JP2018080328A - Foamable polyurethane composition for on-site spraying - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a foaming heat-insulation material for on-site spraying that adheres to a base material even at a fire, holds the adhesiveness and therefore does not come off.SOLUTION: The present invention provides a polyol composition that reacts with a polyisocyanate compound to obtain a foamable polyurethane composition for on-site spraying. The polyol composition contains a polyol compound, a flame retardant, and a catalyst. As the flame retardant, the composition contains at least red phosphorus.SELECTED DRAWING: None

Description

  The present invention relates to a polyol composition for obtaining a foamable polyurethane composition for in-situ spraying, a foamable polyurethane premix composition for in-situ spraying, a foamable polyurethane composition for in-situ spraying, a flame retardant structure, and a method for producing the same. .

  A urethane resin composition is used as a heat insulating material for buildings such as apartment houses such as apartment buildings, detached houses, various facilities of schools, commercial buildings, and the like because of its excellent heat insulating properties and adhesive properties. Among them, it is useful as an in-situ foaming urethane.

JP 2014-193995 International Publication WO2016 / 047767 JP2015-078357

  The foamable urethane resin composition adheres and foams to various substrates based on its adhesiveness and foamability, and exhibits heat insulation properties. However, it does not work as a heat insulator because it burns and disappears in the event of a fire. was there. In recent years, fires caused by ignition of urethane have increased, and there is a demand for foamed heat insulating materials that are difficult to burn.

  The inventors of the present application have made various studies in order to achieve the above object, and by adding red phosphorus as a flame retardant to urethane, the adhesiveness is maintained by adhering to the base material (especially steel) even in the event of a fire. As a result, it has been found that a foamed heat insulating material that does not easily fall off from the substrate can be obtained, and the present invention has been completed.

  That is, the present invention is as follows.

[1] A polyol composition for mixing with a polyisocyanate compound to obtain a foamable polyurethane composition for in-situ spraying,
Contains a polyol compound, a flame retardant, and a catalyst,
A polyol composition comprising at least red phosphorus as the flame retardant.

  [2] The polyol composition according to [1], further comprising a needle-like filler and / or a boron-containing flame retardant as the flame retardant.

  [3] The trimerization catalyst is contained as the catalyst, and the trimerization catalyst is contained in an amount of 0.4 to 38 parts by mass with respect to 100 parts by mass of the polyol compound. Polyol composition.

  [4] The urethanization catalyst is contained as the catalyst, and the urethanization catalyst is contained in an amount of 0.4 to 38 parts by mass with respect to 100 parts by mass of the polyol compound. The polyol composition according to any one of the above.

  [5] A foamable polyurethane premix composition for on-site spraying, comprising the polyol composition according to any one of [1] to [4] and an isocyanate compound separately.

  [6] A foamable urethane resin composition for on-site spraying, which is a mixture of the polyol composition according to any one of [1] to [4] and an isocyanate compound.

  [7] The foamable urethane resin composition for on-site spraying according to [6] for spraying on a steel substrate.

  [8] The foamable urethane resin composition for in-situ spraying according to [6] for spraying on a concrete substrate.

  [9] A method for producing a flame-retardant structure, comprising a step of spraying a foamable urethane resin composition for on-site spraying according to any one of [6] to [8] onto a substrate.

  [10] The method for producing a flame-retardant structure according to [9], wherein the base material is steel or concrete.

  [11] The method for producing a flame-retardant structure according to [9] or [10], comprising a step of mixing a foamable urethane resin composition for on-site spraying on-site.

  [12] A flame-retardant structure in which a urethane foam obtained by curing the foamable urethane resin composition for on-site spraying according to any one of [6] to [8] is laminated on a base material that is steel or concrete.

  Polyol composition, foamable polyurethane premix composition, foamable urethane resin composition, and adhesive for forming a foamed heat insulating material that retains adhesiveness and does not fall off according to the present invention by spraying the substrate on site Provided are a flame retardant structure having a foamed heat insulating material that retains its properties and does not fall off, and a method for manufacturing the same.

The present invention includes the following aspects.
(I) A polyol composition for reacting with a polyisocyanate compound to obtain a foamable polyurethane composition for on-site spraying, comprising a polyol compound, a flame retardant, and a catalyst, and red phosphorus as the flame retardant A polyol composition characterized by comprising,
(Ii) a foamable polyurethane premix composition for in-situ spraying, characterized by comprising separately the polyol composition and polyisocyanate compound;
(Iii) a foamable polyurethane composition for in-situ spraying, which is a mixture of the polyol composition and a polyisocyanate compound;
(Iv) A method for producing a flame-retardant structure, comprising the step of spraying the foamable urethane resin composition for in-situ spraying onto a base material, and (v) the foamability for in-situ spraying on a base material that is steel or concrete. Flame retardant structure in which urethane foam is cured urethane resin composition.

  The polyol composition of the present invention contains a polyol, a polyol compound, a flame retardant, a catalyst, and optionally other components. Examples of other components include, but are not limited to, foam stabilizers, catalysts, and foaming agents.

  The polyol composition is, for example, a solution or a dispersion.

  The polyisocyanate as the main component of the urethane resin and the polyol as the curing agent of the urethane resin are cured by a chemical reaction to form a urethane resin.

  Hereinafter, each component will be described.

1. Polyols Examples of polyols that are curing agents for urethane resins include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.

  Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.

  Examples of the polycarbonate polyol include a polyol obtained by a dealcoholization reaction of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with diethylene carbonate, dipropylene carbonate, and the like. Etc.

  Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, and cresol novolak.

  Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, dimethyldicyclohexylmethanediol, and the like.

  Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

  Examples of the polyester polyol include a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, a polymer obtained by ring-opening polymerization of a lactone such as ε-caprolactone and α-methyl-ε-caprolactone, Examples thereof include condensates of hydroxycarboxylic acid and the above polyhydric alcohol.

  Specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid. Specific examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, neopentyl glycol, and the like. .

  Specific examples of the hydroxycarboxylic acid include castor oil, a reaction product of castor oil and ethylene glycol, and the like.

  Examples of the polymer polyol include a polymer obtained by graft polymerization of an ethylenically unsaturated compound to a polyol compound, a polybutadiene polyol, a modified polyol of a polyhydric alcohol, or a hydrogenated product thereof. Examples of the polyol compound in the polymer obtained by graft polymerization of an ethylenically unsaturated compound to the polyol compound include aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, and the like. Examples of the ethylenically unsaturated compound in the polymer obtained by graft polymerization of an ethylenically unsaturated compound with respect to a polyol include acrylonitrile, styrene, methyl acrylate, and methacrylate.

  Examples of the modified polyol of the polyhydric alcohol include those modified by reacting the raw material polyhydric alcohol with an alkylene oxide.

As the polyhydric alcohol, for example,
Trihydric alcohols such as glycerin and trimethylolpropane;
Tetravalent to octavalent alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methylglucoside and derivatives thereof;
Phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, anthrol, 1,4,5,8 -Phenol polybutadiene polyols such as tetrahydroxyanthracene, 1-hydroxypyrene;
Castor oil polyol; (co) polymer of hydroxyalkyl (meth) acrylate and polyfunctional polyol (eg 2 to 100 functional groups) such as polyvinyl alcohol, condensate of phenol and formaldehyde (novolak)
Is mentioned.

  The method for modifying the polyhydric alcohol is not particularly limited. As a method for modifying the polyhydric alcohol, a method of adding alkylene oxide (hereinafter abbreviated as AO) is preferably used.

  As AO, C2-C6 AO, for example, ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propyloxide, 1,2- Examples include butylene oxide and 1,4-butylene oxide.

  Among these, from the viewpoints of properties and reactivity, PO, EO, and 1,2-butylene oxide are preferable, and PO and EO are more preferable. When two or more types of AO are used (for example, PO and EO), block addition or random addition may be used, or a combination thereof may be used.

  As the polyether polyol, for example, ring-opening polymerization of at least one alkylene oxide such as ethylene oxide, propylene oxide, and tetrahydrofuran in the presence of at least one kind of low molecular weight active hydrogen compound having two or more active hydrogens. The polymer obtained by making it contain is mentioned.

  Examples of the low molecular weight active hydrogen compound having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol, and triols such as glycerol and trimethylolpropane. And amines such as ethylenediamine and butylenediamine.

  The polyol used in the present invention is preferably a polyester polyol or a polyether polyol because the effect of reducing the total calorific value upon combustion is great.

  Among them, it is more preferable to use a polyester polyol having a molecular weight of 200 to 800, and it is more preferable to use a polyester polyol having a molecular weight of 300 to 500.

2. Polyisocyanate compound Examples of the polyisocyanate compound that is a main component of the urethane resin include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.

  Examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

  Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

  One or more polyisocyanate compounds can be used. The main component of the urethane resin is preferably an aromatic polyisocyanate such as diphenylmethane diisocyanate because it is easy to use and easily available.

  In the composition of the present invention, the isocyanate index is preferably 150 or more and 1000 or less, more preferably 200 or more and 800 or less, further preferably 250 or more and 700 or less, and most preferably 300 or more and 600 or less.

The isocyanate index (INDEX) is calculated by the following method.
INDEX = isocyanate equivalent number / (polyol equivalent number + water equivalent number) × 100
here,
Equivalent number of isocyanate = number of polyisocyanate used × NCO content (%) ÷ 100 / NCO molecular weight,
Equivalent number of polyol = OHV × number of used parts of polyol ÷ molecular weight of KOH, OHV is hydroxyl value of polyol (mg KOH / g),
Equivalent number of water = number of used parts of water × number of OH groups of water / molecular weight of water. In the above formula, the unit of the number of parts used is weight (g), the molecular weight of the NCO group is 42, and the NCO content is the percentage of the NCO group in the polyisocyanate compound expressed by mass%. For convenience of unit conversion, the molecular weight of KOH is 56100, the molecular weight of water is 18, and the number of OH groups in water is 2.

3. Catalyst Examples of the catalyst include a trimerization catalyst. A trimerization catalyst makes the isocyanate group contained in the polyisocyanate which is the main ingredient of a polyurethane resin react and trimerize, and further promotes the production | generation of an isocyanurate ring.

In order to further promote the formation of the isocyanurate ring, for example, as a trimerization catalyst,
Nitrogen-containing aromatic compounds such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine;
Carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate, potassium octylate;
Tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt;
Quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt and tetraphenylammonium salt can be used.

  The content of the trimerization catalyst is preferably in the range of 0.3 to 38 parts by mass, more preferably in the range of 0.3 to 30 parts by mass with respect to 100 parts by mass of the polyol. The range of 0.3 to 23 parts by mass is more preferable, and the range of 3 to 23 parts by mass is most preferable. In a foaming polyurethane composition, it can be set as the range of 0.1 mass part-10 mass parts with respect to 100 mass parts of urethane resins, and it is more preferable that it is the range of 0.1 mass part-8 mass parts. Preferably, it is in the range of 0.1 to 6 parts by mass, and more preferably in the range of 1 to 6 parts by mass. When the amount is not less than the above lower limit value, the formation of an isocyanurate ring is sufficiently promoted, and when it is not more than the above upper limit value, an appropriate foaming rate can be maintained and the handling is easy.

  Moreover, a urethanization catalyst can also be used as a catalyst. The urethanization catalyst is a catalyst that causes a polymerization reaction simultaneously with the curing and urethanization reaction.

Urethane catalysts include tertiary amine catalysts such as alkylated polyalkylene polyamines, triethylamine, triethylenediamine, N-ethylmorpholine, diethylethanolamine, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N′-trimethyl. Aminoethyl-ethanolamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, diaminobicyclooctane, 1,2-dimethylimidazole, 1-methylimidazole, 1-isobutyl-2-methylimidazole, bis (dimethylaminoethyl) ether, 1,8-diazabicyclo- [5,4,0] -undecene-7;
Metal catalysts such as stannous octylate, dibutylstannic dilaurate, lead octylate, bismuth carboxylate, zirconium complexes;
And combinations thereof.

  The content of the urethanization catalyst is preferably in the range of 0 to 38 parts by mass, more preferably in the range of 0.3 to 38 parts by mass with respect to 100 parts by mass of the polyol. More preferably, it is in the range of 3 parts by mass to 27 parts by mass, and most preferably in the range of 1 part by mass to 15 parts by mass. In a foamable polyurethane composition, it can be set as the range of 0-10 mass parts with respect to 100 mass parts of urethane resins, It is more preferable that it is the range of 0.1-7 mass parts, 1 mass parts- More preferably, it is in the range of 4 parts by mass.

  One type or two or more types of catalysts can be used.

4). Examples of the foam stabilizer include surfactants such as a polyoxyalkylene foam stabilizer such as polyoxyalkylene alkyl ether, and a silicone foam stabilizer such as organopolysiloxane.

  If an example shows content of a foam stabilizer, if it is the range of 0.3 mass part-38 mass parts with respect to 100 mass parts of polyols, for example, it is preferable. In a foaming polyurethane composition, it sets suitably according to a urethane resin, and if it shows an example, it shall be the range of 0.1 mass part-10 mass parts with respect to 100 mass parts of urethane resins, for example. it can.

  One or more foam stabilizers can be used.

5. Foaming agent Foaming agent promotes foaming of urethane resin. As a foaming agent, for example,
water;
Low boiling point hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane;
Chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride;
Fluorine compounds such as CHF ₃ , CH ₂ F ₂ , and CH ₃ F;
Trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane) )) And other hydrochlorofluorocarbon compounds;
Hydrofluorocarbons such as HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane);
Hydrofluoroolefins such as HFO-1233zd (1-chloro-3,3,3-trifluoropropene);
Organic physical foaming agents such as ether compounds such as diisopropyl ether, or mixtures of these compounds,
Examples thereof include inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas.

  The content of the foaming agent is not particularly limited. The content of the foaming agent is, for example, preferably from 0.3 to 112 parts by weight, more preferably from 0.3 to 67 parts by weight, and even more preferably 1 to 100 parts by weight of polyol. The range is from 6 parts by mass to 68 parts by mass, and most preferably from 3 parts by mass to 47 parts by mass. In a foaming polyurethane composition, it can be set as the range of 0.1 mass part-30 mass parts with respect to 100 mass parts of urethane resins, and it is more preferable that it is the range of 0.1 mass part-18 mass parts. Preferably, the range is 0.5 to 18 parts by mass, and most preferably 1 to 15 parts by mass. The content of the foaming agent is in the range of 3 to 38 parts by weight with respect to 100 parts by weight of the polyol, or in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the urethane resin in the foamable polyurethane composition. It can also be.

  When the water range is not less than the above lower limit, foaming is promoted, and the density of the resulting molded product can be reduced. When the range is not more than the above upper limit, the foam does not foam and no foam is formed. Can be prevented.

  One or two or more foaming agents can be used.

6). Flame retardant A flame retardant can be used by appropriately selecting a commercially available product. The present invention includes at least red phosphorus as a flame retardant. There is no limitation in red phosphorus used for this invention, A commercial item can be selected suitably and can be used.

  Moreover, it is preferable that content of red phosphorus used for this invention is the range of 4.6 mass parts-194 mass parts with respect to 100 mass parts of polyols, In the range of 4.6 mass parts-75 mass parts. More preferably, it is in the range of 6.2 to 56 parts by mass, and most preferably in the range of 6.2 to 38 parts by mass. In a foaming polyurethane composition, it can be set as the range of 1.5 mass parts-52 mass parts with respect to 100 mass parts of urethane resins, and it is more preferable that it is the range of 1.5 mass parts-20 mass parts. Preferably, the range is 2.0 parts by mass to 15 parts by mass, and most preferably the range is 2.0 parts by mass to 10 parts by mass.

  When the range of the red phosphorus is not less than the above lower limit, the self-extinguishing property of the foam is maintained, and when it is not more than the above upper limit, foaming of the foamable urethane composition is not inhibited. By using red phosphorus, it is considered that combustion of the urethane foam during heating can be suppressed, and the urethane foam can be prevented from falling off from the base material.

  The present invention can contain an acicular filler and / or a boron-containing flame retardant as the flame retardant.

  The acicular filler may be an organic filler or an inorganic filler. The acicular filler is preferably an inorganic filler. The aspect ratio of the acicular filler is 5 to 50, preferably 8 to 40, more preferably 10 to 40, still more preferably 10 to 35, and most preferably 8 to 25. Here, the aspect ratio of the filler in the present specification is the minimum thickness of the maximum length of the filler that is confirmed by an image obtained by observing the acicular filler with a scanning electron microscope (relative to the maximum length). (The vertical direction) (also referred to as the diameter / thickness ratio), a sufficient number of fillers, an average of 250 or more.

  The average particle diameter of the acicular filler is 0.1 μm or more and less than 15 μm, preferably 0.1 μm or more and 14 μm or less, more preferably 0.3 to 10 μm. The average particle size is determined by an X-ray transmission type sedimentation method particle size distribution analyzer. The melting point of the acicular filler is 750 ° C. or higher, preferably 800 ° C. or higher, more preferably 1,000 ° C. or higher.

  As the needle-like inorganic filler, basic magnesium sulfate, aluminum borate, wollastonite, zonolite, dosonite, elastadite, boehmite, rod-like hydroxyapatite, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, Silicon-based whisker, acicular alumina, acicular ceramic, asbestos, acicular calcium carbonate, gypsum fiber, glass fiber, asbestos fiber, silica fiber, alumina fiber, silica / alumina fiber, zirconia fiber, carbon fiber (fiber such as carbon nanotube) , Needle-like or spherical new carbon such as fullerene), graphite fiber, boron nitride fiber, boron fiber, metal fiber and the like.

  The acicular filler prevents at least one of shrinkage and deformation. In this specification, “shrinkage” refers to changes in length including length in the length direction, length in the width direction, and length in the thickness direction, and “deformation” refers to a shape such as warpage. It refers to a change, particularly a change in shape in the thickness direction. The needle shape means that the major axis is three times or more the minor axis, and includes not only a so-called needle shape but also a spindle shape, a cylindrical shape, and the like.

  In one embodiment, the acicular filler is an acicular inorganic filler having an aspect ratio of 5 to 50 and an average particle diameter of 0.1 μm or more and less than 15 μm. Preferred acicular fillers are wollastonite or potassium titanate whiskers.

  The content of the acicular filler is preferably in the range of 3 parts by mass to 94 parts by mass, more preferably in the range of 3 parts by mass to 56 parts by mass with respect to 100 parts by mass of the polyol. More preferably, it is the range of -38 mass parts. In a foaming urethane resin composition, it is preferable that it is 1-25 mass parts with respect to 100 mass parts of urethane resins, It is more preferable that it is 1-15 mass parts, 1 mass part-10 mass parts More preferably.

  Examples of the boron-containing flame retardant include borax, boron oxide, boric acid, and borate. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide. Examples of borates include alkali metals, alkaline earth metals, Group 4 elements, Group 12 elements, Group 13 elements, and ammonium borates. Specifically, alkali metal borate such as lithium borate, sodium borate, potassium borate, cesium borate, alkaline earth metal borate such as magnesium borate, calcium borate, barium borate, boron Examples thereof include zirconium acid, aluminum borate, and ammonium borate. The boron-containing flame retardant used in the present invention is preferably a borate.

  One or two or more boron-containing flame retardants can be used.

  The content of the boron-containing flame retardant used in the present invention is preferably in the range of 3 parts by mass to 94 parts by mass with respect to 100 parts by mass of the polyol, and is preferably in the range of 3 parts by mass to 56 parts by mass. More preferably, it is in the range of 3 parts by mass to 38 parts by mass. In a foaming urethane resin composition, it is preferable that it is 1-25 mass parts with respect to 100 mass parts of urethane resins, It is more preferable that it is 1-15 mass parts, 1 mass part-10 mass parts More preferably.

  By using an acicular filler and / or a boron-containing flame retardant, it is possible to maintain the residue of the urethane foam during heating and maintain the adhesion of the urethane foam to the substrate.

  Furthermore, as the flame retardant, at least one selected from a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide can also be used.

  The phosphate ester used in the present invention is not particularly limited. As the phosphate ester, it is preferable to use, for example, a monophosphate ester or a condensed phosphate ester.

  There is no limitation in particular as monophosphate ester. Examples of monophosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, tris (isopropylphenyl) phosphate, Tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate , 2-methacryloyloxyethyl acid phosphate, dipheny 2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resist Examples include lucinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, and tris (β-chloropropyl) phosphate.

  There is no limitation in particular as condensed phosphate ester. Examples of the condensed phosphate ester include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name PX-200), hydroquinone poly (2, 6-xylyl) phosphate and condensed phosphate esters such as condensates thereof.

  Examples of commercially available condensed phosphate esters include resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade name CR-741), aromatic condensed phosphate ester (trade name CR747), and resorcinol. Examples thereof include polyphenyl phosphate (manufactured by ADEKA, trade name ADK STAB PFR), bisphenol A polycresyl phosphate (trade names FP-600, FP-700), and the like.

  Among these, it is preferable to use a monophosphate ester because the effect of reducing the viscosity in the composition before curing and the effect of reducing the initial calorific value are high, and tris (β-chloropropyl) phosphate is used. Is more preferable.

  Phosphoric acid ester can use 1 type, or 2 or more types.

  The content of the phosphate ester is preferably in the range of 4.6 to 194 parts by mass, more preferably in the range of 4.6 to 75 parts by mass with respect to 100 parts by mass of the polyol. The range of 6.2 parts by mass to 56 parts by mass is more preferable, and the range of 6.2 parts by mass to 38 parts by mass is most preferable. In a foaming polyurethane composition, it can be set as the range of 1.5 mass parts-52 mass parts with respect to 100 mass parts of urethane resins, and it is more preferable that it is the range of 1.5 mass parts-20 mass parts. Preferably, the range is 2.0 parts by mass to 15 parts by mass, and most preferably the range is 2.0 parts by mass to 10 parts by mass.

  When the range of the phosphoric acid ester is not less than the above lower limit, the molded product made of the foamable polyurethane composition can be prevented from cracking the dense residue formed by the maturity of the fire, and when the range is not more than the above upper limit, Foaming of the polyurethane composition is not inhibited.

  The phosphate-containing flame retardant used in the present invention contains phosphoric acid. There is no particular limitation on the phosphoric acid moiety used in the phosphate-containing flame retardant. Examples of the phosphoric acid moiety include various phosphoric acids such as monophosphoric acid, pyrophosphoric acid, polyphosphoric acid, and combinations thereof.

  Examples of the phosphate-containing flame retardant include phosphoric acid comprising salts of various phosphoric acids and at least one metal or compound selected from metals of Group IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. Mention may be made of salts. Examples of the metals of Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.

  Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like.

  Aromatic amines include pyridine, triazine, melamine, ammonium and the like.

  The phosphate-containing flame retardant may be subjected to a known water resistance improving treatment such as silane coupling agent treatment or coating with a melamine resin, and a known foaming aid such as melamine or pentaerythritol may be added. May be.

  Specific examples of the phosphate-containing flame retardant include monophosphate, pyrophosphate, polyphosphate, and the like.

The monophosphate is not particularly limited. As monophosphates, for example,
Ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate;
Sodium salts such as phosphoric acid-sodium, disodium phosphate, trisodium phosphate, phosphite-sodium, disodium phosphite, sodium hypophosphite;
Potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, potassium hypophosphite;
Lithium salts such as phosphoric acid-lithium, dilithium phosphate, trilithium phosphate, phosphorous acid-lithium, dilithium phosphite, lithium hypophosphite;
Barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, barium hypophosphite;
Magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium hypophosphite;
Examples thereof include calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite.

  Moreover, it does not specifically limit as a polyphosphate. Examples of polyphosphate include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, aluminum polyphosphate, and the like.

  Among these, since the self-extinguishing property of the phosphate-containing flame retardant is improved, it is preferable to use a monophosphate, and it is more preferable to use ammonium dihydrogen phosphate.

  One or two or more phosphate-containing flame retardants can be used.

  The content of the phosphate-containing flame retardant used in the present invention is preferably in the range of 4.6 parts by mass to 194 parts by mass with respect to 100 parts by mass of the polyol, and 4.6 parts by mass to 75 parts by mass. Is more preferable, it is still more preferable that it is the range of 6.2 mass parts-56 mass parts, and it is most preferable that it is the range of 6.2 mass parts-38 mass parts. In a foaming polyurethane composition, it can be set as the range of 1.5 mass parts-52 mass parts with respect to 100 mass parts of urethane resins, and it is more preferable that it is the range of 1.5 mass parts-20 mass parts. Preferably, the range is 2.0 parts by mass to 15 parts by mass, and most preferably the range is 2.0 parts by mass to 10 parts by mass.

  The bromine-containing flame retardant used in the present invention is not particularly limited as long as it is a compound containing bromine in the molecular structure. Examples of bromine-containing flame retardants include aromatic brominated compounds.

Specific examples of the aromatic brominated compound include, for example,
Hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, ethylene-bis (tetrabromophthalimide), Monomeric organic bromine compounds such as tetrabromobisphenol A;
Brominated polycarbonates such as polycarbonate oligomers produced from brominated bisphenol A as raw materials, copolymers of polycarbonate oligomers and bisphenol A;
Brominated epoxy compounds such as diepoxy compounds produced by reaction of brominated bisphenol A with epichlorohydrin, monoepoxy compounds obtained by reaction of brominated phenols with epichlorohydrin;
Poly (brominated benzyl acrylate);
Brominated polyphenylene ether;
Condensates of brominated bisphenol A, cyanuric chloride and brominated phenol;
Brominated polystyrene such as brominated (polystyrene), poly (brominated styrene), cross-linked brominated polystyrene;
Halogenated bromine compound polymers such as crosslinked or non-crosslinked brominated poly (-methylstyrene).

  From the viewpoint of controlling the calorific value at the initial stage of combustion, brominated polystyrene, hexabromobenzene and the like are preferable, and hexabromobenzene is more preferable.

  One or more bromine-containing flame retardants can be used.

  The content of the bromine-containing flame retardant used in the present invention is preferably in the range of 4.6 to 194 parts by mass with respect to 100 parts by mass of the polyol, and in the range of 4.6 to 75 parts by mass. It is more preferable that it is in the range of 6.2 to 56 parts by mass, and it is most preferable to be in the range of 6.2 to 38 parts by mass. In a foaming polyurethane composition, it can be set as the range of 1.5 mass parts-52 mass parts with respect to 100 mass parts of urethane resins, and it is more preferable that it is the range of 1.5 mass parts-20 mass parts. Preferably, the range is 2.0 parts by mass to 15 parts by mass, and most preferably the range is 2.0 parts by mass to 10 parts by mass.

  Examples of the antimony-containing flame retardant used in the present invention include antimony oxide, antimonate, pyroantimonate and the like. Examples of the antimony oxide include antimony trioxide and antimony pentoxide. Examples of the antimonate include sodium antimonate and potassium antimonate. Examples of pyroantimonate include sodium pyroantimonate and potassium pyroantimonate. The antimony-containing flame retardant used in the present invention is preferably antimony oxide. One or more antimony-containing flame retardants can be used.

  The content of the antimony-containing flame retardant is preferably in the range of 4.6 to 194 parts by mass, more preferably in the range of 4.6 to 75 parts by mass with respect to 100 parts by mass of the polyol. Preferably, it is in the range of 6.2 parts by mass to 56 parts by mass, and most preferably in the range of 6.2 parts by mass to 38 parts by mass. In a foaming polyurethane composition, it can be set as the range of 1.5 mass parts-52 mass parts with respect to 100 mass parts of urethane resins, and it is more preferable that it is the range of 1.5 mass parts-20 mass parts. Preferably, the range is 2.0 parts by mass to 15 parts by mass, and most preferably the range is 2.0 parts by mass to 10 parts by mass.

  Examples of the metal hydroxide used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, copper hydroxide, and vanadium hydroxide. And tin hydroxide.

  One or two or more metal hydroxides can be used.

  The content of the metal hydroxide is preferably in the range of 4.6 to 194 parts by mass and more preferably in the range of 4.6 to 75 parts by mass with respect to 100 parts by mass of the polyol. Preferably, it is in the range of 6.2 parts by mass to 56 parts by mass, and most preferably in the range of 6.2 parts by mass to 38 parts by mass. In a foaming polyurethane composition, it can be set as the range of 1.5 mass parts-52 mass parts with respect to 100 mass parts of urethane resins, and it is more preferable that it is the range of 1.5 mass parts-20 mass parts. Preferably, the range is 2.0 parts by mass to 15 parts by mass, and most preferably the range is 2.0 parts by mass to 10 parts by mass.

  The total content of the flame retardant used in the present invention is preferably in the range of 16 parts by mass to 260 parts by mass and more preferably in the range of 16 parts by mass to 149 parts by mass with respect to 100 parts by mass of the polyol. Preferably, the range is from 16 parts by mass to 112 parts by mass. In a foamable polyurethane composition, it can be set as the range of 4.5 mass parts-70 mass parts with respect to 100 mass parts of urethane resins, and it is more preferable that it is the range of 4.5 mass parts-40 mass parts. More preferably, it is in the range of 4.5 to 30 parts by mass.

  When the range of the flame retardant is not less than the above lower limit, the molded product made of the foamable polyurethane composition can be prevented from cracking the dense residue formed by the heat of fire, and when the range is not more than the above upper limit, the foamable polyurethane The foaming of the composition is not inhibited.

7). Other Components The composition of the present invention may further contain an inorganic filler. There is no limitation in particular as an inorganic filler. For example, as an inorganic filler, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, dosonite, Hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salt of calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica parun, nitriding Aluminum, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon parun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum porate, Molybdenum, silicon carbide, stainless steel fiber, various magnetic powder, slag fibers, fly ash, silica-alumina fiber, alumina fiber, silica fiber, zirconia fiber, and the like. However, the component corresponding to the “needle filler” is not included in the “other components”.

  One or more inorganic fillers can be used.

  The composition of the present invention is within a range that does not impair the object of the present invention, as necessary, phenolic, amine-based, sulfur-based antioxidants, heat stabilizers, metal harm-preventing agents, antistatic agents, A stabilizer, a crosslinking agent, a lubricant, a softening agent, a pigment, an auxiliary component such as a tackifier resin, and a tackifier such as a polybutene and a petroleum resin can be included.

  Above 1. ~ 7. Since the foamable polyurethane composition in which the above components are mixed reacts and cures, its viscosity changes with time. Therefore, before using the foamable polyurethane composition, the foamable polyurethane composition is divided into two or more to prevent the foamable polyurethane composition from reacting and curing (foamable polyurethane premix composition). And when using a foamable polyurethane composition, a foamable polyurethane composition is obtained by mixing the foamable polyurethane composition divided | segmented into two or more, and putting them together.

  When the foamable polyurethane composition is divided into two or more, each component of the foamable polyurethane composition divided into two or more does not start to cure, and after mixing each component of the foamable polyurethane composition Each component may be divided so that the curing reaction starts.

  Curing of the foamable polyurethane composition may be performed by mixing and at room temperature, or each component may be heated in advance.

  The foam stabilizer, catalyst, blowing agent and flame retardant may be mixed with either a polyol or a polyisocyanate, or may be provided separately from the polyol and the polyisocyanate. Preferably, the polyol, foam stabilizer, catalyst, foaming agent, and flame retardant are provided as a polyol premix containing the polyol and these components (polyol composition for reacting with a polyisocyanate compound to obtain a polyurethane foam). object). In addition, the above 7. These other components may also be mixed with either the polyol or polyisocyanate, or may be provided separately from the polyol and polyisocyanate. Above 7. These other components are preferably included in the polyol premix.

  Polyols, polyisocyanates, foam stabilizers, catalysts, foaming agents, and flame retardants, preferably polyisocyanates mixed with polyol premixes containing polyols, foam stabilizers, catalysts, foaming agents, and flame retardants The foamable polyurethane composition is foamed and cured to form a polyurethane foam.

The fire resistance of the urethane foam composition and polyurethane foam of the present invention can be evaluated by a cone calorimeter test based on the test method of ISO-5660. Specifically, in this fire resistance test, a polyurethane foam made of a foamable polyurethane composition is cut into a length of 10 cm, a width of 10 cm and a thickness of 5 cm to prepare a sample for a corn calorimeter test. Next, based on the test method of ISO-5660, the total calorific value when heated at a radiant heat intensity of 50 kW / m ^{2 for} 20 minutes is measured with a corn calorimeter using a sample for corn calorimeter test.

In this specification, "nonflammability" means what comprises all the following conditions (1) to (3).
(1) The total calorific value for 20 minutes after starting heating at a radiant heat intensity of 50 kW / m ² is 8 MJ / m ² or less.
(2) The heating rate exceeding 200 kW / m ² does not continue for more than 10 seconds in 20 minutes after the start of heating.
(3) No deformation such as cracks or holes harmful to fire prevention occurs for 20 minutes after the start of heating.

  The foamable polyurethane composition of the present invention is used for repairing foams used for vehicle or building insulation, or used to fill openings or gaps in buildings. Here, “building” includes any structure constituting the building, and includes not only structural materials of the building such as walls, ceilings, roofs, floors, but also windows (drawing windows, open windows, raising and lowering windows, etc.). ), Shoji screens, doors (ie doors), doors, bran, and balustrades. In addition, “opening” refers to any opening that occurs in a building, including joints that occur between building structural materials and holes that occur in one structural material. Between two facing members or parts, such as between a structural material, between a structural material, between a structural material and a joinery, between a joinery and a joinery, between a structural material or joinery and furniture (such as a kitchen sink) Refers to the opening.

  Polyurethane foams obtained by foaming and curing foamable polyurethane compositions are excellent in waterproofness, airtightness, and flame retardancy, so water, smoke, flames, or combustion from openings or gaps in buildings It is possible to effectively block the intrusion of the generated gas or the like.

  The foamable polyurethane composition of the present invention forms a foam by spraying the substrate on site in order to repair, for example, a slight opening or gap in the field without using a large apparatus such as an aerosol type. Used for field spray applications.

  The on-site spraying can be performed using a spraying device (for example, manufactured by GRACO: A-25) and a spray gun (for example, manufactured by Gasmer: D gun). On-site spraying can be performed by adjusting the temperature of the first and second liquids in separate containers in the spraying device, colliding and mixing the two liquids at the tip of the spray gun, and misting the mixed liquid with air pressure. . Spraying devices and spray guns are known and commercially available products can be used.

  Moreover, it can implement using apparatuses, such as a cartridge gun and a discharge device. For on-site spraying, both a two-liquid mixing container in which the first liquid and the second liquid are contained in separate containers and a two-liquid mixing container in which the first liquid and the second liquid are accommodated in one container can be used. . The mixing vessel can be used in combination with the above-described device together with a stirring device as necessary. Cartridge guns are also known and commercially available products can be used.

  On-site spraying can be performed on any base material (structural material). Examples of the substrate include metal (for example, steel), cement board, concrete, gypsum board and the like.

  As used herein, steel refers to structural steel materials exemplified in JIS G 3101, JIS G 3106, JIS G 3114, JIS G 3136, deck plates exemplified in JIS G 3352, JIS G 3352, JIS G 3455, Steel materials for piping exemplified in JIS G 3456, JIS G 3457, etc., plated steel sheets exemplified in JIS G 3302, JIS G 3313, JIS G 3317, JIS G 3321, JIS G 3302, JIS G 3313, JIS G 3317 And stainless steel sheets exemplified in JIS G 3321 and the like.

  The excellent characteristics of the foam of the present invention are suitably exhibited when using steel as a base material, which has high thermal conductivity and is difficult to exhibit the effect of flame retardancy.

  In water-containing base materials such as concrete, cement, and gypsum board, moisture absorbs heat during heating, and the urethane resin at the interface is not easily decomposed, and there is a tendency that adhesion of foamed urethane to the base material is easily maintained. On the other hand, steel has high thermal conductivity and there is no water to absorb heat, so the urethane resin at the interface is easily carbonized, and further, decomposition gas accumulates at the interface between the urethane resin and steel, creating pressure and further peeling. Cheap. The foam heat insulating material provided by the present invention retains adhesiveness even during heating and does not fall off.

  The thickness (spraying thickness) at which the foamable urethane resin composition is sprayed onto the substrate is not particularly limited. The spraying thickness can be 1 to 100 mm, preferably 10 to 100 mm, particularly preferably 15 to 100 mm. The spraying thickness can be 15 to 100 mm, preferably 20 to 100 mm, particularly preferably 25 to 100 mm.

  This invention also provides the manufacturing method of a flame-retardant structure characterized by including the step which sprays said foamable urethane resin composition for on-site spraying to a base material (structural material). The method for producing a flame-retardant structure according to the present invention preferably includes a step of mixing the polyol composition and the isocyanate compound on-site.

  The flame-retardant structure is produced by foaming and curing the foamable urethane resin composition sprayed on the base material, and adhering to the base material.

  The present invention also includes a flame retardant structure that is a laminate obtained by the above-described production method. In the flame-retardant structure (laminate) of the present invention, a foam obtained by curing the foamable urethane resin composition for in-situ spraying of the present invention is laminated on a base material.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

1. Production of in-situ foaming polyurethane composition With the formulation shown in Table 1, in-situ foaming polyurethane compositions according to Examples and Comparative Examples were prepared. Specifically, the in-situ foamable polyurethane composition is prepared from (A) a polyisocyanate, (B) a polyol, (C) a trimerization catalyst, (D) a urethanization catalyst, (E) a foaming agent, and (F) an adjustment agent. It was prepared in two parts: a foam premix, (G) phosphate ester, (H) red phosphorus, and (I) a polyol premix consisting of a powder flame retardant. The details of each component in the table are as follows.

(A) Polyisocyanate compound 4,4′-diphenylmethane diisocyanate (4,4′-MDI) (manufactured by Wanhua Chemical Japan, product name: PM200).

(B) Polyol p-phthalic acid polyester polyol (manufactured by Kawasaki Chemical Industry Co., Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mgKOH / g).

(C) Trimerization catalyst Trimerization catalyst (manufactured by San Apro Co., Ltd., product name: U-CAT 18X)
Trimerization catalyst (product name: TOYOCAT (registered trademark) -TR20, manufactured by Tosoh Corporation)
Trimerization catalyst (product name: k-zero G, manufactured by Momentive Performance Materials).

(D) Urethane catalyst Catalyst Urethane catalyst (Product name: U-CAT 202, manufactured by San Apro Co., Ltd.)
Urethane catalyst (product name: TOYOCAT (registered trademark) -RX5, manufactured by Tosoh Corporation)
Urethane catalyst (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark) -TT)
Urethane catalyst (manufactured by Nitto Kasei Co., Ltd., product name: U-830).

(E) Foaming agent water HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Central Glass Co., Ltd.)
HFC-245fa (1,1,1,3,3-pentafluoropropane, manufactured by Nippon Solvay)
HFO (trans-1-chloro-3,3,3-trifluoropropene, manufactured by Honeywell, product name: Solstice LBA).

(F) Foam stabilizer Polyalkylene glycol foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193).

Flame retardant and liquid flame retardant (G) Phosphate ester Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP, referred to as “TMCPP”).
-Powder flame retardant (H) Red phosphorus Red phosphorus (Rin Chemical Industry Co., Ltd., product name: Nova Excel 140).

(I) Acicular filler wollastonite (SiO ₂ · CaO; acicular filler) (manufactured by Kinsei Matec, product name: SH-1250)
(J) Zinc borate (product name: Firebrake ZB, manufactured by Hayakawa Shoji Co., Ltd.)
(K) Hexabromobenzene (manac product, product name: HBB-B, hereinafter referred to as “HBB”).

  Components other than polyisocyanate were weighed into a 20 L plastic pail can and stirred to prepare a polyol composition. After stirring, the solution was stabilized for about 1 hour.

2. Evaluation [Evaluation Method]
Using a Graco spray machine “HV-R” and a gasmer spray gun “D gun”, each substrate was sprayed at a thickness of 40 mm under the conditions shown in Table 1. After spraying and curing for one day, using a corn calorimeter III manufactured by Toyo Seiki, heating was performed at a radiant heat of 50 kW / m ^{2 for} 20 minutes.

[Remaining interface]
Regarding the residue after combustion, the case where carbonization at the interface of the base material did not occur was marked with ○, and the case where all carbonization occurred was marked with ×.

[Removal of residue]
The residue after combustion was tilted by 45 °, and the residue was slid off from the base material was marked with x, and the one where adhesion was observed was marked with ◯.

[Adhesive strength]
The carbonized portion was removed from the residue that did not fall off, and a 50 mm × 50 mm jig was affixed to the foam and the substrate surface with an adhesive (urethane system, no solvent). After the adhesive was cured, a tensile test was performed at a speed of 10 mm / min using a Tensilon tester, and the adhesive strength was calculated. The evaluation results are shown in Table 2.

  Even when the spraying was performed in the same manner except that the spraying was performed at a thickness of 25 mm, the in-situ blowing foams of Examples 1 to 5 did not fall off after combustion, and good adhesive force was recognized. On the other hand, all of Comparative Examples 1 and 2 dropped out after combustion.

Claims (12)

A polyol composition for mixing with a polyisocyanate compound to obtain a foamable polyurethane composition for in-situ spraying,
Contains a polyol compound, a flame retardant, and a catalyst,
A polyol composition comprising at least red phosphorus as the flame retardant.   The polyol composition according to claim 1, further comprising an acicular filler and / or a boron-containing flame retardant as the flame retardant.   The polyol composition according to claim 1 or 2, comprising a trimerization catalyst as the catalyst, and containing 0.4 to 38 parts by mass of the trimerization catalyst with respect to 100 parts by mass of the polyol compound.   The urethanization catalyst is contained as the catalyst, and the urethanization catalyst is contained in an amount of 0.4 to 38 parts by mass with respect to 100 parts by mass of the polyol compound. The polyol composition described.   A foamable polyurethane premix composition for on-site spraying, comprising the polyol composition according to any one of claims 1 to 4 and an isocyanate compound separately.   A foamable urethane resin composition for in-situ spraying, which is a mixture of the polyol composition according to any one of claims 1 to 4 and an isocyanate compound.   The foamable urethane resin composition for in-situ spraying according to claim 6 for spraying on a steel substrate.   The foamable urethane resin composition for in-situ spraying according to claim 6, for spraying onto a concrete base material.   A method for producing a flame retardant structure comprising the step of spraying a foamable urethane resin composition for in-situ spraying according to any one of claims 6 to 8 onto a substrate.   The method for producing a flame-retardant structure according to claim 9, wherein the base material is steel or concrete.   The method for producing a flame-retardant structure according to claim 9 or 10, comprising a step of mixing the foamable urethane resin composition for on-site spraying on-site.   A flame-retardant structure in which a urethane foam obtained by curing the foamable urethane resin composition for on-site spraying according to any one of claims 6 to 8 is laminated on a base material that is steel or concrete.