Composition for Flame-Retardant Foam

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 at least one of a bromine-based flame retardant and a chlorine-based flame retardant.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a flame-retardant foam composition, and more particularly to a flame-retardant foam composition that forms a polyisocyanurate foam without using a polyol. [Background technology]

[0002] Conventionally, polyurethane foam has been widely used as a heat insulating material. However, the use of polyurethane foam as a foam is limited because the constituent material is flammable. Therefore, methods for making the foam flame-retardant by blending flame retardants have been proposed, but they have not yet met the recent strict demands for flame retardancy. On the other hand, of the polyol and polyisocyanate which are urethane raw materials, a technique for improving flame retardancy by not using polyol is disclosed in the following Patent Document 1. Furthermore, Patent Document 2 below discloses a technique for improving flame retardancy by using a trimerization catalyst to form an isocyanurate ring from a polyisocyanate while still using a polyol. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2009-149760 A [Patent Document 2] International Publication No. 2014-112394 Brochure Summary of the Invention [Problem to be solved by the invention]

[0004] The technology of Patent Document 1 achieves high flame retardancy compared to urethane foam, but only meets the level of quasi-noncombustibility in ISO5660, and does not meet the level of noncombustibility. In addition, there is a problem that the construction situation is limited. That is, the technology of Patent Document 1 is a technology in which the raw material components are mixed together and molded, and cannot be constructed on site. In the fields of architecture and civil engineering, insulation is formed by spraying on site, and gaps are filled by foaming and filling. That is, by construction on site, complicated operations such as pasting together pre-cut foam and filling gaps are eliminated, and the required shape can be completely matched without gaps. However, compositions that can be constructed on site need to be stored in separate portions to prevent reactions, and each of the separated raw materials needs to be in an appropriate liquid state so that the components can be quickly mixed in the appropriate amounts during construction. In this respect, the technology of Patent Document 1 is insufficient.

[0005] On the other hand, the technology of Patent Document 2 shows an example that meets the level of non-combustibility, and is considered to have excellent flame retardancy, and furthermore, it is a technology that can be applied on site. However, there is a problem that the polyol component is essential and the polyol component cannot be eliminated. That is, in order to ensure on-site applicability, at least two liquid bases, the polyol component and the polyisocyanate component, are required. Therefore, if the polyol component is eliminated, on-site applicability cannot be obtained, and there is a problem that lump-sum mixing is required as with the technology of Patent Document 1.

[0006] In addition, foam materials generally have a core layer (main body) containing many foam cells, and a skin layer (surface layer) formed on the surface of the core layer and substantially free of foam cells, but the material (resin) of urethane foam obtained using polyol is itself flammable, so the skin layer is easily flammable. When the skin layer burns, the heat generation increases and the self-extinguishing property decreases, creating a chain reaction, so there is a problem that it is difficult to achieve sufficient flame retardancy or non-flammability while having a skin layer.

[0007] The present invention has been made in consideration of the above-mentioned circumstances, and has an object to provide a flame-retardant foam composition that can achieve both high flame retardancy and on-site workability while eliminating polyol components. [Means for solving the problem]

[0008] That is, the present invention is as follows. [1] The flame-retardant foam composition of the present invention is a flame-retardant foam composition for forming a polyisocyanurate foam without using a polyol, A polyisocyanate, a trimerization catalyst for the polyisocyanate, a flame retardant, and a blowing agent, The composition is composed of two or more kinds of chemical solutions, and the polyisocyanate, the flame retardant, and the trimerization catalyst are contained in different chemical solutions, The flame retardant includes a liquid flame retardant and a solid flame retardant, The solid flame retardant contains red phosphorus and at least one of a bromine-based flame retardant and a chlorine-based flame retardant. [2] In the flame-retardant foam composition of the present invention, the liquid flame retardant can account for 25 to 60 mass % of the chemical liquid, when the entire chemical liquid including the flame retardant is taken as 100 mass %. [3] In the flame-retardant foam composition of the present invention, the liquid flame retardant may include an organic phosphate ester and / or a chlorine-based flame retardant. [4] In the flame-retardant foam composition of the present invention, the total amount of the solid flame retardant is 100 mass %, and the content of the red phosphorus is M S1 (mass%), and the total content of the brominated flame retardant and the chlorine-based flame retardant is M S2 (mass%), M S1 <M S2 It can be said that: [5] In the flame-retardant foam composition of the present invention, the red phosphorus can be in the form of granules having an average particle size of 15 μm or more. [6] In the flame-retardant foam composition of the present invention, the viscosity of the liquid flame retardant can be set to 100 to 1000 mPa·s. [7] In the flame-retardant foam composition of the present invention, the solid flame retardant may further include an antimony-containing flame retardant. [8] The flame-retardant foam composition of the present invention is composed of two chemical liquids, liquid A and liquid B, The liquid A contains the polyisocyanate, the B solution 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. [9] The flame-retardant foam composition of the present invention is composed of three liquids, namely, liquid A, liquid B, and liquid C. The liquid A contains the polyisocyanate, The liquid B contains the flame retardant, the liquid C 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.

[10] The flame-retardant foam composition of the present invention is composed of three liquids, namely, liquid A, liquid B, and liquid C. The liquid A contains the polyisocyanate, the B solution contains the flame retardant and the trimerization catalyst, The liquid C may contain the foaming agent.

[11] The composition for flame-retardant foam of the present invention is composed of four liquids, namely, liquid A, liquid B, liquid C, and liquid D. The liquid A contains the polyisocyanate, The liquid B contains the flame retardant, the liquid C contains the trimerization catalyst, The liquid D may contain the foaming agent. Effect of the Invention

[0009] The flame-retardant foam composition of the present invention has an object to provide a flame-retardant foam composition that combines high flame retardancy with on-site workability while eliminating a polyol component. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention will be described below. The matters described herein are for illustrative purposes and for illustrative purposes of the embodiments of the present invention, and are described for the purpose of providing what is believed to be the most effective and easy-to-understand explanation of the principles and conceptual features of the present invention. In this respect, it is not intended to show the structural details of the present invention beyond a certain degree that are necessary for a fundamental understanding of the present invention, and the present description will make it clear to those skilled in the art how some aspects of the present invention can be actually embodied.

[0011] The flame-retardant foam composition of the present invention (hereinafter, also simply referred to as "the composition") is a flame-retardant foam composition that forms a polyisocyanurate foam without using a polyol, A polyisocyanate, a trimerization catalyst for the polyisocyanate, a flame retardant, and a blowing agent, The composition is composed of two or more kinds of chemical solutions, and the polyisocyanate, the flame retardant, and the trimerization catalyst are contained in different chemical solutions, The flame retardant includes a liquid flame retardant and a solid flame retardant, The solid flame retardant contains red phosphorus and at least one of a bromine-based flame retardant and a chlorine-based flame retardant.

[0012] (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 polymer, the compound (monomer) constituting the polymer may be only one type (mononuclear) or may be two or more types (polynuclear). Furthermore, a mixture of a monomer and a polymer may be used. The monomer of polyisocyanate includes aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, etc. These may be used alone or in combination of two or more types.

[0013] Among the above, examples of aromatic polyisocyanates include diphenylmethane diisocyanate [2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate], tolylene diisocyanate [2,4-tolylene 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 diisocyanate, Examples of the isocyanate include 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, isopropylidene bis (4-cyclohexyl isocyanate), triphenylmethane diisocyanate, triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, tris(isocyanatephenyl)-thiophosphoric acid, etc. These may be used alone or in combination of two or more.

[0014] Among the above, examples of the aliphatic polyisocyanate include hexamethylene diisocyanate [1,6-hexamethylene diisocyanate], trimethylhexamethylene diisocyanate [2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate], lysine diisocyanate, lysine triisocyanate, dimer acid diisocyanate, etc. These may be used alone or in combination of two or more. Furthermore, among the above, examples of the alicyclic polyisocyanate 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], etc. These may be used alone or in combination of two or more. The above-mentioned various monomers may be modified products thereof (isocyanurate modified products, carbodiimide modified products, etc.), blocked products thereof, hydrogenated products thereof, etc. These may be used alone or in combination of two or more kinds.

[0015] Among the above, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (monomeric MDI, polymeric MDI, crude MDI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate (IPDI), and the like are preferred, and further, 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 mass %, 10 to 50 mass %, 15 to 45 mass %, or 20 to 40 mass %.

[0016] (2) Trimerization catalyst The trimerization catalyst is a catalyst (isocyanurate catalyst) that promotes the formation of an isocyanurate ring. That is, it is a catalyst (isocyanurate catalyst) that promotes the trimerization of isocyanate groups. The trimerization catalyst may have the function of the trimerization catalyst, and the type is not limited. Examples of the trimerization catalyst include quaternary ammonium salts, tertiary ammonium salts, nitrogen-containing aromatic compounds, alkali metal carboxylates (alkali metal organic acid salts), alkali metal oxides, and alkali metal alkoxides. These may be used alone or in combination of two or more.

[0017] Among the above, the quaternary ammonium salt is composed of a quaternary ammonium cation and another cation. Among them, the quaternary ammonium cation is not limited, and for example, an aliphatic ammonium cation, an alicyclic ammonium cation, a hydroxyammonium cation, etc. can be used. These can be used alone or in combination of two or more kinds. Among these, the aliphatic ammonium cation includes tetraalkylammonium. That is, it is an ammonium cation having four alkyl groups. Each alkyl group can be a hydrocarbon group having 1 to 20 carbon atoms, but at least two or more of the four alkyl groups can be the same, and furthermore, three or more of the alkyl groups can be the same. Examples of the aliphatic ammonium cation having the four alkyl groups that are the same include tetramethylammonium, tetraethylammonium, etc. These may be used alone or in combination of two or more.

[0018] In addition, examples of the aliphatic ammonium cation in which the three alkyl groups are the same include alkyltrimethylammonium, alkyltriethylammonium, etc. These may be used alone or in combination of two or more kinds. Among these, examples of alkyl trimethyl ammonium include ethyl trimethyl ammonium, propyl trimethyl ammonium, butyl trimethyl ammonium, pentyl trimethyl ammonium, hexyl trimethyl ammonium, heptyl trimethyl ammonium, octyl trimethyl ammonium, nonyl trimethyl ammonium, decyl trimethyl ammonium, undecyl trimethyl ammonium, dodecyl trimethyl ammonium, tridecyl trimethyl ammonium, tetradecyl trimethyl ammonium, heptadecyl trimethyl ammonium, hexadecyl trimethyl ammonium, heptadecyl trimethyl ammonium, octadecyl trimethyl ammonium, etc. These may be used alone or in combination of two or more.

[0019] Examples of alkyl triethyl ammonium include methyl triethyl ammonium, propyl triethyl ammonium, butyl triethyl ammonium, pentyl triethyl ammonium, hexyl triethyl ammonium, heptyl triethyl ammonium, octyl triethyl ammonium, nonyl triethyl ammonium, decyl triethyl ammonium, undecyl triethyl ammonium, dodecyl triethyl ammonium, tridecyl triethyl ammonium, tetradecyl triethyl ammonium, heptadecyl triethyl ammonium, hexadecyl triethyl ammonium, heptadecyl triethyl ammonium, and octadecyl triethyl ammonium. These may be used alone or in combination of two or more.

[0020] Examples of the alicyclic ammonium cation include 1-methyl-1-azania-4-azabicyclo[2,2,2]octanium, 1,1-dimethyl-4-methylpiperidinium, 1-methylmorpholinium, 1-methylpiperidinium, etc. These may be used alone or in combination of two or more. Further, examples of the hydroxyammonium cation include (2-hydroxypropyl)trimethylammonium, hydroxyethyltrimethylammonium, trimethylaminoethoxyethanol, hydroxyethyl-2-hydroxypropyldimethylammonium, etc. These may be used alone or in combination of two or more.

[0021] On the other hand, the anion constituting the quaternary ammonium salt is not limited, and organic anions and / or inorganic anions can be used. Among them, examples of organic anions include formic acid group, acetic acid group, caproic acid group (hexanoic acid group), heptanoic acid group, octanoic acid group, octylic acid group (2-ethylhexanoic acid group), oleic acid group, 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, methylcarbonic acid group, sulfonic acid group (alkylbenzenesulfonic acid group, toluenesulfonic acid group, benzenesulfonic acid group, etc.), and phosphoric acid ester group. These may be used alone or in combination of two or more. Examples of inorganic anions include halogen group, hydroxy group, hydrogen carbonate group, and carbonate group. These may be used alone or in combination of two or more.

[0022] Catalysts containing such quaternary ammonium salts are available, for example, under the names "U-CAT 18X" and "U-CAT 2313" (both manufactured by San-Apro Co., Ltd.), "Kao Raiser No. 410" and "Kao Raiser No. 420" (both manufactured by Kao Corporation), etc. These may be used alone or in combination of two or more kinds.

[0023] Among the above, the tertiary ammonium salt may be trimethylammonium salt, triethylammonium salt, triphenylammonium salt, etc. These may be used alone or in combination of two or more. In addition, the anion constituting the tertiary ammonium salt may be the same as those exemplified as the anion constituting the quaternary ammonium salt.

[0024] Among the above, the alkali metal carboxylate is a salt of a carboxylic acid and an alkali metal, and among these, the carboxylic acid is preferably an aliphatic carboxylic acid having 1 to 8 carbon atoms. More specifically, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octylic acid, etc. can be mentioned. These may be used alone or in combination of two or more. On the other hand, the alkali metal can be lithium, potassium, sodium, etc. These may be used alone or in combination of two or more. More specifically, potassium acetate, potassium octylate, potassium caprylate, etc. can be mentioned. In addition, as the carboxylate metal salt, for example, iron oxalate can be mentioned. These may be used alone or in combination of two or more.

[0025] Among the above, the nitrogen-containing aromatic compound may be an aromatic compound having a tertiary amino group as a functional group (aromatic tertiary amines). The tertiary amino group is a group represented by -NR2R3, where R2 and R3 are each a straight-chain, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms, and more preferably, the tertiary amino group is a functional group represented by -R1-NR2R3, where R1 is a straight-chain or branched hydrocarbon group having 1 to 6 carbon atoms. That is, examples of the tertiary amino group include a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a diethylaminomethyl group, a diethylaminoethyl group, and a diethylaminopropyl group. These may be used alone or in combination of two or more. 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 to 6, and is preferably 2 to 4. Specific examples include tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and tris(dimethylaminopropyl)hexahydrotriazine.

[0026] Among the above-mentioned trimerization catalysts, in the present invention, it is preferable to use at least one of a quaternary ammonium salt and an alkali metal carboxylate. By using these, better flame retardancy can be obtained. In addition, in the present invention, when a quaternary ammonium salt is used, only one type may be used, but it is more preferable to use two or more types of quaternary ammonium salts in combination. This makes it possible to reduce the density of the resulting foam while obtaining even better flame retardancy. In addition, the reduced density can improve workability.

[0027] The amount of the trimerization catalyst is not limited, but when the total amount of polyisocyanate contained in the composition is 100 parts by mass, the amount of the trimerization catalyst can be 0.5 parts by mass or more and 10 parts by mass or less. In this range, the composition can effectively promote trimerization (isocyanuration) between isocyanate groups, and can obtain excellent flame retardancy. In addition, a curing speed corresponding to a wide range of application methods can be obtained. The 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, even more preferably 1.2 parts by mass or more and 4.0 parts by mass or less, particularly preferably 1.3 parts by mass or more and less than 3.0 parts by mass, and particularly preferably 1.4 parts by mass or more and 2.9 parts by mass or less. In these preferred ranges, a curing speed excellent in on-site application can be obtained while achieving a higher level of flame retardancy due to isocyanuration in the obtained flame-retardant foam.

[0028] In the present invention, the trimerization catalyst may be used alone, but may also be used in combination with a resinification catalyst. By using a resinification catalyst in combination, the stickiness of the resulting flame-retardant foam can be reduced or prevented. The resinification catalyst may be an organometallic compound of a metal of Groups 14-15. Specifically, it may be a metal organic acid salt or an organometallic compound. The metal of Groups 14-15 may be bismuth, tin, lead, or the like. On the other hand, an aliphatic carboxylic acid having 5 to 15 carbon atoms may be used as the organic acid constituting the metal organic acid salt. That is, for example, hexanoic acid, heptanoic acid, octylic acid (2-ethylhexyl acid), decanoic acid, neodecanoic acid, naphthenic acid, and the like may be mentioned. Specifically, it may be bismuth octylate, bismuth neodecanoate (bismuth neododecanoate), bismuth naphthenate, lead naphthenate, tin octylate, lead octylate, and the like. These may be used alone or in combination of two or more kinds. In addition, examples of the organometallic compound include organotin compounds. Specific examples include dibutyltin compounds (dibutyltin dilaurate, etc.), dioctyltin compounds (dioctyltin malate, dibutyltin oxide, etc.), etc. These may be used alone or in combination of two or more.

[0029] When a resinification catalyst is used, its amount is not limited, but when the total polyisocyanate contained in the present composition is 100 parts by mass, the resinification catalyst can be 0.01 parts by mass or more and 5 parts by mass or less. In this range, the present composition can reduce the stickiness of the obtained flame-retardant foam while achieving both flame retardancy and on-site workability. The 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, even more preferably 0.10 parts by mass or more and 3.5 parts by mass or less, particularly preferably 0.13 parts by mass or more and less than 3.0 parts by mass, and particularly preferably 0.16 parts by mass or more and 2.5 parts by mass or less. In these preferred ranges, the stickiness of the obtained flame-retardant foam can be further reduced or prevented while achieving both flame retardancy and on-site workability.

[0030] In the present invention, in addition to the above-mentioned resinification catalyst, an amine catalyst not included in the above-mentioned trimerization catalyst and resinification catalyst can be used in combination with the trimerization catalyst. By using an amine catalyst in combination, the stickiness of the obtained flame-retardant foam can be reduced or prevented. In addition, workability can be improved by reducing odor. Examples of the amine catalyst include reactive amine compounds having OH groups and / or NH groups, and cyclic amine compounds having a cyclic structure. These may be used alone or in combination of two or more. Among these, the use of reactive amine compounds can provide more effective odor reduction.

[0031] 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, etc. These may be used alone or in combination of two or more. Examples of the cyclic amine compound 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, etc. These may be used alone or in combination of two or more.

[0032] When an amine catalyst is used, the amount of the amine catalyst is not limited, but when the total amount of polyisocyanate contained in the composition is 100 parts by mass, the amount of the amine catalyst can be 0.01 parts by mass or more and 7 parts by mass or less. In this range, the composition can obtain the effect of reducing the stickiness of the obtained flame-retardant foam and the effect of improving workability by reducing odor. The amount of the amine catalyst 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, even more preferably 0.10 parts by mass or more and 4.0 parts by mass or less, particularly preferably 0.13 parts by mass or more and less than 3.0 parts by mass, and particularly preferably 0.16 parts by mass or more and 2.5 parts by mass or less. In these preferred ranges, the effect of reducing the stickiness of the obtained flame-retardant foam and the effect of improving workability by reducing odor can be obtained more advantageously.

[0033] (3) Flame retardants In the present composition, the flame retardant is a component that imparts flame retardancy to the resulting foam. The flame retardant includes liquid flame retardants and solid flame retardants.

[0034] The amount of the flame retardant (liquid flame retardant and solid flame retardant combined) is not limited, but when the entire chemical solution including the flame retardant that constitutes the present composition is taken as 100% by mass, it can be, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 65% ​​by mass or more, even more preferably 70% by mass or more, particularly preferably 75% by mass or more, and especially preferably 80% by mass or more, and although the upper limit is not limited, it can also be 100% by mass (for example, when a catalyst, a foaming agent, etc. is included in another chemical solution). That is, among the chemical solutions constituting the present composition, the chemical solution containing a 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, the content can be, for example, 99% by mass or less. This proportion can further be 95% by mass or less, or 90% by mass or less.

[0035] (3-1) Liquid flame retardants The liquid flame retardant is a flame retardant that is liquid at temperatures of 0 to 40°C. That is, it is a flame retardant that has fluidity (a temperature at which it does not decompose) at temperatures of 0 to 40°C. Although there are no limitations on the degree of fluidity, it is preferable that the viscosity measured at 25°C using a B-type viscometer in accordance with JIS K7117-1 is 50 mPa·s or more. The upper limit of this viscosity is not limited, but can be, for example, 10,000 mPa·s or less.

[0036] Usually, when a composition that can be applied on site is to be obtained, even a polyisocyanurate foam composition requires a liquid polyol, as in the case of a polyurethane foam composition. This is because a liquid-divided composition is required to obtain on-site application. That is, in order to perform on-site application, it is necessary to divide the components so that they do not react with each other. On the other hand, even if the number of divisions is large, the preparation on site becomes complicated, so it is preferable that the composition before mixing is divided into 2 to 5 types. Furthermore, in order to mix each component in an appropriate mixture, the necessary components must be mixed in an appropriate amount in the divided liquid composition, and appropriate fluidity must be maintained in the mixture. In this way, by dividing the composition in liquid form, the desired foam can be obtained on site by simply mixing. However, as mentioned above, various conditions are required for liquid division, so the degree of freedom of division is narrower than expected. For this reason, even a polyisocyanurate foam composition currently requires a polyol as a liquefied base. Therefore, if polyol is not used, the above-mentioned polyol cannot be used as a liquefaction base, which causes a problem that liquid division that can be applied on site cannot be performed. In this respect, in the present composition, a liquid flame retardant is used as a part of the flame retardant, and this liquid flame retardant can be used as a liquefaction base instead of a polyol. This makes it possible to perform liquid division that can be applied on site.

[0037] As such a liquid flame retardant, an organic phosphate ester and / or a chlorine-based flame retardant can be used. Also, as the liquid flame retardant, an organic phosphate ester and / or a chlorine-based flame retardant can be used. The organic phosphate ester includes an organic phosphate monoester, an organic phosphate diester, and an organic phosphate triester. These may be used alone or in combination of two or more. Furthermore, the organic phosphate ester includes a monophosphate ester and a condensed phosphate ester. These may be used alone or in combination of two or more.

[0038] Specifically, examples of monophosphate esters include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, tris(isopropylphenyl) phosphate, trinaphthyl phosphate, xylenyl diphenyl phosphate, diphenyl(2-ethylhexyl) phosphate, di(isopropylphenyl)phenyl phosphate, and monoisodecyl phosphate. Examples of the phosphate include 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resylcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), phosphaphenanthrene, etc. These may be used alone or in combination of two or more. Examples of the condensed phosphate ester include trialkyl polyphosphate, resorcinol polyphenyl phosphate, hydroquinone poly(2,6-xylyl) phosphate, and condensates thereof. These may be used alone or in combination of two or more.

[0039] Chlorine-based flame retardants are classified into liquid ones (hereinafter simply referred to as "liquid chlorine-based flame retardants") and solid ones (hereinafter simply referred to as "solid chlorine-based flame retardants"), and among these, liquid chlorine-based flame retardants can be used as the liquid flame retardant of the present composition. Note that solid chlorine-based flame retardants can be used as the solid flame retardant of the present composition, and solid chlorine-based flame retardants will be described later in "(3-2) Solid Flame Retardants".

[0040] Examples of liquid chlorine-based flame retardants include chlorinated paraffin, chlorinated organic phosphate ester, etc. These may be used alone or in combination of two or more. Among these, chlorinated paraffins include short-chain chlorinated paraffins, medium-chain chlorinated paraffins, long-chain chlorinated paraffins, etc. From the viewpoint of the impact on the environment, medium-chain chlorinated paraffins and long-chain chlorinated paraffins are preferred. These may be used alone or in combination of two or more kinds. The chlorinated paraffin may be liquid, and the carbon number is not limited, but may be, for example, 10 to 30, further 14 to 30, or further 18 to 30. The number average molecular weight is not limited, but may be, for example, 250 to 1000, further 330 to 700, or further 350 to 650. The chlorination rate is not limited, but may be, for example, 30 to 80%, further 35 to 70%, or further 40 to 60%. On the other hand, examples of chlorinated organic phosphates include tris(2-chloro-1-methylethyl) phosphate, tris(2-chloroethyl) phosphate, tris(1,3-dichloro-2-propyl) phosphate, etc. These may be used alone or in combination of two or more.

[0041] Among the liquid flame retardants, phosphate-based liquid flame retardants are available under the names "ADK STAB PFR", "ADK STAB FP-900L", "ADK STAB FP-600" (all manufactured by ADEKA CORPORATION), "CR-504L", "CR-570", "CR-733S", "CR-741", "DAIGUARD-540", "DAIGUARD-580", "DAIGUARD-610", "DAIGUARD-880" (all manufactured by Daihachi Chemical Industry Co., Ltd.), etc. These may be used alone or in combination of two or more kinds.

[0042] Among the liquid flame retardants, liquid chlorine-based flame retardants can be obtained, for example, under the names "TOYOPARAX A-40", "TOYOPARAX A-50", "TOYOPARAX 145", and "TOYOPARAX 150" (all manufactured by Tosoh Corporation), and under the names "EMPARA 40", "EMPARA K-45", "EMPARA K-47", "EMPARA K-50", and "EMPARA AR-500" (all manufactured by Ajinomoto Fine-Techno Co., Ltd.). These may be used alone or in combination of two or more kinds.

[0043] The viscosity of the liquid flame retardant is not limited, but as described above, the viscosity measured at 25 ° C. using a B-type viscometer in accordance with JIS K7117-1 is preferably 50 mPa·s or more, 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 chemical solution containing the liquid flame retardant can be improved. In addition, the upper limit of the viscosity of the liquid flame retardant is not limited, but is preferably 5000 mPa·s or less. In this range, the composition can better achieve both high flame retardancy and on-site workability while excluding the polyol component. The viscosity is preferably 100 to 4000 mPa·s, more preferably 100 to 3000 mPa·s, even more preferably 100 to 2500 mPa·s, particularly preferably 120 to 1500 mPa·s, and particularly preferably 150 to 1000 mPa·s. Within these preferred ranges, a higher level of flame retardancy and on-site workability can be achieved while eliminating the polyol component. In preparing the present flame-retardant foam composition, the viscosity of the liquid flame retardants can be adjusted during blending by mixing a plurality of liquid flame retardants together or by mixing a solvent or the like.

[0044] The amount of the liquid flame retardant is not limited, but the content ratio M of the liquid flame retardant in the liquid that constitutes the present composition is 100 mass %. L The ratio M can be 20 to 80% by mass. In this range, the composition can achieve both high flame retardancy and on-site workability while eliminating the polyol component. L is preferably 20 to 75 mass%, more preferably 20 to 70 mass%, further preferably 25 to 65 mass%, particularly preferably 25 to 60 mass%, and particularly preferably 30 to 60 mass%. Within these preferred ranges, a high level of flame retardancy and on-site applicability can be achieved while excluding the polyol component, and good on-site spray application can be performed.

[0045] (3-2) Solid flame retardants The composition contains red phosphorus as a solid flame retardant and at least one of a bromine-based flame retardant and a solid chlorine-based flame retardant. That is, the composition may contain three solid flame retardants, i.e., red phosphorus, a bromine-based flame retardant, and a solid chlorine-based flame retardant, or may contain two solid flame retardants, i.e., red phosphorus and a bromine-based flame retardant, or may contain two solid flame retardants, i.e., red phosphorus and a solid chlorine-based flame retardant.

[0046] A solid flame retardant is a flame retardant that is solid at temperatures between 0 and 40° C. In other words, it is a flame retardant that does not have fluidity (temperature at which it does not decompose) at temperatures between 0 and 40° C. and has a fixed shape and volume. In other words, a solid flame retardant is a flame retardant whose viscosity cannot be measured using a B-type viscometer. The solid flame retardant preferably has no fluidity and can be processed into a finely divided solid (granules, flakes, powder, etc.).

[0047] The amount of the solid flame retardant is not limited, but the total amount of the chemical solution that constitutes the present composition, including the flame retardant, is taken as 100 mass %, and the content of the liquid flame retardant is taken as ML (mass%), and the content of solid flame retardant is M S (mass%), M L ≦M S However, M L >M S It is preferable that the composition contains more liquid flame retardant than solid flame retardant in terms of mass. In this composition, by using a liquid flame retardant in combination, it is possible to achieve high flame retardancy and on-site workability while eliminating the polyol component in this range. Furthermore, when this ratio is set to M S / M L When converted as 0.10≦M S / M L ≦0.90, more preferably 0.20≦M S / M L ≦0.75, and more preferably 0.30≦M S / M L ≦0.65, and 0.35≦M S / M L It is particularly preferable that the ratio is ≦0.55. Within these preferable ranges, by using a liquid flame retardant in combination, it is possible to achieve a higher level of both flame retardancy and on-site workability while eliminating the polyol component.

[0048] (3-2-1) Red phosphorus Red phosphorus reacts with water and carbon generated by burning flammable gases produced by pyrolysis of resin, forming a carbonized layer on the resin surface, and this carbonized layer has the effect of extinguishing fire by blocking oxygen. Red phosphorus alone may be used, but red phosphorus having a coating layer can be used. By having a coating layer, handling and workability are improved. In addition, dispersibility in the obtained flame-retardant foam can be improved, and the effect of adding can be improved. The coating layer may be formed from any material, but is particularly formed from resin, metal hydroxide, metal oxide, etc. Among these, thermosetting resins can be suitably used as the resin. Specific examples include phenolic resins, furan resins, xylene-formaldehyde resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, aniline resins, and silicone resins. These may be used alone or in combination of two or more. In addition, examples of metal hydroxides include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide, etc. These may be used alone or in combination of two or more. Further, examples of metal oxides include aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, etc. These may be used alone or in combination of two or more. In the case of red phosphorus having a coating layer on the particle surface, the proportion of the coating layer in the whole is not limited, but may be, for example, 1 to 30 parts by mass when the whole of the red phosphorus having the coating layer is taken as 100 parts by mass.

[0049] Such red phosphorus is available, for example, under the trade names "Nova Red", "Nova Excel", and "Novaquel" (all manufactured by Rinkagaku Kogyo Co., Ltd.), "HISHIGUARD" (manufactured by Nippon Kagaku Kogyo Co., Ltd.), and "EXOLIT RP" (manufactured by Clariant Chemicals Co., Ltd.), etc. These may be used alone or in combination of two or more kinds.

[0050] The average particle size of the red phosphorus used in this composition (R P ) is not limited, but is usually 1 to 100 μm, preferably 5 to 70 μm, and more preferably 10 to 60 μm, but R PTherefore, the thickness is more preferably 15 to 50 μm, particularly preferably 15 to 45 μm, and particularly preferably 17 to 43 μm. In addition, the average particle size of red phosphorus is R P (μm), and the average particle size of the brominated flame retardants and solid chlorine-based flame retardants described later is R BC (μm), the size of the average particle diameter of red phosphorus R P The average particle size R of brominated flame retardants and solid chlorinated flame retardants BC In this case, R P and R BC and are equivalent, or R P R BC This can prevent re-ignition more effectively than when R is smaller than . BC / 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. BC / R P The lower limit is not limited, but is usually 0.01 or more, and can be 0.05 or more.

[0051] The average particle size of red phosphorus and the average particle size of the bromine-based flame retardant and solid chlorine-based flame retardant do not usually change before blending into the flame-retardant foam composition, in the flame-retardant foam composition, or in the resulting flame-retardant foam. In addition, before blending into the flame-retardant foam composition, they are measured by a particle size distribution measuring device. In addition, the average particle size in the flame-retardant foam composition and in the resulting flame-retardant foam can be obtained from the particle size distribution measured by a laser diffraction particle size distribution measuring device or the like. Specifically, a microtrack particle size analyzer (product name: MT3200II) manufactured by Nikkiso Co., Ltd. was used to determine the particle size distribution of the sample, and the particle size at 50% of the cumulative value was taken as the average particle size (D50).

[0052] The amount of red phosphorus is not limited, but when the entire solid flame retardant is taken as 100% by mass, the amount of red phosphorus can be 1 to 90% by mass. In this range, the composition can achieve both high flame retardancy and on-site workability while excluding the polyol component. The 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. In these preferred ranges, it is possible to achieve both high flame retardancy and on-site workability while excluding the polyol component, and a good carbonized layer can be formed. In addition, from the viewpoint of suppressing ignition by red phosphorus itself, when the entire chemical solution (usually, solution B) containing the solid flame retardant is taken as 100% by mass, the content of red phosphorus is preferably 30% by mass or less, more preferably 20% by mass or less.

[0053] (3-2-2) Brominated flame retardants and solid chlorinated flame retardants Bromine-based flame retardants and solid chlorine-based flame retardants are generally substances also called halogen-based flame retardants. Bromine-based flame retardants and solid chlorine-based flame retardants play a role in improving flame retardant performance when used in combination with the above-mentioned red phosphorus. That is, bromine-based flame retardants and solid chlorine-based flame retardants are gasified by heating during combustion, and capture hydroxyl radicals that promote the combustion reaction of resin in the gas phase. Furthermore, bromine-based flame retardants and solid chlorine-based flame retardants promote the formation of a carbonized layer by red phosphorus in the solid phase, thereby improving the air blocking effect and heat insulating effect of the carbonized layer. Therefore, the present composition containing bromine-based flame retardants and solid chlorine-based flame retardants can improve flame retardant performance, particularly the effect of preventing reignition.

[0054] Brominated flame retardants are compounds that contain bromine atoms, and examples of such flame retardants include brominated organic compounds. Examples of brominated organic compounds include brominated monocyclic aromatic compounds having one aromatic ring such as hexabromobenzene and pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylene bis(pentabromophenyl), and tetrabromobisphenol A, and other brominated polycyclic aromatic compounds having two or more aromatic rings, hexabromocyclodecane, ethylene bis(tetrabromophthalimide), brominated polycarbonate, brominated epoxy compound (brominated epoxy resin), poly(brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, condensation product of cyanuric chloride and brominated phenol, brominated polystyrene, and brominated polymethylstyrene. These may be used alone or in combination of two or more.

[0055] The solid chlorine-based flame retardant is a component containing chlorine atoms. Examples of the solid chlorine-based flame retardant include chlorinated polyphenyl, chlorinated polyethylene, diphenyl chloride, triphenyl chloride, chlorinated paraffin, pentachlorinated fatty acid ester, perchloropentacyclodecane, chlorinated naphthalene, and tetrachlorophthalic anhydride. These may be used alone or in combination of two or more.

[0056] The average particle size (R BC ) is not limited, but is usually 0.05 to 50 μm, preferably 0.1 to 35 μm, more preferably 0.3 to 30 μm, further preferably 0.5 to 25 μm, and particularly preferably 0.7 to 20 μm. The average particle size is measured as described above.

[0057] The amount of the bromine-based flame retardant and / or the solid chlorine-based flame retardant is not limited. Assuming that bromine-based flame retardants and solid chlorine-based flame retardants are used in combination, the total amount of solid flame retardants is taken as 100 mass%, and the content of red phosphorus is taken as M S1(mass%), and the total content of brominated flame retardants and solid chlorine-based flame retardants is M S2 (mass%), M S1 ≧M S2 However, M S1 <M S2 It is preferable that: In addition, when either a bromine-based flame retardant or a solid chlorine-based flame retardant is used, the content of the bromine-based flame retardant or the solid chlorine-based flame retardant is set to M S2 (% by mass) M S1 ≧M S2 However, M S1 <M S2 It is preferable that:

[0058] That is, it is preferable to contain a larger amount of bromine-based flame retardant and / or solid chlorine-based flame retardant than red phosphorus in terms of mass. In this composition, by using a liquid flame retardant in combination, it is possible to achieve a good balance between high flame retardancy and on-site workability while excluding the polyol component. Furthermore, the above content ratio is M S2 / M S1 When converted as 0.6≦M S2 / M S1 ≦30, and further 0.8≦M S2 / M S1 ≦20, and 1.05≦M S2 / M S1 ≦15 is more preferable, and 1.5≦M S2 / M S1 It is more preferable that the ratio is ≦10. In these preferable ranges, by using a liquid flame retardant in combination, it is possible to achieve a higher level of both flame retardancy and on-site workability while eliminating the polyol component, prevent re-ignition, and reduce the amount of heat generated.

[0059] (3-2-3) Other solid flame retardants The present composition may contain, as the solid flame retardant, other solid flame retardants in addition to the above-mentioned red phosphorus, bromine-based flame retardant and / or solid chlorine-based flame retardant. Examples of the other solid flame retardants include antimony-containing flame retardants, solid phosphate ester-based flame retardants, boron-based flame retardants, metal stannates, water-releasing substances, etc. These may be used alone or in combination of two or more. On the other hand, the present composition contains red phosphorus and a bromine-based flame retardant and / or a solid chlorine-based flame retardant as the solid flame retardant, and thus can be substantially free of the above-mentioned other solid flame retardants, such as antimony-containing flame retardants, boron-based flame retardants, solid phosphate ester-based flame retardants, water-releasing substances, etc. More specifically, for example, the content of the other solid flame retardants can be 20% by mass or less, 10% by mass or less, 5% by mass or less, or 1% by mass or less, when the entire chemical solution containing the flame retardant is taken as 100% by mass.

[0060] Among the above, in the present composition, an antimony-containing flame retardant is preferred. The antimony-containing flame retardant is a component that contains an antimony atom, and when used in combination with a bromine-based flame retardant and / or a solid chlorine-based flame retardant, it is possible to synergistically improve the flame retardant performance. Examples of antimony-containing flame retardants include antimony oxides such as antimony trioxide and antimony pentoxide; antimonate salts such as sodium antimonate and potassium antimonate; and pyroantimonate salts such as sodium pyroantimonate and potassium pyroantimonate.

[0061] When using antimony-containing flame retardants, the amount of antimony is not limited, but the content of red phosphorus is set to M S1 (mass%), and the content of antimony-containing flame retardant is M S3 (mass%), M S1 <M S3 However, M S1 ≧M S3It is preferable that the antimony-containing flame retardant is contained in an amount equal to or less than that of red phosphorus in terms of mass. In this composition, by using a liquid flame retardant in combination, it is possible to achieve high flame retardancy and on-site workability in this range while eliminating the polyol component. Furthermore, this ratio is preferably M S3 / M S1 When converted as 0.1≦M S3 / M S1 ≦1.5, and further 0.2≦M S3 / M S1 ≦1.2, and 0.3≦M S3 / M S1 ≦0.9, and 0.4≦M S3 / M S1 It is more preferable that the ratio is ≦0.8. Within these preferable ranges, by using a liquid flame retardant in combination, it is possible to achieve a higher level of both flame retardancy and on-site workability while eliminating the polyol component.

[0062] As other solid flame retardants, there may be mentioned various solid phosphate-based flame retardants such as monophosphates, pyrophosphates, polyphosphates, and organic phosphinates. Among these, examples of monophosphates include phosphates, hydrogen phosphates, phosphites, hypophosphites, etc. Examples of cations constituting these salts include ammonium ions, alkali metal ions (sodium, potassium, lithium, etc.), alkaline earth metal ions (calcium, magnesium, barium, etc.), zinc ions, etc.

[0063] Examples of 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, and 2,4-diamino-6-hydroxy-1,3,5-triazine 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, and 2-amino-4,6-dimercapto-1,3,5-triazine pyrophosphate. Furthermore, examples of the polyphosphate include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate.

[0064] In addition, the organic phosphinate salt may be an organic phosphinic acid having 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 the phosphorus atom constituting the phosphinic acid, and various known cations are bonded to the organic phosphinic acid to form a salt. For example, a methyl group, an ethyl group, or a phenyl group is bonded to the phosphorus atom, and the metal element constituting the cation may be Mg, Al, Ca, Ti, or Zn. Specifically, zinc (mono- or di-)methylphosphinate, zinc (mono- or di-)ethylphosphinate, zinc (mono- or di-)phenylphosphinate, aluminum (mono- or di-)methylphosphinate, aluminum (mono- or di-)ethylphosphinate, aluminum (mono- or di-)phenylphosphinate, etc. may be mentioned.

[0065] The boron-based flame retardants include boric acids, borates, boron-based nonmetallic compounds, borate minerals, organic boron-based compounds, etc. These may be used alone or in combination of two or more. Examples of boric acids include boric acid, orthoboric acid, and metaboric acid. Examples of borates include salts of the above-mentioned borates with metal ions and salts of ammonium ions. Examples of metal species constituting the metal ions include sodium, potassium, calcium, magnesium, barium, aluminum, and zinc. Examples of boron-based nonmetallic compounds include boron oxide and boron nitride. Examples of borate minerals include borax, colemanite, and ulexite. Examples of organic boron-based compounds include boric acid esters, boronates, and boroxines. These may be used alone or in combination of two or more.

[0066] Examples of the metal stannate include zinc stannate, barium stannate, sodium stannate, potassium stannate, cobalt stannate, and magnesium stannate.

[0067] The water-releasing substance is a substance that can be dehydrated or dehydrated upon decomposition when heated to a predetermined temperature. The water-releasing substance is not limited as long as it can release water by heating, but from the viewpoint of increasing the water-releasing temperature, inorganic compounds are preferred. Examples of inorganic compounds that are water-releasing substances include metal hydroxides, hydrates of metal compounds (excluding metal hydroxides), clay minerals, etc. These may be used alone or in combination of two or more. Among these, examples of the metal hydroxide include aluminum hydroxide (aluminum hydroxide), alkaline earth metal hydroxides (magnesium hydroxide, calcium hydroxide, etc.), and hydrates thereof, etc. These may be used alone or in combination of two or more. Examples of the hydrates of metal compounds include calcium silicate hydrate, aluminum oxide hydrate, aluminum chloride hydrate, aluminum sulfate hydrate, magnesium chloride hydrate, magnesium sulfate hydrate, etc. These may be used alone or in combination of two or more. Furthermore, examples of clay minerals include clay, kaolin, hydrotalcite, etc. These may be used alone or in combination of two or more kinds.

[0068] (4) Foaming agent The foaming agent is a component that forms a foamed state of the resulting flame-retardant foam. The type of foaming agent is not limited, and for example, organic foaming agents, inorganic foaming agents, etc. can be used. These may be used alone or in combination of two or more.

[0069] Of these, non-fluorocarbon and fluorocarbon blowing agents and sources of non-fluorocarbon and fluorocarbon blowing agents can be used as organic blowing agents. Specifically, fluorocarbons include hydrofluorocarbons (HFCs), non-fluorocarbons include hydrocarbons (HCs), and halogenated olefins (halogenated alkenes) called hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs). These may be used alone or in combination of two or more.

[0070] Among these, examples of the hydrocarbon include propane, normal pentane, isopentane, cyclopentane, butane, isobutane, hexane, isohexane, neohexane, heptane, and isoheptane. Specific examples of the hydrofluorocarbon 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), and 1,1,1,2,3,3,3-heptafluoropropane. Examples of the halogenated olefins include 1,1,1,3,3-pentafluoropropane (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, etc. Furthermore, examples of the halogenated olefins include unsaturated hydrocarbon derivatives having 2 to 6 carbon atoms and having halogen substituents of fluorine and / or chlorine, and further examples of the halogenated olefins include alkenes having 3 to 6 carbon atoms and having halogen substituents of fluorine and / or chlorine (propene, butene, pentene, hexene, etc.). Specific examples include tetrafluoropropene, pentafluoropropene, hexafluorobutene, fluorochloropropene, trifluoromonochloropropene, and fluorochlorobutene.

[0071] Examples of hydrofluoroolefins (HFOs) include pentafluoropropenes such as 1,2,3,3,3-pentafluoropropene (HFO1225ye); tetrafluoropropenes such as 1,3,3,3-tetrafluoropropene (HFO1234ze), 2,3,3,3-tetrafluoropropene (HFO1234yf), and 1,2,3,3-tetrafluoropropene (HFO1234ye); and trifluoropropenes such as 3,3,3-trifluoropropene (HFO1243zf). tetrafluorobutene isomers (HFO1354); pentafluorobutene isomers (HFO1345); hexafluorobutene isomers (HFO1336) such as 1,1,1,4,4,4-hexafluoro-2-butene (HFO1336mzz); heptafluorobutene isomers (HFO1327); heptafluoropentene isomers (HFO1447); octafluoropentene isomers (HFO1438); and nonafluoropentene isomers (HFO1429).

[0072] Examples of hydrochlorofluoroolefins (HCFOs) 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), and 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc).

[0073] On the other hand, examples of inorganic foaming agents include water, carbon dioxide, etc. These may be used alone or in combination of two or more. Of these, water functions as a foaming agent by generating carbon dioxide in the presence of polyisocyanate. Therefore, as described below, when water is used as a foaming agent, it is preferable that water and polyisocyanate are present as different chemical liquids before foaming the present composition. Carbon dioxide can be used in the form of liquefied carbon dioxide. For this reason, as described below, it is preferable that carbon dioxide exists alone as a liquid chemical different from other components before the composition is foamed.

[0074] The amount of the foaming agent is not limited and can be appropriately adjusted depending on the density and expansion ratio of the desired flame-retardant foam, but for example, when the total amount of polyisocyanate contained in the composition is 100 parts by mass, the amount of the foaming agent can be 0.1 parts by mass or more and 100 parts by mass or less. This amount can be further adjusted to 0.5 parts by mass or more and 70 parts by mass or less, further adjusted to 1 part by mass or more and 50 parts by mass or less, further adjusted to 2 parts by mass or more and 40 parts by mass or less, further adjusted to 3 parts by mass or more and less than 30 parts by mass, and further adjusted to 5 parts by mass or more and 20 parts by mass or less.

[0075] The density of the flame retardant foam is, for example, 60 kg / m 3 It is preferable to set it to 58 kg / m or less. 3 Below that, 55kg / m 3 Below that, 53kg / m 3 It is more preferable that the density is set to 45 kg / m or less. There is no lower limit to this density. 3 Above 47kg / m 3 Above 48kg / m 3 It is preferable to set the number of times to more than this.

[0076] (5) Other ingredients In the present composition, other components may be blended as necessary in addition to the above-mentioned polyisocyanate, catalyst, flame retardant, and blowing agent. Examples of other components include foam stabilizers, viscosity modifiers, and fillers. These may be used alone or in combination of two or more.

[0077] (5-1) Foam stabilizer The 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 for example, silicone-based foam stabilizers (silicone, etc.), nonionic surfactants, polyoxyalkylene-modified dimethylpolysiloxane, polysiloxane oxyalkylene copolymers, polyoxyethylene sorbitan fatty acid esters, castor oil ethylene oxide adducts, lauryl fatty acid ethylene oxide adducts, etc. can be used. These may be used alone or in combination of two or more. Among the foam stabilizers, for example, silicone-based foam stabilizers are preferred, and further, polyoxyalkylene-modified dimethylpolysiloxane, polysiloxane oxyalkylene copolymers, etc. can be preferably used. When a foam stabilizer is used, the amount of the foam stabilizer is not limited. For example, when the total amount of the foaming agents used in the present composition is 100 parts by mass, the amount of the foam stabilizer can be 0.1 parts by mass or more and 20 parts by mass or less, and further, can be 0.5 parts by mass or more and 10 parts by mass or less.

[0078] (5-2) Viscosity modifier The viscosity adjuster is a component that adjusts the viscosity of each liquid drug that constitutes the present composition. For example, a viscosity reducer can be used as the viscosity adjuster. That is, a component that reduces the viscosity can be used. The type of the viscosity reducer is not limited, but for example, alcohols, ethers, esters, petroleum-based hydrocarbons, etc. can be used. These can be used alone or in combination of two or more types. Among these, examples of alcohols include methanol, ethanol, etc. Examples of ethers include ethyl cellosolve, butyl cellosolve, etc. Examples of esters include cyclic esters such as propylene carbonate, etc.; esters (non-cyclic esters) such as dicarboxylic acid methyl ester, ethylene glycol monomethyl ether acetate, etc.

[0079] (5-3) Filler The filler is a component that has the effect of increasing the volume of the obtained flame-retardant foam and the effect of improving the strength of the obtained flame-retardant foam. The type of filler is not limited, and inorganic fillers and organic fillers can be used. These may be used alone or in combination of two or more. Of these, inorganic fillers are more preferably used from the viewpoint of improving flame retardancy. The type of inorganic filler is not limited, and examples thereof include calcium carbonate, barium sulfate, silica, clay, talc, white carbon (diatomaceous earth), etc. These may be used alone or in combination of two or more.

[0080] (6) Composition of the drug solution The composition is composed of two or more chemical liquids, and further, in the composition, the polyisocyanate, the flame retardant, and the trimerization catalyst are contained in different chemical liquids. The composition may be composed of two or more kinds of chemicals, and is usually composed of five or less kinds of chemicals, and is preferably composed of four or less kinds of chemicals from the viewpoint of workability. More specifically, the composition may be composed of the following chemicals, for example, <1> to <4>.

[0081] <1> A composition may be formed from two kinds of chemical liquids, liquid A and liquid B, in which liquid A contains a polyisocyanate, liquid B contains a flame retardant and a trimerization catalyst, and at least one of liquid A and liquid B contains a blowing agent. More specifically, <1-1> A composition may be formed in which liquid A contains a polyisocyanate, and liquid B contains a flame retardant, a trimerization catalyst, and a blowing agent. Also, <1-2> A composition may be formed in which liquid A contains a polyisocyanate and a blowing agent, and liquid B contains a flame retardant and a trimerization catalyst.

[0082] <2> The composition may be composed of three kinds of chemical liquids, namely, liquid A, liquid B, and liquid C, in which liquid A contains a polyisocyanate, liquid B contains a flame retardant, liquid C contains a trimerization catalyst, and at least one of liquid A, liquid B, and liquid C contains a blowing agent. More specifically, <2-1> the composition may be composed of liquid A containing a polyisocyanate, liquid B containing a flame retardant, and liquid C containing a trimerization catalyst and a blowing agent. Also, <2-2> the composition may be composed of liquid A containing a polyisocyanate, liquid B containing a flame retardant and a blowing agent, and liquid C containing a trimerization catalyst. Also, <2-3> the composition may be composed of liquid A containing a polyisocyanate and a blowing agent, liquid B containing a flame retardant, and liquid C containing a trimerization catalyst.

[0083] <3> A composition can be made that is composed of three kinds of chemical liquids, namely, liquid A, liquid B, and liquid C, in which liquid A contains a polyisocyanate, liquid B contains a flame retardant and a trimerization catalyst, and liquid C contains a blowing agent. This chemical liquid composition can be said to be a suitable composition when carbon dioxide or the like is used as a blowing agent. Note that liquid A and liquid B may contain a blowing agent other than carbon dioxide as necessary.

[0084] <4> A composition can be made that is composed of four kinds of chemical liquids, namely, liquid A, liquid B, liquid C, and liquid D, in which liquid A contains a polyisocyanate, liquid B contains a flame retardant, liquid C contains a trimerization catalyst, and liquid D contains a blowing agent. This chemical liquid configuration can be said to be a suitable configuration when carbon dioxide or the like is used as a blowing agent. Note that liquid A, liquid B, and liquid C may contain a blowing agent other than carbon dioxide as necessary.

[0085] In addition, regardless of which of the chemical liquid compositions of <1> to <4> is used, it is preferable that the chemical liquid containing polyisocyanate does not substantially contain water. Specifically, when the entire chemical liquid containing polyisocyanate is taken as 100 mass%, the content of water is preferably 1 mass% (may be 0 mass%), further 0.5 mass% (may be 0 mass%), and particularly preferably 0.1 mass% (may be 0 mass%).

[0086] In addition, when the liquid A is a chemical liquid containing a polyisocyanate and the liquid B is a chemical liquid containing a flame retardant, the viscosity of each of the liquids A and B is not limited, but the upper limit of the viscosity measured at 25°C using a B-type viscometer in accordance with JIS K7117-1 can be 100,000 mPa·s or less, preferably 50,000 mPa·s or less, more preferably 10,000 mPa·s or less, even more preferably 6,000 mPa·s or less, particularly preferably 5,000 mPa·s or less, and particularly preferably 3,000 mPa·s or less. In addition, 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. The viscosities of the liquids A and B may be different, but it is preferable that the difference is not excessively large. More specifically, the viscosity of the liquid A is V A (mPa s), and the viscosity of B liquid is V B (mPa·s), for example, 0.6≦V A / V B It can be ≦1.4.

[0087] Furthermore, the reaction time when the chemicals are mixed (the time from mixing to obtaining a flame-retardant foam) is preferably 20 minutes or less. When the reaction time is 20 minutes or less, a sufficient curing speed and sufficient mechanical strength can be obtained in the obtained cured body even at low temperatures such as in winter. Furthermore, this 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 preferred range, clogging of the injection tube can be more reliably prevented, and sufficient time for penetration into the injection site after injection can be provided.

[0088] From this composition, a flame-retardant foam can also be obtained by filling a mold with a mixed liquid obtained by mixing the chemicals constituting this composition and molding it. On the other hand, as described above, since this composition has excellent on-site applicability, it is particularly suitable for use in an embodiment in which a flame-retardant foam layer made of a flame-retardant foam is formed on the surface of an adherend by spraying a mixed liquid obtained by mixing chemicals or a chemical liquid mixed in an apparatus onto an adherend. It is also suitable for use in an embodiment in which a filler made of a flame-retardant foam is formed in a gap by spraying a mixed liquid obtained by mixing chemicals or a chemical liquid mixed in an apparatus into a gap formed in a structure or the like.

[0089] (7) Uses of the 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 (architecture and civil engineering). That is, the present composition can be used, for example, as a composition for flame-retardant foam in the field of construction and civil engineering. Among these, for example, in the field of construction, the present composition can be used for flame-retardant foam for walls, flame-retardant foam for ceilings, flame-retardant foam for floors, insulation for walls, insulation for ceilings, insulation for floors, on-site spraying during the manufacture of structures, filling internal gaps, and reinforcing structures that have deteriorated over time. In addition, in the field of civil engineering, the present composition can be injected into natural ground, underground, soil, ground, bedrock, gaps between these and structures (architectural structures), and even gaps within structures, and the like, and then foamed and cured, thereby filling and reinforcing the injected parts. EXAMPLES

[0090] The present invention will be described in more detail below with reference to examples. However, these examples are merely illustrative and are not intended to limit the present invention in any way.

[0091] [1] Preparation of the composition The following components were mixed in the combinations and proportions shown in Tables 1 to 5 below to obtain flame-retardant foam compositions having Liquid A and Liquid B of Examples 1 to 12 and Comparative Examples 1 to 10.

[0092] (1) Polyisocyanate Polymeric MDI (Wannate, manufactured by Wanka Chemical Japan Co., Ltd., product name "PM-130", viscosity (25°C): 150 mPa s)

[0093] (2) Polyol Phthalic acid-based polyester polyol (Kawasaki Chemical Industries, Ltd., product name "RDK133", hydroxyl value 315mgKOH / g)

[0094] (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 (Kao Corporation, product name "Kao Raiser No. 420")

[0095] (4) Resinification catalyst Bismuth octylate (manufactured by Nippon Chemical Industry Co., Ltd., product name "Pucat 25")

[0096] (5) Foam stabilizer Silicone foam stabilizer (manufactured by Momentive Performance Materials Japan, LLC, product name "Niax Silicone L-6100")

[0097] (6) Flame retardants - Liquid flame retardants Organic phosphate ester (1): Polyphosphate ester (manufactured by ADEKA Corporation, product name "ADEKA STAB PFR", viscosity (25°C): 560 mPa s) Organic phosphate ester (2): TCPP / tris(1-chloro-2-propyl)phosphate (Wanxiang Co., Ltd., viscosity (25°C): 70 mPa·s)

[0098] (7) Flame retardants - Solid flame retardants - Solid organic phosphate esters Solid organic phosphate ester: Tris(tribromoneopentyl)phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name "CR-900", powder

[0099] (8) Flame retardants - solid flame retardants - red phosphorus Red phosphorus: Red phosphorus (manufactured by Rinkagaku Kogyo Co., Ltd., product name "Nova Excel 140", phosphorus concentration: 94% by mass, average particle size: 30 μm)

[0100] (9) Flame retardants - Solid flame retardants - Brominated flame retardants EBPBP: Ethylene-1,2-bis(pentabromophenyl) (manufactured by Albemarle Japan Co., Ltd., product name "SAYTEX (trademark) 8010"), a brominated polycyclic aromatic compound HBB: Hexabromobenzene (manufactured by Manac Corporation, product name "HBB-B"), a brominated monocyclic aromatic compound

[0101] (10) Flame retardants - Solid flame retardants - Chlorine-based flame retardants Chlorinated paraffin: (manufactured by Tosoh Corporation, product name "TOYOPARAX (trademark)")

[0102] (11) Flame retardants - Solid flame retardants - Antimony-containing flame retardants Antimony trioxide: (manufactured by Nihon Seiko Co., Ltd., product name "PATOX-C")

[0103] (12) Foaming agent HCFO-1233zd: 1-chloro-3,3,3-trifluoropropene (Honeywell) HFO-1336mzz: 1,1,1,4,4,4-hexafluoro-2-butene (manufactured by Chemours) HFC245fa / HFC365mfc (=8 / 2): A blowing agent made by mixing HFC245fa, a 1,1,1,3,3-pentafluoropropane manufactured by Central Glass Co., Ltd., and HFC365mfc, a 1,1,1,3,3-pentafluorobutane manufactured by SOLVAY Co., Ltd., in an 8:2 ratio.

[0104] [2] Manufacturing of foams (flame-retardant foams) The flame-retardant foam compositions of Examples 1 to 12 and Comparative Examples 1 to 10 obtained in [1] above were used in such a way that the volume ratio of A liquid to B liquid was 1:1, and spraying was performed once under and once over on the surface of the adherend, an inorganic flexible board (910 mm x 910 mm), at an ambient temperature of 15°C, using an on-site spray foaming machine (name: A-25, manufactured by Graco). As a result, a foam layer (thickness: about 60 mm) with a under-spray layer of about 5 mm and a top-spray layer of 50 to 60 mm was obtained. Note that spraying could not be performed on the four points of Comparative Examples 5, 6, 7, and 8.

[0105] [Table 1] In addition, M in the table L , M S , M S1 and M S2 Each of the following has the following meaning: L = Liquid flame retardant / total B liquid (mass%), M S = Solid flame retardant / total B solution (mass%), M S1 = Red phosphorus / total solid flame retardant (mass%), M S2 = Total of brominated flame retardants and chlorinated flame retardants / Total solid flame retardants (mass%)

[0106] [Table 2] In addition, M in the table L , M S , M S1 and M S2 Each of the following has the following meaning: L = Liquid flame retardant / total B liquid (mass%), M S = Solid flame retardant / total B solution (mass%), M S1 = Red phosphorus / total solid flame retardant (mass%), M S2 = Total of brominated flame retardants and chlorinated flame retardants / Total solid flame retardants (mass%)

[0107] [Table 3] In addition, M in the table L , M S , MS1 and M S2 Each of the following has the following meaning: L = Liquid flame retardant / total B liquid (mass%), M S = Solid flame retardant / total B solution (mass%), M S1 = Red phosphorus / total solid flame retardant (mass%), M S2 = Total of brominated flame retardants and chlorinated flame retardants / Total solid flame retardants (mass%)

[0108] [Table 4] In addition, M in the table L , M S , M S1 and M S2 Each of the following has the following meaning: L = Liquid flame retardant / total B liquid (mass%), M S = Solid flame retardant / total B solution (mass%), M S1 = Red phosphorus / total solid flame retardant (mass%), M S2 = Total of brominated flame retardants and chlorinated flame retardants / Total solid flame retardants (mass%)

[0109] [Table 5] In addition, M in the table L , M S , M S1 and M S2 Each of the following has the following meaning: L = Liquid flame retardant / total B liquid (mass%), M S = Solid flame retardant / total B solution (mass%), M S1 = Red phosphorus / total solid flame retardant (mass%), M S2 = Total of brominated flame retardants and chlorinated flame retardants / Total solid flame retardants (mass%)

[0110] [3] Measurement and evaluation The foams of the 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 4. Furthermore, the flame-retardant foam compositions of Examples 1, 5 and 8 obtained in [1] above were evaluated as shown in (7) below. Table 5 shows the results.

[0111] (1) Density measurement From the obtained foam (thickness: about 60 mm), a test piece with a thickness of 50 mm is cut out while leaving the surface skin layer, and a test piece of 100 mm x 100 mm x 50 mm is taken. The dimensions of this test piece are accurately measured using a vernier caliper, and its mass is measured using an electronic balance. From the obtained measured values, the density of the test piece is calculated in accordance with JIS K7222.

[0112] (2) Measurement of maximum heat release rate and total heat release The test piece in (1) above was subjected to a radiant heat intensity of 50 kW / m in accordance with the combustion test method specified in ISO-5660. 2 The maximum heat release rate and total heat release amount are measured when heated for 20 minutes at 40°C.

[0113] (3) Measurement of self-extinguishing time In the above test (2), the time from ignition by heating to extinguishing of the flame is measured.

[0114] (4) Evaluation of reignition after self-extinguishing In the above test (2), if a flame re-ignited after the flame went out from the ignition by heating, it was judged as having re-ignition, and if it did not re-ignite, it was judged as not having re-ignition. Three samples were measured, and the samples that did not re-ignite were rated as "◎", those that did not re-ignite were rated as "○", those that re-ignited were rated as "△", and those that re-ignited were rated as "×".

[0115] (5) Crack evaluation Of the test pieces obtained after completing the test in (2) above, those that have no cracks on the surface are evaluated as "○", those that have cracks on the surface are evaluated as "×", and those that have cracks that reach from the front side to the back side of the test piece are evaluated as "XX".

[0116] (6) Measurement of heat release rate 3 minutes after ignition In the above test (2), the heat release rate is 10 kW / m 3 minutes or more after ignition.2 Those below 10kW / m 2 Anything exceeding this will be evaluated as "X".

[0117] (7) Evaluation of mixture characteristics Solution B was stirred in a disperser at 1000 rpm for 3 minutes, and after stirring, it was allowed to stand for 10 minutes. The appearance of solution B was then visually inspected and the mixing characteristics were evaluated based on the following criteria. ◯: Uniform, no separation observed after standing. △: Partial separation was observed after standing. ×: Significant separation occurs.

[0118] [4] Effects of the embodiment From Tables 1 to 4, in Comparative Examples 1 to 4, 9, and 10, the total calorific value is 10.1 to 18.2 MJ / m 2 In contrast, in Examples 1 to 12, the total calorific value was 5.7 to 6.9 MJ / m 2 In addition, in Comparative Examples 1 to 4, 9, and 10, the maximum heat generation rate was 121 to 162 kW / m 2 In contrast, in Examples 1 to 12, the maximum heat generation rate was 54 to 82 kW / m 2 In addition, the self-extinguishing time is effectively suppressed to a small value of 8 to 13 seconds in Examples 1 to 12, whereas Comparative Examples 1 to 4, 9, and 10 have a long self-extinguishing time of 22 to 34 seconds. In addition, in the Comparative Examples in which a foam could be formed, the heat release rate 3 minutes after ignition was 10 kW / m 2 In contrast, in Examples 1 to 13, the 2 was kept below.

[0119] The difference between the above-mentioned Examples and Comparative Examples is believed to be due to the fact that Comparative Examples 1 to 4 contain polyol, and Comparative Examples 9 and 10 do not contain red phosphorus. That is, it is believed that in Examples 1 to 12, the total heat generation amount and the maximum heat generation rate can be suppressed by excluding polyol. However, as described above, in the past, polyol functioned as a liquid base, so it was not easy to eliminate it. In contrast, the present composition uses a liquid flame retardant as a liquid base, and then uses red phosphorus and a bromine-based flame retardant and / or a chlorine-based flame retardant as a solid flame retardant in combination, thereby making it possible to make a composition that can be applied on site and to achieve excellent flame retardancy at the same time. Furthermore, in this test, no cracks were observed in any of the examples, even though the foam including the skin layer was burned. From this, it is considered that the formation of the carbonized layer on the surface of the foam after ignition can be promoted and the occurrence of cracks on the surface can be suppressed. This is considered to prevent combustion from the cracks and to prevent an increase in the amount of heat generated.

[0120] In addition, from Tables 1 to 4, among the comparative examples in which foams could be formed, re-ignition of flame after self-extinguishing was observed in all of Comparative Examples 2 to 4. In contrast, in Examples 1 to 12, extremely excellent results were obtained in which no re-ignition of flame was observed in any of the three samples. It is believed that the mechanism of excluding polyol also contributes greatly to this effect. On the other hand, flame reattack was observed in only one of the three samples in Example 4. This result shows that in the combination of components in this composition, the use of a brominated polycyclic aromatic compound as the brominated flame retardant can more effectively suppress flame reattack than the use of a brominated monocyclic aromatic compound.

[0121] In Example 12, re-ignition was observed in only one of the three samples. This is thought to be due to the influence of the inclusion of water. In other words, it is thought that the inclusion of water resulted in the consumption of isocyanate after mixing of the A and B liquids, resulting in less isocyanurate formation than in the other Examples, which resulted in re-ignition. Therefore, it is clear that it is preferable for this composition to be structured so as to contain as little water as possible.

[0122] Furthermore, when Examples 1 to 3 are compared, as the blending ratio of the bromine-based flame retardant is increased relative to the blending ratio of red phosphorus, that is, M S2 / M S1 It can be seen that increasing the value of can reduce the maximum heat release rate and the total heat release amount. Furthermore, as shown in Examples 5 and 7 and Examples 1 and 6, in the present composition, the total calorific value can be reduced by using red phosphorus in combination with a bromine-based flame retardant and / or a chlorine-based flame retardant as a solid flame retardant, and further using an antimony-containing flame retardant in combination. [Industrial Applicability]

[0123] It is suitably used in the fields of architecture and civil engineering (architecture and civil engineering). For example, in the field of architecture, it can be used for flame-retardant foam for walls, flame-retardant foam for ceilings, flame-retardant foam for floors, insulation for walls, insulation for ceilings, insulation for floors, filling internal gaps during the manufacture of structures, reinforcing structures that have deteriorated over time, etc. In the field of civil engineering, the composition can be injected into natural ground, underground, soil, foundation, bedrock, gaps between these and structures (architectural structures), and even gaps within structures, and the like, and then foamed and cured, thereby filling and reinforcing the injected portions.

Claims

1. 1. A flame retardant foam composition for forming a polyol-free polyisocyanurate foam, comprising: A polyisocyanate, a trimerization catalyst for the polyisocyanate, a flame retardant, and a blowing agent, The composition is composed of two or more kinds of chemical solutions, and the polyisocyanate, the flame retardant, and the trimerization catalyst are contained in different chemical solutions, The flame retardant includes a liquid flame retardant and a solid flame retardant, 1. A flame-retardant foam composition, comprising: a solid flame retardant comprising red phosphorus and at least one of a brominated flame retardant and a chlorinated flame retardant.

2. The flame-retardant foam composition according to claim 1, wherein the liquid flame retardant accounts for 25 to 60 mass % of the chemical liquid when the entire chemical liquid including the flame retardant is taken as 100 mass %.

3. The flame-retardant foam composition according to claim 1 or 2, wherein the liquid flame retardant comprises an organic phosphate ester and / or a chlorine-based flame retardant.

4. The total amount of the solid flame retardant is taken as 100 mass %, and the content of the red phosphorus is taken as M Ｓ１ (mass%), and the total content of the brominated flame retardant and the chlorine-based flame retardant is M Ｓ２ (mass%), M Ｓ１ <M Ｓ２ The flame-retardant foam composition according to any one of claims 1 to 3, wherein

5. 5. The flame-retardant foam composition according to claim 1, wherein the red phosphorus is in the form of granules with an average particle size of 15 μm or more.

6. 6. The flame-retardant foam composition according to claim 1, wherein the liquid flame retardant has a viscosity of 100 to 1000 mPa·s.

7. 7. The flame retardant foam composition of claim 1, wherein the solid flame retardant further comprises an antimony-containing flame retardant.

8. It is composed of two types of chemical liquids, A and B, The solution A contains the polyisocyanate, The B solution contains the flame retardant and the trimerization catalyst, The flame-retardant foam composition according to claim 1 , wherein the foaming agent is contained in at least one of the liquid A and the liquid B.

9. It is composed of three types of chemical liquids: A, B, and C. The solution A contains the polyisocyanate, The liquid B contains the flame retardant, the liquid C contains the trimerization catalyst, The flame-retardant foam composition according to claim 1 , wherein the foaming agent is contained in at least one of the liquid A, the liquid B, and the liquid C.

10. It is composed of three types of chemical liquids: A, B, and C. The solution A contains the polyisocyanate, The B solution contains the flame retardant and the trimerization catalyst, The flame-retardant foam composition according to claim 1 , wherein the liquid C contains the foaming agent.

11. It is composed of four types of chemical liquids: A, B, C, and D. The solution A contains the polyisocyanate, The liquid B contains the flame retardant, the liquid C contains the trimerization catalyst, The flame-retardant foam composition according to claim 1 , wherein the liquid D contains the blowing agent.

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