ｂ液全体（質量％）、Ｍ_Ｓ＝固体難燃剤／Ｂ液全体（質量％）、Ｍ_Ｓ１＝赤リン／固体難燃剤全体（質量％）、Ｍ_Ｓ２＝水放出物質／固体難燃剤全体（質量％）

M _L , M _S , M _S1 and M _S2 in the table respectively have the following meanings. M _L = liquid flame retardant/total B component (mass %), M _S = solid flame retardant/total B component (mass %), M _S1 = red phosphorus/total solid flame retardant (mass %), M _S2 = water release Total substance/solid flame retardant (% by mass)

尚、表中のＭ_Ｌ、Ｍ_Ｓ、Ｍ_Ｓ１及びＭ_Ｓ２は、各々以下の意味を有する。Ｍ_Ｌ＝液体難燃剤／Ｂ液全体（質量％）、Ｍ_Ｓ＝固体難燃剤／Ｂ液全体（質量％）、Ｍ_Ｓ１＝赤リン／固体難燃剤全体（質量％）、Ｍ_Ｓ２＝水放出物質／固体難燃剤全体（質量％）

M _L , M _S , M _S1 and M _S2 in the table respectively have the following meanings. M _L = liquid flame retardant/total B component (mass %), M _S = solid flame retardant/total B component (mass %), M _S1 = red phosphorus/total solid flame retardant (mass %), M _S2 = water release Total substance/solid flame retardant (% by mass)

[3] Measurement and Evaluation The foams of Examples and Comparative Examples obtained in [2] above were subjected to the measurements and evaluations shown in (1) to (6) below, and the results are shown in Tables 1 to 3.
Furthermore, the flame-retardant foam compositions of Examples 1, 6, 7 and 8 obtained in [1] above were evaluated as shown in (7) below, and the results are shown in Table 4.

(1) Density measurement From the obtained foam (thickness: about 60 mm), a test piece having a thickness of 50 mm was cut out while leaving the skin layer on the surface, and a test piece of 100 mm × 100 mm × 50 mm to collect. The dimensions of this test piece are accurately measured using vernier calipers, the mass is measured using an electronic balance, and the density of the test piece is calculated according to JIS K7222 from the obtained measurement values.

(2) Measurement of maximum heat release rate and total calorific value When the test piece of (1) above is heated for 20 minutes at a radiant heat intensity of 50 kW/ ^m2 in accordance with the combustion test method specified in ISO-5660. The maximum heat release rate and total heat release are measured, respectively.

(3) Measurement of self-extinguishing time In the test of (2) above, measure the time from ignition by heating to extinguishing.

(4) Evaluation of flame re-ignition after self-extinguishing In the test of (2) above, after the ignition by heating extinguished, the flame was ignited again, and the flame was not ignited. Neglected. Three samples were measured, and three samples had no reattachment flames with "◎", one sample had reattachment flames as "○", and two samples had reattachment flames. was evaluated as "Δ", and those with redeposition flames in all three samples were evaluated as "x".

(5) Evaluation of cracks In the test piece obtained after the test in (2) above, if no cracks are observed on the surface, it is indicated as "○", and if cracks are observed on the surface, it is indicated as "×". Those that reach from the surface side of the piece to the back surface are evaluated as "xx".

(6) Measurement of heat release rate after 3 minutes from ignition In the test of (2) above, those with a heat release rate of 10 kW / ^m2 or less after 3 minutes or more from ignition are "○", 10 kW / m Those exceeding ² are evaluated as "x".

(7) Evaluation of Mixing Properties Liquid B was stirred with a disper at 1000 rpm for 3 minutes, and after standing for 10 minutes after stirring, the appearance of Liquid B was visually observed, and mixing properties were evaluated based on the following criteria.
◯: Uniform, no separation after standing.
Δ: Partial separation is observed after standing.
x: Significant separation.

[4] Effects of Examples From Tables 1 to 3, Comparative Examples 1 to 5 have a large total calorific value of 10.5 to 14.3 MJ/m ² , while Examples 1 to 13 all have The total calorific value is effectively reduced to 6.4-7.8 MJ/m ² . In addition, Comparative Examples 1 to 5 have a high maximum heat release rate of 105 to 131 kW/m ² , whereas Examples 1 to 13 all have effectively low maximum heat release rates of 69 to 98 kW/m ² . suppressed. Furthermore, in Comparative Examples 1 to 5, the self-extinguishing time is as long as 29 to 43 seconds, whereas in Examples 1 to 13, the self-extinguishing time is effectively reduced to 8 to 16 seconds. . In addition, in the comparative examples in which foams could be formed, the heat generation rate after 3 minutes from ignition was high, exceeding 10 kW/m ² . On the other hand, in Examples 1 to 13, all were suppressed to 10 kW/m ² or less.

Such differences are believed to be due to the inclusion of polyol in Comparative Examples 1-5. That is, in Examples 1 to 13, it is considered that the total heat value and maximum heat release rate can be suppressed by eliminating the polyol. However, as described above, conventionally, the polyol functioned as a liquid base and could not be easily discharged. On the other hand, the present composition uses a liquid flame retardant as a liquid base, and uses red phosphorus and a water-releasing substance together as a solid flame retardant, thereby making it a composition that can be applied on site. In addition, it can be seen that excellent flame retardancy can be achieved at the same time.
Furthermore, in this test, no cracks were observed in any of the examples, despite the fact that the foam containing the skin layer was burned. From this, it is considered that the formation of a carbonized layer on the surface of the foam can be promoted after ignition, and the occurrence of cracks on the surface can be suppressed. As a result, it is thought that combustion from the cracks can also be prevented and an increase in the amount of heat generated can be prevented.

Further, from Tables 1 to 3, among the comparative examples in which foams could be formed, in all of Comparative Examples 2 to 5 and 8, reheating flames were observed after self-extinguishing. In contrast, in Examples 1 to 4 and 6 to 12, excellent results were obtained in which no redeposition flame was observed in any of the three samples. This effect is also considered to be due largely to the mechanism of removing polyol and combining red phosphorus and a water-releasing substance as a solid flame retardant.
On the other hand, in Example 5, redeposition flame was observed only in one of the three samples. This is considered to be influenced by the particle size of the water-releasing substance. That is, since the dispersibility is improved by suppressing the particle diameter of the water-releasing substance, it is considered that the reattachment flame can be suppressed in the present composition in the examples other than Example 5.

Also in Example 13, redeposition flame was observed only in one of the three samples. It is considered that this is influenced by the content of water. That is, due to the inclusion of water, the isocyanate was consumed after mixing the liquids A and B. As a result, less isocyanurate was formed than in the other examples, and redeposition flame was not observed. It is thought that Therefore, it can be seen that the present composition preferably has a structure containing as little water as possible.

Furthermore, when comparing Examples 1 to 3, the density decreases as the blending ratio of the water-releasing substance increases relative to the blending ratio of red phosphorus, that is, as the value of M _S2 /M _S1 increases. It can be seen that a higher flame retardancy can be obtained.
Further, as shown in Examples 9 to 10, in the present composition, red phosphorus and a water-releasing substance are used in combination as solid flame retardants, and a boron-based flame retardant is also used in combination. It can be seen that the lowest total calorific value is obtained at .

It is preferably used in the construction and civil engineering field (construction field and civil engineering field). Among these, for example, in the construction field, flame-retardant foam for walls, flame-retardant foam for ceilings, flame-retardant foam for floors, wall insulation, ceiling insulation, floor insulation, structures It can be used to fill internal gaps during product manufacturing and to reinforce structures that have deteriorated over time. In the field of civil engineering, the present composition is injected into natural ground, underground, soil, ground, bedrock, gaps between these and structures (building structures), further, gaps in structures, etc. to foam. By curing, the injection site can be filled and reinforced.

Claims (14)

A flame-retardant foam composition for forming a polyol-free polyisocyanurate foam,
comprising a polyisocyanate, a trimerization catalyst for said polyisocyanate, a flame retardant and a blowing agent;
Consisting of two or more chemical solutions, the polyisocyanate, the flame retardant and the trimerization catalyst are contained in different chemical solutions,
The flame retardant comprises a liquid flame retardant and a solid flame retardant,
A flame retardant foam composition, wherein the solid flame retardant comprises red phosphorus and a water releasing material. The composition for a flame-retardant foam according to claim 1, wherein the liquid flame retardant accounts for 25 to 60% by mass of the chemical solution when the total amount of the chemical solution containing the flame retardant is 100% by mass. 3. The composition for a flame-retardant foam according to claim 1, wherein the liquid flame retardant is an organic phosphate ester. When the content of the solid flame retardant is 100% by mass, the content of the red phosphorus is M _S1 (% by mass), and the content of the water-releasing substance is M _S2 (% by mass), M _S1 <M _S2 The composition for a flame-retardant foam according to any one of claims 1 to 3. 5. The composition for a flame-retardant foam according to any one of claims 1 to 4, wherein said red phosphorus is in the form of particles having an average particle diameter of 15 µm or more. 6. The composition for a flame-retardant foam according to any one of claims 1 to 5, wherein the water-releasing substance is a particulate material having an average particle size of 35 µm or less. 7. The composition for a flame-retardant foam according to any one of claims 1 to 6, wherein the average particle size of said red phosphorus is larger than the average particle size of said water-releasing substance. The composition for a flame-retardant foam according to any one of claims 1 to 7, wherein the water-releasing substance is one or more selected from metal hydroxides, inorganic hydrates and clay minerals. thing. The flame-retardant foam composition according to any one of claims 1 to 8, wherein the liquid flame retardant has a viscosity of 100 to 1000 mPa·s. 10. The composition for flame-retardant foam according to any one of claims 1 to 9, wherein the solid flame retardant further comprises a boron-based flame retardant. Consists of two types of chemical liquids, A liquid and B liquid,
The A liquid contains the polyisocyanate,
The B liquid contains the flame retardant and the trimerization catalyst,
The composition for a flame-retardant foam according to any one of claims 1 to 10, wherein the foaming agent is contained in at least one of the A liquid and the B liquid. Consists of three types of chemical liquids, A liquid, B liquid and C liquid,
The A liquid contains the polyisocyanate,
The B liquid contains the flame retardant,
The C solution contains the trimerization catalyst,
The composition for a flame-retardant foam according to any one of claims 1 to 10, wherein the foaming agent is contained in at least one of the A liquid, the B liquid and the C liquid. Consists of three types of chemical liquids, A liquid, B liquid and C liquid,
The A liquid contains the polyisocyanate,
The B liquid contains the flame retardant and the trimerization catalyst,
The composition for a flame-retardant foam according to any one of claims 1 to 10, wherein the liquid C contains the foaming agent. Consists of four types of chemicals, A liquid, B liquid, C liquid and D liquid,
The A liquid contains the polyisocyanate,
The B liquid contains the flame retardant,
The C solution contains the trimerization catalyst,
11. The composition for a flame-retardant foam according to any one of claims 1 to 10, wherein the D liquid contains the foaming agent.