JP2018100405A - Polyol composition for spray coating, foamable polyurethane premix composition, and foamable polyurethane composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyol composition for spray coating that has excellent flame retardancy, and can be sprayed even at low temperature without liquid dripping.SOLUTION: A polyol composition is to react with a polyisocyanate compound to obtain a polyurethane foam. The composition contains a polyol, a catalyst, a foaming agent, a foam stabilizer, and a flame retardant, with the viscosity of 50-2000 mPa s.SELECTED DRAWING: None

Description

  The present invention relates to a polyol composition for spray coating, a foamable polyurethane premix composition, and a foamable polyurethane composition.

  Although an in-situ foaming system for forming a flame-retardant polyurethane foam in the field is described in Patent Document 1, the composition of Patent Document 1 exhibits non-flammability, but the reaction is slow. Will occur and workability is poor.

  Moreover, even if the polyol composition of patent document 1 can be sprayed at normal temperature (25 degreeC), reaction is slow at low temperature (5 degreeC), and cannot respond to in-situ foaming at low temperature. On the other hand, if the amount of the catalyst is increased too much in order to enhance the reaction, the desired flame retardancy cannot be obtained because the catalyst is a combustible component.

WO2015 / 129850

  An object of the present invention is to provide a polyol composition for spray coating, a foamable polyurethane premix composition, and a foamable polyurethane composition that have excellent flame retardancy and can be sprayed at low temperatures without dripping. That is.

  In order to achieve the above object, the present inventors include a catalyst and a flame retardant in a polyol composition, and by setting the viscosity of the polyol composition to a specific range, flame retardancy and prevention of dripping The present inventors have found that a composition suitable for spray coating that exhibits both effects can be achieved, and the present invention has been completed.

  According to the present invention, a polyol composition for spray coating for reacting with a polyisocyanate compound to obtain a polyurethane foam, comprising a polyol, a catalyst, a foaming agent, a foam stabilizer, a flame retardant, and a viscosity A polyol composition for spray coating is provided, wherein is from 50 to 2000 mPa · s.

  According to the present invention, the foamable polyurethane composition can be sprayed quickly on site.

  The present invention is (i) a polyol composition for spray coating for reacting with a polyisocyanate compound to obtain a polyurethane foam, comprising a polyol, a catalyst, a foaming agent, a foam stabilizer, and a flame retardant, A polyol composition for spray coating having a viscosity of 50 to 2000 mPa · s, (ii) a foamable polyurethane premix composition for spray coating, comprising the polyol composition and the polyisocyanate compound separately, (iii) A foamable polyurethane composition for spray coating, which is a mixture of the polyol composition and a polyisocyanate compound, and (iv) a polyurethane foam obtained by curing the foamable polyurethane composition.

  The polyol composition for spray coating contains a polyol, a catalyst, a foaming agent, a foam stabilizer, a flame retardant, and optionally other components.

  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. Polyisocyanate Examples of the polyisocyanate compound include aromatic polyisocyanate, alicyclic polyisocyanate, and aliphatic polyisocyanate.

  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 diphenylmethane diisocyanate for reasons such as ease of use and availability.

  The ratio of the polyisocyanate compound content to the polyol content (polyisocyanate compound content: polyol) is not particularly limited, but is preferably 10: 1 to 1:10 by weight ratio, and 1: 1 to More preferably, it is 5: 1.

2. 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 such as acrylonitrile, styrene, methyl acrylate, and methacrylate on an aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, or the like, polybutadiene Examples thereof include polyols, modified polyols of polyhydric alcohols, and hydrogenated products thereof.
Examples of the modified polyol of the polyhydric alcohol include those modified by reacting the raw material polyhydric alcohol with an alkylene oxide.

  Examples of the polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane; pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc., sucrose, glucose, mannose, fructose, methylglucoside and Tetravalent to octavalent alcohols such as derivatives thereof; phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene , Antrol, 1,4,5,8-tetrahydroxyanthracene, 1-hydroxypyrene, etc .; polybutadiene polyol; castor oil polyol; hydroxyalkyl (meth) Polyfunctional (e.g. functionality 2 to 100) polyol such as (co) polymers and polyvinyl alcohol acrylate include condensates of phenol and formaldehyde (novolac) it is.

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

  AO includes 2 to 6 carbon atoms such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propylene oxide, and 1,2-butylene. Examples thereof include 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, in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogens, at least one alkylene oxide such as ethylene oxide, propylene oxide, and tetrahydrofuran is subjected to ring-opening polymerization. The obtained polymer 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, triols such as glycerin and trimethylolpropane, and ethylenediamine. And amines such as 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.
A polyol can use 1 type, or 2 or more types.

3. Catalyst Examples of the catalyst include triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N′-trimethylaminoethyl. -Nitrogen atom-containing catalysts such as ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl, N'-dimethylaminoethylpiperazine, imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group Etc.

  The addition amount of the catalyst used for the foamable polyurethane composition is in the range of 10 to 56 parts by weight with respect to 100 parts by weight of the polyol. When the amount of the catalyst is less than 10 parts by weight, the cream time becomes long (for example, more than 1 second), and dripping occurs. In the foamable polyurethane composition, the addition amount of the catalyst is in the range of 3 to 14 parts by weight with respect to 100 parts by weight of the urethane resin composed of the polyisocyanate compound and the polyol. When the amount of the catalyst is less than 3 parts by weight, the cream time becomes longer (for example, more than 1 second) and dripping occurs. When the amount of the catalyst is more than 14 parts by weight, the flame retardancy of the urethane resin composition is impaired.

  The cream time refers to the time until the mixture of the polyol composition and the polyisocyanate compound starts to foam and becomes a creamy liquid before it starts to expand. It can be measured with the naked eye as the time when the color of the solution of the mixture starts to change color. The time from the start of expansion of the mixture to the end of expansion is referred to as the rise time, and the time from the end of the rise (expansion) of the mixture to the curing of the surface is referred to as the set time.

  Preferred catalysts include trimerization catalysts and urethanization catalysts.

  The trimerization catalyst is a catalyst that promotes the formation of an isocyanurate ring by reacting an isocyanate group contained in a polyisocyanate compound that is a main component of a polyurethane resin to cause trimerization.

  Trimerization catalysts include nitrogen-containing aromatic compounds such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine ; Potassium acetate, potassium 2-ethylhexanoate, alkali metal carboxylate; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt; tetramethylammonium salt, tetraethylammonium salt, tetraphenylammonium salt, etc. And quaternary ammonium salts.

  The addition amount of the trimerization catalyst used in the polyol composition for spray coating is preferably in the range of 3 to 28 parts by weight with respect to 100 parts by weight of the polyol. In the foamable polyurethane composition, the addition amount of the trimerization catalyst is preferably in the range of 1 to 7 parts by weight with respect to 100 parts by weight of the urethane resin.

  A urethanization catalyst is a catalyst that causes a polymerization reaction simultaneously with curing and urethanization reactions.

  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-dimethyl Imidazole, 1-methylimidazole, 1-isobutyl-2-methylimidazole, bis (dimethylaminoethyl) ether, 1,8-diazabicyclo- [5,4,0] -undecene-7; metal catalysts such as octylic acid Stannous, dibutylstannic dilaurate, octylic acid , Bismuth carboxylate, zirconium complexes; is and combinations thereof.

  The addition amount of the urethanization catalyst used in the polyol composition for spray coating is preferably in the range of 0.3 to 28 parts by weight with respect to 100 parts by weight of the polyol. In the foamable polyurethane composition, the addition amount of the urethanization catalyst is preferably in the range of 0.1 to 7 parts by weight with respect to 100 parts by weight of the urethane resin.

  The catalyst is preferably 3 to 28 parts by weight of a trimerization catalyst and 0.3 to 28 parts by weight of a urethanization catalyst with respect to 100 parts by weight of polyol. In the flame-retardant foaming polyurethane composition, the catalyst is composed of 1 to 7 parts by weight trimerization catalyst and 0.1 to 7 parts by weight urethanization catalyst with respect to 100 parts by weight of the urethane resin. Preferably there is. In this case, the cream time is less than 1 second even at low temperatures, and dripping does not occur and good spray coating is possible. Moreover, the self-extinguishing property of the foamable polyurethane resin composition is also maintained.

  Furthermore, the weight ratio of the trimerization catalyst to the urethanization catalyst is preferably 10: 1 to 1:70. In this case, in this case, the cream time is within 1 second even at a low temperature, and a good spray coating is possible without dripping. Moreover, the self-extinguishing property of the foamable polyurethane resin composition is also maintained.

4). Foaming agent The foaming agent used in the foamable polyurethane composition promotes foaming of the urethane resin.

Specific examples of the blowing agent include, for example, water; hydrocarbons having a low boiling point such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane; dichloroethane, propyl chloride, isopropyl chloride, Chlorinated aliphatic hydrocarbon compounds such as butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride; Fluorine compounds such as CHF ₃ , CH ₂ F ₂ , CH ₃ F; trichloromonofluoromethane, trichlorotrifluoroethane, dichloromono Hydrochlorofluorocar, such as fluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)) Bon compounds; hydrofluorocarbons such as HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane) HFO-1233zd (E) Hydrofluoroolefins such as (trans-1-chloro-3,3,3-trifluoropropene); ether compounds such as diisopropyl ether; organic physical foaming agents such as mixtures of these compounds; nitrogen gas, oxygen gas; Examples thereof include inorganic physical foaming agents such as argon gas and carbon dioxide gas.

  The range of the blowing agent is preferably 0.3 to 112 parts by weight with respect to 100 parts by weight of the polyol. In the foamable polyurethane composition, the foaming agent is preferably in the range of 0.1 to 30 parts by weight, and in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. More preferably, the range is 0.5 to 18 parts by weight.

When the range of the foaming agent is 0.1 parts by weight or more with respect to 100 parts by weight of the urethane resin, the formation of air bubbles is promoted and a good foam is obtained. Can be prevented from becoming coarse.
One or two or more foaming agents can be used.

5. Examples of the foam stabilizer used in the foamable polyurethane composition include a surfactant such as a polyoxyalkylene foam stabilizer such as polyoxyalkylene alkyl ether, a silicone foam stabilizer such as organopolysiloxane, and the like. It is done.

  The amount of the foam stabilizer used for the urethane resin cured by the chemical reaction is appropriately set depending on the urethane resin cured by the chemical reaction to be used. It is preferable that it is 40 to 40 weight part. In the foamable polyurethane composition, it is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. One or more foam stabilizers can be used.

6). Next, the flame retardant used in the foamable polyurethane composition of the present invention will be described.

  The flame retardant used in the present invention is classified into a liquid flame retardant and a powder flame retardant.

  Examples of the liquid flame retardant include phosphate esters. Examples of the powder flame retardant include red phosphorus, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, metal hydroxide, and inorganic filler.

  Although the phosphate ester used for this invention is not specifically limited, It is preferable to use a monophosphate ester, condensed phosphate ester, etc.

  Examples of the monophosphate ester include, but are not limited to, 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, Diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenylmethanephosphonate, diethyl phenylphosphonate, Resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, tris (β-chloropropyl) phosphate and the like.

  Although it does not specifically limit as condensed phosphate ester, For example, a trialkyl polyphosphate, a resorcinol polyphenyl phosphate, a resorcinol poly (di-2, 6- xylyl) phosphate (the Daihachi Chemical Industry make, brand name PX-200) , Hydroquinone poly (2,6-xylyl) phosphate, and condensed phosphates 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 (trade name ADK STAB PFR, manufactured by ADEKA), and bisphenol A polycresyl phosphate (trade names FP-600 and FP-700).

  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 addition amount of the phosphate ester is preferably 9 to 198 parts by weight with respect to 100 parts by weight of the polyol, and in the range of 2.5 to 50 parts by weight with respect to 100 parts by weight of the urethane resin. Preferably there is.

  When the range of the phosphate ester is 2.5 parts by weight or more, the self-extinguishing property is maintained, and when it is 50 parts by weight or less, foaming of the foamable polyurethane composition is not inhibited.

  According to the present invention, the flame retardant preferably contains red phosphorus. In one embodiment, the flame retardant includes red phosphorus and a phosphate ester.

  There is no limitation in red phosphorus used for this invention, A commercial item can be selected suitably and can be used.

  The total amount of the powder flame retardant used in the fire-resistant urethane resin composition according to the present invention is preferably 13 to 99 parts by weight with respect to 100 parts by weight of the polyol. In the foamable polyurethane composition, the powder flame retardant is more preferably in the range of 4 to 25 parts by weight with respect to 100 parts by weight of the urethane resin.

  The amount of red phosphorus used in the fireproof urethane resin composition according to the present invention is preferably 13 to 59 parts by weight with respect to 100 parts by weight of polyol. In a foaming polyurethane composition, it is preferable that it is the range of 1-15 weight part with respect to 100 weight part of urethane resins, and it is more preferable that it is the range of 4-15 weight part.

  When the range of red phosphorus is 4 parts by weight or more with respect to 100 parts by weight of urethane resin, the self-extinguishing property of the foamable polyurethane composition is maintained, and when it is 15 parts by weight or less, foaming of the foamable polyurethane composition Is not disturbed.

  In a preferred embodiment, the powder flame retardant is 13 to 99 parts by weight and the red phosphorus is 13 to 59 parts by weight with respect to 100 parts by weight of the polyol. In the foamable polyurethane composition, the powder flame retardant is 4 to 25 parts by weight and the red phosphorus is 4 to 15 parts by weight with respect to 100 parts by weight of the urethane resin.

  In addition, as a flame retardant, flame retardants other than red phosphorus and phosphate ester may be further added. For example, at least one selected from the group consisting of a phosphate-containing flame retardant, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide instead of or in addition to the phosphate ester. Two powder flame retardants may be added.

  The phosphate-containing flame retardant contains phosphoric acid. Although the phosphoric acid used for a phosphate containing flame retardant is not specifically limited, Various phosphoric acids, such as monophosphoric acid, pyrophosphoric acid, polyphosphoric acid, are mentioned.

  The phosphate-containing flame retardant is selected from, for example, the various phosphoric acids and metals in groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. Examples thereof include phosphates composed of a salt with at least one metal or compound.

  Examples of the metals in 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.

  Examples of the aromatic amine include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, and 3- (trifluoromethyl) aniline.

  Examples of the heterocyclic compound containing nitrogen in the ring include pyridine, triazine, melamine and the like.

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

  The polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate.

  The said phosphate containing flame retardant can use 1 type, or 2 or more types.

  Although it does not specifically limit to the addition amount of the phosphate containing flame retardant used for this invention, It is preferable that it is the range of 0.4 weight part-99 weight part with respect to 100 weight part of polyols. In the foamable polyurethane composition, the addition amount of the phosphate-containing flame retardant is preferably in the range of 0.1 to 25 parts by weight with respect to 100 parts by weight of the urethane resin, The range is more preferably 21 parts by weight, still more preferably 3 to 21 parts by weight, and most preferably 3.0 to 10 parts by weight.

  When the range of the phosphate-containing flame retardant is 0.1 parts by weight or more with respect to 100 parts by weight of the urethane resin, the self-extinguishing property of the fire-resistant urethane resin composition according to the present invention is maintained, and the urethane resin 100 In the case of 25 parts by weight or less with respect to parts by weight, foaming of the refractory urethane resin composition according to the present invention is not inhibited.

  Although it will not specifically limit as a bromine containing flame retardant if it is a compound which contains bromine in molecular structure, For example, a brominated aromatic ring containing aromatic compound etc. are mentioned.

Specific examples of the brominated aromatic ring-containing aromatic compound include, for example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, Monomeric organic bromine compounds such as bis (pentabromophenoxy) ethane, ethylenebis (pentabromophenyl), ethylenebis (tetrabromophthalimide), tetrabromobisphenol A,
A polycarbonate oligomer produced from brominated bisphenol A as a raw material, a brominated polycarbonate such as a copolymer of the polycarbonate oligomer 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,
A condensate 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, ethylene bis (pentabromophenyl), ethylene bis (tetrabromophthalimide), hexabromobenzene and the like are preferable, and hexabromobenzene is more preferable.

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

  Although it does not specifically limit to the addition amount of the bromine containing flame retardant used for this invention, It is preferable that it is the range of 0.4 weight part-99 weight part with respect to 100 weight part of polyols. In the foamable polyurethane composition, the addition amount of the bromine-containing flame retardant is preferably in the range of 0.1 to 25 parts by weight with respect to 100 parts by weight of the urethane resin, and 0.1 to 21 parts by weight. More preferably, it is in the range of parts by weight, more preferably in the range of 1 to 10 parts by weight, and most preferably in the range of 1.0 to 5.0 parts by weight.

  When the range of the bromine-containing flame retardant is 0.1 parts by weight or more with respect to 100 parts by weight of the urethane resin, the self-extinguishing property of the fire-resistant urethane resin composition according to the present invention is maintained, and 100 parts by weight of the urethane resin. On the other hand, in the case of 25 parts by weight or less, foaming of the refractory urethane resin composition according to the present invention is not inhibited.

  Examples of the boron-containing flame retardant used in the present invention 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.

  Although it does not specifically limit to the addition amount of the boron containing flame retardant used for this invention, It is preferable that it is the range of 0.4 weight part-99 weight part with respect to 100 weight part of polyol. In the foamable polyurethane composition, the addition amount of the boron-containing flame retardant is preferably in the range of 0.1 to 25 parts by weight with respect to 100 parts by weight of the urethane resin, and 0.1 to 21 parts by weight. More preferably, the range is 1 to 10 parts by weight, and most preferably 1.0 to 5.0 parts by weight. When the range of the boron-containing flame retardant is 0.1 parts by weight or more with respect to 100 parts by weight of the urethane resin, the self-extinguishing property of the fire-resistant urethane resin composition according to the present invention is maintained, and 100 parts by weight of the urethane resin. On the other hand, in the case of 25 parts by weight or less, foaming of the refractory urethane resin composition according to the present invention is not inhibited.

  Examples of the antimony-containing flame retardant include antimony oxide, antimonate, pyroantimonate, and the like.

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

  Although it does not specifically limit to the addition amount of the antimony containing flame retardant used for this invention, It is preferable that it is the range of 0.4 weight part-99 weight part with respect to 100 weight part of polyols. In the foamable polyurethane composition, the addition amount of the antimony-containing flame retardant is preferably in the range of 0.1 to 25 parts by weight with respect to 100 parts by weight of the urethane resin, and 0.1 to 21 parts by weight. More preferably, the range is 1 to 10 parts by weight, and most preferably 1.0 to 5.0 parts by weight.

  When the range of the antimony-containing flame retardant is 0.1 parts by weight or more with respect to 100 parts by weight of the urethane resin, the self-extinguishing property of the fire-resistant urethane resin composition according to the present invention is maintained, and the urethane resin has 100 parts by weight. On the other hand, in the case of 25 parts by weight or less, foaming of the refractory urethane resin composition according to the present invention is not inhibited.

  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.

  Although it does not specifically limit to the addition amount of a metal hydroxide, It is preferable that it is the range of 0.4 weight part-99 weight part with respect to 100 weight part of polyols. In the foamable polyurethane composition, the addition amount of the metal hydroxide is preferably in the range of 0.1 to 25 parts by weight with respect to 100 parts by weight of the urethane resin, preferably 0.1 to 21 parts by weight. More preferably, it is in the range of parts by weight, more preferably in the range of 1 to 10 parts by weight, and most preferably in the range of 1.0 to 5.0 parts by weight.

  Examples of the inorganic filler include inorganic fillers and transition metal compounds.

  Inorganic fillers prevent shrinkage and / or deformation. As used herein, “shrinkage” refers to changes in length including the length direction, the length in the width direction, and the length in the thickness direction, and “deformation” refers to a change in shape such as warpage, particularly Indicates a change in shape in the thickness direction.

  The aspect ratio of the inorganic filler is preferably 5-50. Here, the aspect ratio of the filler in the present specification is the minimum thickness of the maximum length of the filler confirmed in an image obtained by observing the filler with a scanning electron microscope (perpendicular to the maximum length). ) (Also referred to as a diameter / thickness ratio), a sufficient number of fillers, an average of 250 or more.

  The average particle size of the inorganic filler is preferably 0.1 μm or more and less than 15 μm. The average particle size is determined by an X-ray transmission type sedimentation method particle size distribution analyzer.

  The shape of the inorganic filler may be either a needle-like filler or a plate-like filler, but preferably the filler is a needle-like filler.

  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. The plate shape includes not only a so-called plate shape but also a scale shape, a flake shape, and the like.

  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.

  Plate-like inorganic fillers are layered clays such as flaky graphite, talc, mica such as muscovite and phlogopite, sericite, kaolinite, chlorite, montmorillonite, halosite, etc. Examples thereof include minerals, plate-like calcium carbonate, plate-like aluminum hydroxide, glass flakes, plate-like iron oxide, and metal plate-like materials.

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

  The addition amount of the inorganic filler is preferably 0.4 to 99 parts by weight with respect to 100 parts by weight of the polyol. In the foamable polyurethane composition, the addition amount of the inorganic filler is preferably in the range of 0.1 to 25 parts by weight with respect to 100 parts by weight of the urethane resin, and is in the range of 1 to 25 parts by weight. Is more preferable, and the range of 1 to 10 parts by weight is still more preferable.

  Examples of the transition metal compound include zinc, copper, iron, tin, lead, bismuth and their metal oxides, organic acid metal salts, inorganic acid metal salts, metal complexes, and the like. Examples of the organic metal salt include acetic acid metal salt, octylic acid metal salt, stearic acid metal salt, and carbonate metal salt, and inorganic acid metal salts include, for example, metal chloride and borate metal salt.

  As the transition metal compound, a zinc compound containing zinc is preferable. Examples of the zinc compound include zinc, zinc oxide, zinc borate, zinc stearate, zinc acetate, zinc octylate, zinc chloride, and zinc carbonate.

  If the compounding quantity of a transition metal compound shows an example, it will be preferable if it is the range of 0.4 weight part-99 weight part with respect to 100 weight part of polyol, for example. In a foaming polyurethane composition, it can be set as the range of 0.1 weight part-25 weight part with respect to 100 weight part of urethane resins.

  By increasing the compounding amount of the transition metal compound, particularly the zinc compound, the speed of the curing reaction of the urethane resin can be improved, and dripping of the foamable polyurethane composition can be prevented. This is particularly useful when dripping becomes a problem, such as on-site foaming.

  In addition, when red phosphorus and a transition metal compound, particularly a zinc compound, are used in combination, the formation of a low-foam skin layer formed on the surface of the urethane resin composition during combustion can be suppressed, and the flame retardancy can be improved. One or more transition metal compounds can be used.

  The total amount of the flame retardant used in the present invention is preferably 23 parts by weight to 296 parts by weight with respect to 100 parts by weight of the polyol. In the foamable polyurethane composition, the flame retardant is preferably in the range of 7 to 75 parts by weight with respect to 100 parts by weight of the urethane resin, preferably 10 to 50 parts by weight. Is more preferable, and the range of 20 to 40 parts by weight is still more preferable.

  When the range of the flame retardant is 7 parts by weight or more with respect to 100 parts by weight of the urethane resin, flame retardancy is exhibited, and when it is 75 parts by weight or less, foaming of the foamable polyurethane composition is not inhibited.

7). Other components Furthermore, the foamable polyurethane composition is a range that does not impair the object of the present invention, as required, antioxidants such as phenols, amines, sulfurs, heat stabilizers, metal harm inhibitors, An antistatic agent, a stabilizer, a crosslinking agent, a lubricant, a softener, a pigment, an auxiliary component such as a tackifier resin, and a tackifier such as polybutene and a petroleum resin can be included.

  As the foamable polyurethane composition reacts and cures, its viscosity changes over 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. And when using a foamable polyurethane composition, a foamable polyurethane composition is obtained by putting together the foamable polyurethane composition divided into two or more.

  In addition, when dividing the foamable polyurethane composition into two or more, curing does not start with each component of the foamable polyurethane composition divided into two or more, but after mixing the respective components of the foamable polyurethane composition Each component may be divided so that the curing reaction starts. Usually, the foamable polyurethane composition is divided into a polyol composition containing a polyol and an isocyanate compound or an isocyanate solution composition containing an isocyanate compound.

  The catalyst, foaming agent, foam stabilizer, 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, catalyst, foaming agent, foam stabilizer, and flame retardant are provided as a polyol premix containing the polyol and these components (spray coating for reacting with a polyisocyanate compound to obtain a polyurethane foam) Polyol composition). The other components may be mixed with either the polyol or the polyisocyanate, and may be provided separately from the polyol and the polyisocyanate, but are preferably included in the polyol premix.

  In one embodiment, the polyol composition for spray coating for reacting with a polyisocyanate compound to obtain a polyurethane foam comprises 10 to 56 parts by weight of catalyst, 0.3 to 112 parts by weight with respect to 100 parts by weight of polyol. A foam stabilizer, 0.3 to 40 parts by weight of a foam stabilizer, and 23 parts by weight to 296 parts by weight of a flame retardant.

  In another embodiment, the foamable polyurethane composition for spray coating comprises 3 to 14 parts by weight of catalyst, 0.1 to 30 parts by weight based on 100 parts by weight of urethane resin comprising the polyisocyanate compound and the polyol. A foam stabilizer, 0.1 to 10 parts by weight of a foam stabilizer, and 7 to 75 parts by weight of a flame retardant.

  The method for producing the foamable polyurethane composition is not particularly limited. For example, the method of mixing each component of the foamable polyurethane composition, the foamable polyurethane composition is suspended in an organic solvent, or heated to melt. Thus, the foamable polyurethane composition can be obtained by a method such as a paint method or a method of dispersing in a solvent to prepare a slurry. Further, when the reaction curable resin component contained in the foamable polyurethane composition contains a component that is solid at room temperature (about 25 ° C.), the foamable polyurethane composition is melted under heating. A foamable polyurethane composition can be obtained.

  The foamable polyurethane composition is prepared by using a known apparatus such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a raikai machine, and a planetary stirring machine for each component of the foamable polyurethane composition. It can be obtained by kneading.

  Alternatively, the main component of urethane resin and the curing agent may be separately kneaded together with a filler or the like and kneaded with a static mixer, a dynamic mixer or the like immediately before injection.

  Further, the components of the foamable polyurethane composition excluding the catalyst and the catalyst can be kneaded in the same manner immediately before injection. A foamable polyurethane composition can be obtained by the method described above.

  Next, a method for curing the foamable polyurethane composition according to the present invention will be described.

  When the respective components of the foamable polyurethane composition are mixed, the reaction starts, the viscosity increases with the passage of time, and the fluidity is lost.

  For example, a foam layer composed of a foamable polyurethane composition is formed on the surface of the structure by spraying and curing the foamable polyurethane composition on a structure such as a building, furniture, automobile, train, ship, etc. A structure in which the foamable polyurethane composition is laminated can be obtained.

  The viscosity at 25 ° C. of the polyol composition for spray coating of the present invention is in the range of 50 to 2000 mPa · s. When the viscosity is 50 mPa · s or more and the viscosity is 2000 mPa · s or less, the polyol composition and the polyisocyanate can be mixed uniformly and sprayed uniformly on the structure, so that the workability is good. If the viscosity is less than 50 mPa · s, the viscosity is too low and dripping occurs, resulting in poor coating. If the viscosity exceeds 2000 mPa · s, the viscosity is too high and spray coating becomes difficult.

  The workability of the foamable polyurethane composition of the present invention can also be confirmed by measuring cream time. Cream time is measured, for example, at normal temperature (20 ° C.) and / or low temperature (5 ° C.). If the cream time when the temperature of the coated structure to which the foamable polyurethane composition is sprayed is 5 ° C. is within 1 second, it can be determined that the workability is good.

The flame retardancy of a foamed polyurethane composition or a molded article comprising the foamable polyurethane composition of the present invention can be confirmed by a corn calorimeter test.
First, a foamed polyurethane composition or a molded body made of a foamable polyurethane composition sprayed on a coated structure (manufactured by Yoshino Gypsum Co., Ltd .: ordinary gypsum board 12.5 mm) is 100 mm long, 100 mm wide and 20 mm thick (coated structure). Prepare a cone calorimeter test sample.

Next, using the sample for corn calorimeter test, the total calorific value by the corn calorimeter test when heated for 10 minutes and 20 minutes at a radiant heat intensity of 50 kW / m ² is measured according to the test method of ISO-5660. To do. The case where the total calorific value when heated for 10 minutes was 8 MJ / m ² or less was evaluated as acceptable. Moreover, when the total calorific value when heated for 20 minutes is 8 MJ / m ² or less, it can be evaluated that the flame retardancy is more excellent.

  As mentioned above, although embodiment of this invention was described concretely, this invention is not limited to the above-mentioned embodiment, Various deformation | transformation based on the technical idea of this invention is possible.

  For example, the configurations, methods, processes, shapes, materials, numerical values, and the like given in the above-described embodiments are merely examples, and different configurations, methods, processes, shapes, materials, numerical values, and the like are used as necessary. Also good.

The configurations, methods, steps, shapes, materials, numerical values, and the like of the above-described embodiments can be combined with each other without departing from the gist of the present invention.
The present invention can also employ the following configurations.
[1] A polyol composition for spray coating for reacting with a polyisocyanate compound to obtain a polyurethane foam, which contains a polyol, a catalyst, a foaming agent, a foam stabilizer, and a flame retardant, and has a viscosity of 50 to 50 A polyol composition for spray coating, which is 2000 mPa · s.
[2] The polyol composition for spray coating according to [1], wherein the catalyst contains 3 to 28 parts by weight of a trimerization catalyst and 0.3 to 28 parts by weight of a urethanization catalyst with respect to 100 parts by weight of the polyol. object.

[3] The polyol composition for spray coating according to [1] or [2], wherein the weight ratio of the trimerization catalyst to the urethanization catalyst is 10: 1 to 1:70.
[4] A foamable polyurethane premix composition for spray coating containing the polyol composition for spray coating and the polyisocyanate compound according to any one of [1] to [3].
[5] A foamable polyurethane composition for spray coating, which is a mixture of the polyol composition for spray coating according to any one of [1] to [3] and a polyisocyanate compound.

[6] Based on 100 parts by weight of a urethane resin composed of a polyisocyanate compound and a polyol,
The total amount of trimerization catalyst and urethanization catalyst is in the range of 3-14 parts by weight,
The trimerization catalyst is in the range of 1 to 7 parts by weight,
The urethanization catalyst is in the range of 0.1 to 7 parts by weight,
The foaming agent is in the range of 5 to 30 parts by weight,
The foam stabilizer is in the range of 0.1 to 10 parts by weight,
The phosphate is in the range of 1-20 parts by weight,
The total amount of the powder flame retardant is in the range of 4 to 25 parts by weight,
A foamable polyurethane resin composition for spray coating, characterized in that red phosphorus is in the range of 1 to 15 parts by weight.
[7] A polyurethane foam obtained by curing the foamable polyurethane composition for spray coating according to [5] or [6].
[8] The polyurethane foam according to [7], which is a molded body.

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

1. Manufacture of a polyol composition and a foamable urethane resin composition By the mixing | blending shown in Table 1, the polyol composition and foamable urethane resin composition which concern on Examples 1-15 and Comparative Examples 1-2 were prepared. Details of each component in the table are as follows.
(1) Isocyanate compound (hereinafter referred to as “polyisocyanate”)
(A) 4,4′-diphenylmethane diisocyanate (4,4′-MDI) (manufactured by Wanhua Chemical Japan, product name: PM200).

(2) Polyol composition / polyol (B)
p-phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RFK-087, hydroxyl value = 200 mgKOH / g)
・ Trimerization catalyst (C)
(C-1) Trimerization catalyst (manufactured by San Apro Co., Ltd., product name: U-CAT 18X).
(C-2) Trimerization catalyst (product name: TOYOCAT-TR20, manufactured by Tosoh Corporation)
(C-3) Trimerization catalyst (Momentive Performance Material Japan, product name: K-zero G)

・ Urethane catalyst (D)
(D-1) Urethane catalyst (manufactured by San Apro, product name: U-CAT 202)
(D-2) N, N, N′-trimethylaminoethylethanolamine (manufactured by Tosoh Corporation, trade name: TOYOCAT-RX5)
(D-3) Urethane catalyst (manufactured by Tosoh Corporation, product name: TOYOCAT-TT)
(D-4) Urethane catalyst (manufactured by Nitto Kasei Co., Ltd., product name: U-830)
・ Foaming agent (E)
(E-1) Water (E-2) HFC HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Nippon Solvay)
(E-3) HFC-245fa (1,1,1,3,3-pentafluoropropane, manufactured by Central Glass Co., Ltd.)
(E-4) LBA (Honeywell Japan, product name: Solstice LBA)
・ Foam stabilizer (F)
Polyalkylene glycol-based foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193)
・ Flame retardant Liquid flame retardant (G)
Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP, hereinafter referred to as “TMCPP”)
Powder flame retardant (H) Red phosphorus (Rin Chemical Industry Co., Ltd., product name: Nova Excel 140)
(I) Wollastonite (SiO 2 · CaO) (manufactured by Kinsei Tech Co., inorganic filler, product name: SH-1250).
(J) Zinc borate (made by Hayakawa Shoji Co., Ltd., transition metal compound, product name: Firebrake ZB)
(K) Hexabromobenzene (manac product, product name: HBB-b, hereinafter "HBB")

  Using a Graco sprayer “H-VR”, the polyisocyanate compound and the polyol composition were sprayed on the subject under the mechanical conditions shown in the examples. As a gun to be sprayed, a Gasmer D gun was used. As an object to be sprayed, a normal gypsum board (12.5 mm) manufactured by Yoshino Gypsum Co., Ltd. was used. One layer was sprayed on the object with a thickness of 20 mm.

  The obtained foamable urethane resin composition lost fluidity over time, and the foamed foamed urethane resin compositions of Examples 1 to 15 and Comparative Examples 1 and 2 were obtained.

2. Evaluation of Foam The above foam was evaluated according to the following criteria, and the results are shown in Table 1 (the proportion of each component is expressed in parts by weight relative to 100 parts by weight of the urethane resin).
[Measurement of viscosity]
Components other than polyisocyanate were placed in a 1000 mL polypropylene beaker and stirred to prepare a polyol composition. After stirring, the solution was stabilized for about 1 hour, and the polyol composition was weighed out in a 500 mL polypropylene beaker. After preparing the polyol composition in a water bath at 25 ° C., the viscosity was measured using a B-type viscometer manufactured by VISCOTECH. For the measurement, an R3 rotor was used, and the rotation speed was 60 rpm.

[Measurement of cream time]
After spraying the flame retardant urethane resin composition onto the coated structure, the mixed solution of the polyol composition and the polyisocyanate starts to react, and the time when the color of the solution starts to change color is visually observed, cream time It was.
[Measurement of total calorific value]
A sample for a cone calorimeter test was cut out from the cured product so that the size of the foamable urethane resin composition (excluding the thickness of the coated structure) was 100 mm × 100 mm × 20 mm, and radiant heat intensity was 50 kW / in accordance with ISO-5660. Table 1 shows the result of measuring the total calorific value when heated at m ^{2 for} 20 minutes.

  This measurement method is a test method stipulated as corresponding to the standard by the cone calorimeter method at the Building Research Institute, which is a public institution stipulated in Article 108-2 of the Building Standard Law Enforcement Ordinance. It conforms to the test method of ISO-5660.

The total calorific value of the corn calorimeter was 8 MJ / m ² or less when heated for 10 minutes.

  According to Table 1, in the foamable polyurethane compositions of Examples 1 to 15, dripping did not occur and spray coating was good. Moreover, the foamable polyurethane composition had excellent flame retardancy. In Comparative Examples 1 and 2, the foamable polyurethane composition had a high viscosity and was difficult to spray. Moreover, it was impossible to verify cream time and flame retardancy.

Claims (8)

  A polyol composition for spray coating for reacting with a polyisocyanate compound to obtain a polyurethane foam, comprising a polyol, a catalyst, a foaming agent, a foam stabilizer, and a flame retardant, and having a viscosity of 50 to 2000 mPa · s. A polyol composition for spray coating.   The polyol composition for spray coating according to claim 1, wherein the catalyst contains 3 to 28 parts by weight of a trimerization catalyst and 0.3 to 28 parts by weight of a urethanization catalyst with respect to 100 parts by weight of the polyol.   The polyol composition for spray coating according to claim 1 or 2, wherein the weight ratio of the trimerization catalyst to the urethanization catalyst is 10: 1 to 1:70.   A foamable polyurethane premix composition for spray coating comprising the polyol composition for spray coating and the polyisocyanate compound according to claim 1 separately.   The foamable polyurethane composition for spray coating which is a mixture of the polyol composition for spray coating and the polyisocyanate compound in any one of Claims 1-3. Based on 100 parts by weight of a urethane resin composed of a polyisocyanate compound and a polyol,
The total amount of trimerization catalyst and urethanization catalyst is in the range of 3-14 parts by weight,
The trimerization catalyst is in the range of 1 to 7 parts by weight,
The urethanization catalyst is in the range of 0.1 to 7 parts by weight,
The foaming agent is in the range of 5 to 30 parts by weight,
The foam stabilizer is in the range of 0.1 to 10 parts by weight,
The phosphate is in the range of 1-20 parts by weight,
The total amount of the powder flame retardant is in the range of 4 to 25 parts by weight,
A foamable polyurethane resin composition for spray coating, characterized in that red phosphorus is in the range of 1 to 15 parts by weight.   A polyurethane foam obtained by curing the foamable polyurethane composition for spray coating according to claim 5 or 6.   The polyurethane foam according to claim 7, which is a molded body.