JP6626242B2 - Flame retardant insulation composition - Google Patents

Description

  The present invention relates to a flame retardant insulation composition, and more particularly to a flame retardant insulation composition for use in spraying.

Conventionally, a rigid polyurethane spray foam is obtained by spraying a resin composition onto a building material and curing the resin composition on the building material.
By using such a rigid polyurethane spray foam, the heat insulation of building materials such as concrete can be easily improved, and thus the rigid polyurethane spray foam is widely used for architectural applications.
As an example of such a rigid polyurethane spray foam, it is composed of a first liquid containing a polyol component and a second liquid containing an isocyanate component. The first liquid and the second liquid are mixed and sprayed on a surface to be applied. Alternatively, there has been proposed a two-part type heat insulating material composition in which air is mixed with the first liquid and the second liquid, mixed with the air, discharged onto the surface to be processed, foamed and hardened, and foamed polyurethane heat insulating material is formed. (Patent Document 1).
The heat insulating material composition contains two or more polyols as a polyol component of the first liquid, and at least one polyol uses a polyol having a tertiary amine structure.
According to this heat insulating material composition, it is said that construction work can be favorably performed even in a low-temperature environment.

As an example of the rigid polyurethane spray foam, a rigid isocyanurate spray foam for building insulation using a subcritical fluid, a supercritical fluid or carbon dioxide in a liquid state as a foaming agent used in foaming the rigid isocyanurate foam is proposed. (Patent Document 2).
This rigid isocyanurate spray foam for building insulation does not use any chlorofluorocarbons, which are said to reduce atmospheric ozone during production, and therefore does not pose a burden on the environment.

Further, as an example of the rigid polyurethane spray foam, a heat-insulating noncombustible material comprising foamed polyurethane and cement particles hardened by a hydration reaction uniformly dispersed in a matrix of the foamed polyurethane has been proposed (Patent Document 3). ).
This heat-insulating incombustible material is considered to have excellent heat-insulating properties.

  However, the rigid polyurethane spray foam has a problem of easily burning. Therefore, in the case of a rigid polyurethane spray foam containing no cement particles, the specific gravity is small and lightweight, but the flame retardancy is not sufficient. There was a problem that became large.

Since the rigid polyurethane spray foam easily burns, research on a resin foam having excellent flame retardancy has been conducted.
Specifically, a composite heat insulating material in which a resin foam and a cured body of a mortar composition are laminated has been proposed (Patent Document 4). This composite heat insulating material is considered to be excellent in fire resistance because it contains a cured product of a mortar composition containing cement in addition to a resin foam.
A laminate using a cement composition containing expanded organic resin particles has also been proposed (Patent Document 5).
Since this laminate is formed from the cement composition, it is considered to be excellent in flame retardancy.
However, when flame retardancy is improved when cement is used, there is a problem that the weight of the molded body increases. In addition, when a cured product made of cement is used, the resulting product has a property that it is difficult to pass through fire but easily conducts heat, so that the problem of poor heat insulation properties remains.

JP 2008-303350A JP-A-2002-47325 JP-A-2002-38619 JP 2014-79661 A JP 2011-156799 A

  An object of the present invention is to provide a flame-retardant heat-insulating material composition having a small specific gravity, having excellent heat insulating properties and flame retardancy, and being suitable for spray applications.

  As a result of intensive studies by the inventors of the present invention to solve the above-mentioned problems, it has been found that a polyol liquid (X) containing a flame retardant and a flame retardant aid and an isocyanate liquid (Y) are difficult to use for spraying. The present inventors have found that a fuel and heat insulating material composition meets the purpose of the present invention, and have completed the present invention.

That is, the present invention
[1] having at least a polyol liquid (X) containing a polyol compound, a flame retardant, a flame retardant aid and a trimerization catalyst, and an isocyanate liquid (Y) containing a polyisocyanate compound;
The trimerization catalyst is a catalyst for a trimerization reaction of an isocyanate group of a polyisocyanate compound contained in the isocyanate liquid (Y),
The flame retardant contains at least red phosphorus and a phosphate,
The flame retardant aid comprises at least one selected from the group consisting of phosphate-containing flame retardants, bromine-containing flame retardants, metal hydroxides and needle fillers,
Flame retardant for use in spraying, characterized in that the flame retardant is in a range of 5.5 to 80 parts by weight based on 100 parts by weight of a urethane resin comprising the polyol compound and the polyisocyanate compound. A heat insulating composition is provided.

Also, one of the present invention,
[2] At least one selected from the group consisting of a phosphate-containing flame retardant, a bromine-containing flame retardant, a metal hydroxide, and an acicular filler contained in the flame retardant aid is added to 100 parts by weight of the urethane resin. On the other hand, the present invention provides a flame-retardant heat-insulating composition for use in the spray according to the above [1], which has a range of 3.0 to 90 parts by weight.

Also, one of the present invention,
[3] The flame retardant for use in the spray according to [1] or [2], wherein the trimerization catalyst is in a range of 0.01 to 10 parts by weight based on 100 parts by weight of the urethane resin. A heat insulating composition is provided.

Also, the present invention
[4] A method for using the flame-retardant heat-insulating composition for use in the spray according to any one of [1] to [3] above,
Spraying the polyol liquid (X) and the isocyanate liquid (Y) after mixing (1);
Or
Mixing the polyol liquid (X) and the isocyanate liquid (Y) after spraying (2)
It is intended to provide a method for using a flame-retardant heat-insulating composition for use in spraying, having:

Also, one of the present invention,
[5] The method for using a flame-retardant heat-insulating material composition for use in a spray according to the above [4], comprising a step of spraying a flame-retardant heat-insulating material composition for use in the spray on a structural material. To provide.

Also, one of the present invention,
[6] Use of the flame-retardant heat-insulating composition for use in a spray according to the above [5], comprising a step of curing the flame-retardant heat-insulating composition for use in the spray on the structural material. It provides a method.

Also, the present invention
[7] A hard polyurethane obtained by curing the flame-retardant heat-insulating material composition for use in the spray according to the method for using the flame-retardant heat-insulating material composition according to any one of the above [4] to [6]. It provides a spray form.

By using the flame-retardant heat insulating material composition for use in the spray according to the present invention, it is possible to easily obtain a rigid polyurethane spray foam having a small specific gravity and excellent heat insulation and flame retardancy.
This rigid polyurethane spray foam can easily improve the heat insulating property and the flame retardancy of the structural material.

FIG. 1 is a schematic configuration diagram illustrating the configuration of a spray device 100 that sprays the flame-retardant heat-insulating material composition according to the first embodiment. FIG. 2 is a schematic configuration diagram illustrating the configuration of a spray device 110 that sprays the flame-retardant heat-insulating material composition according to the second embodiment. FIG. 3 is a schematic diagram for explaining a method for measuring the adhesive strength of a rigid polyurethane spray foam. FIG. 4 is a schematic diagram for explaining a method for measuring the adhesive strength of a rigid polyurethane spray foam.

The flame-retardant heat insulating material composition for use in the spray of the present invention comprises a polyol liquid (X) containing a polyol compound, a flame retardant, a flame retardant aid and a trimerization catalyst, and an isocyanate liquid (Y) containing a polyisocyanate compound. And at least
A urethane resin is obtained by combining the polyol compound contained in the polyol solution (X) used in the present invention with the polyisocyanate compound contained in the isocyanate solution (Y).
The polyisocyanate compound serves as a main component of the urethane resin, and the polyol compound serves as a curing agent for the urethane resin.

First, a polyisocyanate compound which is a main agent of the urethane resin will be described.
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, and polymethylene polyphenyl polyisocyanate.
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, hexamethylene diisocyanate, and the like.
One or more polyisocyanate compounds can be used.
The main component of the urethane resin is preferably diphenylmethane diisocyanate because of its ease of use and availability.

  Examples of the polyol compound include a polylactone polyol, a polycarbonate polyol, an aromatic polyol, an alicyclic polyol, an aliphatic polyol, a polyester polyol, a polymer polyol, and a polyether polyol.

Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.
As the polycarbonate polyol, for example, a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, nonanediol, and a diethylene carbonate, obtained by a dealcoholation reaction with dipropylene carbonate and the like. Polyols and the like

Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolak, cresol novolak, and the like.
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, hexanediol and the like.
As the polyester polyol, for example, a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, ε-caprolactone, a polymer obtained by ring-opening polymerization of a lactone such as α-methyl-ε-caprolactone And condensates of hydroxycarboxylic acids and the above-mentioned polyhydric alcohols.

Here, specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, succinic acid, and the like.
Specific examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol. Can be
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, for example, graft polymerization of an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, or methacrylate to the aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polyether polyol, or the like. Polymer, a polybutadiene polyol, a modified polyol of a polyhydric alcohol, or a hydrogenated product thereof.

Examples of the modified polyol of the polyhydric alcohol include those modified by reacting a polyhydric alcohol as a raw material with an alkylene oxide.
Examples of the polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane,
4- to octavalent alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol and the like, 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 Phenols such as 1,8-tetrahydroxyanthracene and 1-hydroxypyrene;
Polybutadiene polyol,
Castor oil polyol,
Examples include (co) polymers of hydroxyalkyl (meth) acrylates, polyfunctional (for example, having 2 to 100 functional groups) polyols such as polyvinyl alcohol, and condensates (novolaks) of phenol and formaldehyde.

The method for modifying the polyhydric alcohol is not particularly limited, but a method of adding an alkylene oxide (hereinafter abbreviated as AO) is preferably used.
Examples of the AO include AO having 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 oxide, 1,4-butylene oxide and the like.
Among these, PO, EO and 1,2-butylene oxide are preferred from the viewpoint of properties and reactivity, and PO and EO are more preferred.
When two or more types of AO are used (for example, PO and EO), the addition method may be block addition, random addition, or a combination thereof.

As the polyether polyol, for example, in the presence of at least one kind of low-molecular-weight active hydrogen compound having two or more active hydrogens, ethylene oxide, propylene oxide, at least one kind of alkylene oxide such as tetrahydrofuran is subjected to ring-opening polymerization. And the polymer obtained by the above method.
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,
Examples include amines such as ethylenediamine and butylenediamine.

  As the polyol compound used in the present invention, it is preferable to use a polyester polyol and a polyether polyol because a hard polyurethane spray foam obtained by curing the flame-retardant heat-insulating composition is difficult to ignite.

Next, the compounding ratio between the main agent of the urethane resin and the curing agent will be described.
In the present invention, the index is defined by [equivalent number of isocyanate] × 100 ÷ [equivalent number of polyol + equivalent number of water].
Here, the equivalent number of the polyol compound is represented by [hydroxyl value of polyol compound (mgKOH / g)] × [weight of polyol compound (g)] ÷ [molecular weight of potassium hydroxide].
The equivalent number of the polyisocyanate compound is represented by [molecular weight of isocyanate group] × 100 [weight% of isocyanate group].
The equivalent number of water is represented by [weight of water (g)] × 2 × [molecular weight of water].
The range of the index is preferably in the range of 120 to 700.
When the equivalent ratio is 700 or less, poor foaming can be prevented, and when it is 120 or more, good heat resistance can be obtained.

Further, in the present invention, a urethane resin curing catalyst can be used in addition to the urethane resin.
Examples of the urethane curing catalyst include an amino compound, a tin compound, and a metal salt of acetylacetone.

Examples of the amino compound include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinebis (2-dimethylaminoethyl) ether, bis (2-dimethylaminoethyl) ether, N, N, N ', N ", N" -Pentamethyldiethylenetriamine, N, N, N'-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl, N'-dimethylaminoethylpiperazine, secondary amine function in imidazole ring Compounds in which the group is substituted with a cyanoethyl group, N, N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine, N-methylimidazole, trimethylaminoethylpiperazine, trippropine Luamine,
Tetramethylammonium salt, tetraethylammonium salt, triphenylammonium salt and the like can be mentioned.

  Examples of the tin compound include stannous octylate, dibutyltin diacetate, dibutyltin dilaurate, and the like.

  Examples of the acetylacetone metal salt include aluminum acetylacetone, iron acetylacetone, copper acetylacetone, acetylacetone zinc, acetylacetone beryllium, acetylacetone chromium, acetylacetone indium, acetylacetone manganese, acetylacetone molybdenum, acetylacetone titanium, acetylacetone cobalt, acetylacetone vanadium, acetylacetone zirconium, and the like. Can be

  One or two or more urethane resin curing catalysts can be used.

The amount of the urethane resin curing catalyst used in the flame-retardant heat-insulating material composition according to the present invention is not particularly limited, but is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. , 0.01 to 8.0 parts by weight, more preferably 0.01 to 6.0 parts by weight, even more preferably 0.01 to 1.5 parts by weight. Is most preferred.
When the content is 0.01 part by weight or more and 10 parts by weight or less, handling becomes easy and reaction control becomes easy.

  As the polyurethane resin used in the present invention, a resin in which an isocyanate group contained in a polyisocyanate compound which is a main component of the polyurethane resin is reacted and trimerized to promote generation of an isocyanurate ring can be used.

In order to promote the formation of the isocyanurate ring, for example, as a catalyst, tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro Aromatic compounds such as -S-triazine, quaternary ammonium compounds such as potassium acetate, sodium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate and carboxylic acid salts of tertiary amines, 2-ethylaziridine and the like Amine compounds such as aziridine, etc., lead compounds such as diazabicycloundecene, lead naphthenate, lead octylate, alcoholate compounds such as sodium methoxide, phenolate compounds such as potassium phenoxide, quaternary ammonium salts of carboxylic acid, etc. Should be used.

The addition amount of the trimerization catalyst used in the flame-retardant heat-insulating material composition according to the present invention is not particularly limited, but is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the urethane resin, It is more preferably in the range of 0.01 to 8 parts by weight, further preferably in the range of 0.01 to 6 parts by weight, and most preferably in the range of 0.5 to 1.5 parts by weight.
When the amount is 0.01 part by weight or more, the problem that the trimerization of isocyanate is inhibited does not occur, and when the amount is 10 parts by weight or less, the problem that the urethane bond is inhibited can be reduced.

  One or more of the trimerization catalysts can be used.

As the foaming agent, for example, water,
Low-boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane and cycloheptane;
Chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride,
Fluorine compounds such as trichloromonofluoromethane, trichlorotrifluorofluoroethane, CHF ₃ , CH ₂ F ₂ and CH ₃ F;
Hydrochlorofluorocarbon compounds such as dichloromonofluoroethane, (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane);
Hydrofluorocarbon compounds such as HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane), and hydrofluoroolefin compounds such as HFO ,
Organic physical blowing agents such as ether compounds such as diisopropyl ether, or a mixture of these compounds;
Examples include inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas.

  The foaming agent used in the present invention is preferably pentane, hydrofluorocarbon, hydrofluoroolefin, or water, and more preferably water, hydrofluorocarbon, or hydrofluoroolefin.

  Further, one or more foaming agents can be used in the present invention.

The amount of the blowing agent used in the flame-retardant heat-insulating material composition according to the present invention is not particularly limited, but is preferably in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the urethane resin, It is more preferably in the range of 0.5 to 15 parts by weight, further preferably in the range of 1.0 to 15 parts by weight, and most preferably in the range of 1.5 to 10 parts by weight.
When the range of the water is 0.1 part by weight or more, foaming is promoted, and the density of the obtained molded body can be reduced. When the range is 20 parts by weight or less, cells of the foam break and foam The body can be prevented from being formed.

A foam stabilizer may be used in the flame-retardant heat-insulating composition according to the present invention.
Examples of the foam stabilizer include surfactants such as polyoxyalkylene foam stabilizer such as polyoxyalkylene alkyl ether, and silicone foam stabilizer such as organopolysiloxane.
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.If one example is shown, for example, 100 parts by weight of the urethane resin On the other hand, it is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 4.0 parts by weight, and still more preferably 1.0 to 3.0 parts by weight.

  The foam stabilizers may be used alone or in combination of two or more.

Next, the flame retardant added to the flame retardant insulating material composition used in the present invention will be described.
The flame retardant used in the present invention contains red phosphorus and a phosphate ester. First, red phosphorus will be described.
There is no limitation on the red phosphorus used in the present invention, and commercially available products can be appropriately selected and used.

The amount of red phosphorus used in the flame-retardant heat insulating material composition is in the range of 3.0 to 30 parts by weight based on 100 parts by weight of the urethane resin. The amount of the red phosphorus is preferably in the range of 3.0 to 20 parts by weight, more preferably in the range of 3.0 to 18 parts by weight, and more preferably in the range of 6.0 to 18 parts by weight. Is more preferred.
When the range of the above-mentioned red phosphorus is 3.0 parts by weight or more, the self-extinguishing property of the flame-retardant heat-insulating material composition according to the present invention is maintained. The foaming of the material composition is not hindered.

  The phosphate ester is not particularly limited, but it is preferable to use a monophosphate ester, a condensed phosphate ester, or the like.

  The monophosphate is not particularly limited. For example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, and trixylenyl phosphate , Tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthylphosphate, cresyldiphenylphosphate, xylenyldiphenylphosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenylphosphate, monoisodecylphosphate , 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate Phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, phenylphosphonic acid Examples include diethyl, resircinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, and tris (β-chloropropyl) phosphate.

The condensed phosphoric acid ester is not particularly limited. For example, trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate (trade name PX-, manufactured by Daihachi Chemical Industry Co., Ltd.) 200), hydroquinone poly (2,6-xylyl) phosphate and condensed phosphoric esters such as condensates thereof.
Commercially available condensed phosphate esters include, for example, resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade name CR-741), aromatic condensed phosphate ester (trade name CR747), resorcinol Examples thereof include polyphenyl phosphate (trade name: ADK STAB PFR, manufactured by ADEKA) and bisphenol A polycresyl phosphate (trade names: FP-600, FP-700).

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

  The phosphoric ester may be used alone or in combination of two or more.

The amount of the phosphate ester used in the present invention is in the range of 2.5 to 50 parts by weight based on 100 parts by weight of the urethane resin. The amount of the phosphate ester added is preferably in the range of 3.0 to 50 parts by weight, more preferably in the range of 3.0 to 30 parts by weight, and in the range of 7.0 to 30 parts by weight. More preferred.
When the range of the phosphoric acid ester is 2.5 parts by weight or more, the molded article made of the flame-retardant heat-insulating material composition according to the present invention becomes difficult to ignite. The foaming of the fuel insulation composition is not hindered.

Further, the flame-retardant heat insulating material composition according to the present invention contains a flame-retardant auxiliary.
The flame retardant aid contains at least one selected from the group consisting of a phosphate-containing flame retardant, a bromine-containing flame retardant, a metal hydroxide, and an acicular filler.

First, the phosphate-containing flame retardant used for the flame retardant aid will be described.
The phosphoric acid used for the phosphate-containing flame retardant is not particularly limited, and examples thereof include various phosphoric acids such as monophosphoric acid and pyrophosphoric acid.

Examples of the phosphate-containing flame retardant include, for example, salts of the various phosphoric acids with at least one metal or compound selected from metals of Groups IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. Phosphates.
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, and piperazine.
Examples of the aromatic amine include pyridine, triazine, melamine, and ammonium.
The above-mentioned phosphate-containing flame retardant may be subjected to a known silane coupling agent treatment, a known water resistance improving treatment such as coating with a melamine resin, or a known foaming aid such as melamine or pentaerythritol. May be.

  Specific examples of the phosphate-containing flame retardant include, for example, monophosphate and pyrophosphate.

The monophosphate is not particularly limited, for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and ammonium dihydrogen phosphate;
Sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, sodium hypophosphite,
Potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, potassium hypophosphite,
Lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, 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, and magnesium hypophosphite;
Calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite,
Zinc phosphate, zinc phosphite, zinc salts such as zinc hypophosphite,
Aluminum salts such as aluminum monophosphate, aluminum phosphate dibasic, aluminum tertiary phosphate, aluminum phosphite, aluminum hypophosphite and the like can be mentioned.

  Among these, monophosphates are preferably used because the self-extinguishing property of the phosphate-containing flame retardant is improved, and ammonium dihydrogen phosphate, diammonium hydrogen phosphate, aluminum monophosphate, and phosphoric acid are preferred. It is more preferable to use at least one selected from the group consisting of monosodium and tribasic aluminum phosphate, and it is more preferable to use ammonium dihydrogen phosphate.

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

The addition amount of the phosphate-containing flame retardant used in the present invention is in the range of 1.5 to 20 parts by weight based on 100 parts by weight of the urethane resin. The addition amount of the phosphate-containing flame retardant is preferably in the range of 1.5 to 10 parts by weight, more preferably in the range of 3.0 to 10 parts by weight, and more preferably 3.0 to 8.0 parts by weight. It is more preferable that the content is within the range of parts.
When the range of the monophosphate-containing flame retardant is 1.5 parts by weight or more, the self-extinguishing property of the flame-retardant heat insulating material composition according to the present invention is maintained. The foaming of the flame-retardant heat insulating material composition is not hindered.

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, and examples thereof include an aromatic brominated compound.
Specific examples of the aromatic brominated compound include, for example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentane Monomeric organic bromine compounds such as bromophenoxy) ethane, ethylene-bis (tetrabromophthalimide), and 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 the reaction of brominated bisphenol A and epichlorohydrin, monoepoxy compounds obtained by the reaction of brominated phenols and 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 cross-linked or non-cross-linked brominated poly (-methylstyrene).
From the viewpoint of enhancing the self-extinguishing properties of the flame-retardant heat insulating material composition according to the present invention, a brominated aromatic ring-containing aromatic compound in which a bromine atom is substituted on an aromatic ring is preferable, and brominated polystyrene, hexabromobenzene, and the like are more preferable. And hexabromobenzene are more preferred.

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

The amount of the bromine-containing flame retardant used in the present invention is not particularly limited, but is in the range of 1.5 to 20 parts by weight based on 100 parts by weight of the urethane resin. The amount of the bromine-containing flame retardant is preferably in the range of 1.5 to 10 parts by weight, more preferably in the range of 3.0 to 10 parts by weight, and more preferably in the range of 3.0 to 8.0 parts by weight. It is more preferable if it is within the range.
When the range of the bromine-containing flame retardant is 1.5 parts by weight or more, the self-extinguishing property of the flame-retardant heat-insulating composition according to the present invention is maintained. The foaming of the fuel insulation composition is not hindered.

  Examples of the metal hydroxide used in the present invention include aluminum hydroxide, magnesium hydroxide, dawsonite, calcium aluminate, dihydrate gypsum, and calcium hydroxide.

  One or more kinds of the metal hydroxides can be used.

The amount of the metal hydroxide used in the present invention is not particularly limited, but is in the range of 1.5 to 20 parts by weight based on 100 parts by weight of the urethane resin. The addition amount of the metal hydroxide is preferably in the range of 1.5 to 10 parts by weight, more preferably in the range of 3.0 to 10 parts by weight, and more preferably in the range of 3.0 to 8.0 parts by weight. It is more preferable if it is within the range.
When the range of the metal hydroxide is 1.5 parts by weight or more, the self-extinguishing property of the flame-retardant heat-insulating material composition according to the present invention is maintained. The foaming of the fuel insulation composition is not hindered.

  Examples of the needle filler used in the present invention include, for example, potassium titanate whisker, aluminum borate whisker, magnesium-containing whisker, silicon-containing whisker, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fiber , Asbestos fiber, carbon fiber, graphite fiber, metal fiber, slag fiber, gypsum fiber, silica fiber, alumina fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, stainless fiber and the like.

  The range of the aspect ratio (length / diameter) of the needle filler used in the present invention is preferably from 5 to 50, and more preferably from 10 to 40.

  One or more of the needle fillers can be used.

The amount of the needle filler used in the present invention is not particularly limited, but is preferably in the range of 3.0 to 30 parts by weight, more preferably 3.0 to 20 parts by weight, based on 100 parts by weight of the urethane resin. It is more preferably in the range, more preferably in the range of 3.0 to 18 parts by weight, and most preferably in the range of 6.0 to 18 parts by weight.
When the range of the acicular filler is 3.0 parts by weight or more, the shape of the flame-retardant heat-insulating material composition according to the present invention after burning is maintained. The foaming of the fuel insulation composition is not hindered.

In addition, the flame-retardant heat-insulating material composition according to the present invention can use an inorganic filler.
The inorganic filler is not particularly limited, for example, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony trioxide, ferrites, calcium hydroxide, magnesium hydroxide , Aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc borate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, potassium salts such as calcium sulfate, barium sulfate, calcium silicate, talc, clay, Mica, montmorillonite, bentonite, activated clay, imogolite, sericite, glass beads, silica balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon balun, charcoal powder, various metal powders, magnesium sulfate, Tan lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, various magnetic powder, fly ash, inorganic phosphorus compounds, and the like.

  One or more kinds of the inorganic filler can be used.

  Further, the flame-retardant heat-insulating composition according to the present invention may contain, if necessary, a phenol-based, amine-based, sulfur-based antioxidant, a heat stabilizer, and a metal harm prevention within a range not to impair the object of the present invention. Agents, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, additives such as tackifying resins, and tackifiers such as polybutene and petroleum resins.

Since the flame-retardant heat-insulating composition according to the present invention reacts and cures, its viscosity changes over time.
Therefore, before using the flame-retardant heat insulating material composition according to the present invention, it is divided into at least a polyol liquid (X) containing a foam stabilizer, a foaming agent, a flame retardant and a trimerization catalyst, and an isocyanate liquid (Y). The reaction of the flame-retardant heat-insulating material is prevented from being cured.
Then, the polyol liquid (X) and the isocyanate liquid (Y) are mixed and then sprayed, or the polyol liquid (X) and the isocyanate liquid (Y) are mixed after being sprayed.
When the polyol liquid (X) and the isocyanate liquid (Y) are respectively mixed after spraying, the polyol liquid (X) and the isocyanate liquid (Y) may be mixed simultaneously with the spraying. After spraying at least one of the polyol liquid (X) and the isocyanate liquid (Y), the remaining one may be sprayed and mixed.
The mixed polyol solution (X) and isocyanate solution (Y) undergo a curing reaction and lose their fluidity over time, forming a rigid polyurethane spray foam.

The specific gravity of the rigid polyurethane foam comprising the flame-retardant heat-insulating material composition is not particularly limited, but is preferably in the range of 0.02 to 0.20, and more preferably in the range of 0.02 to 0.10. Preferably, the range of 0.03 to 0.08 is more preferable, and the range of 0.03 to 0.06 is most preferable.
Such a fire-resistant heat-insulating layer has a small specific gravity and is easy to handle.

The rigid polyurethane spray foam obtained by curing the flame-retardant heat-insulating material composition according to the present invention has bubbles inside.
Preferably, the cells are closed cells in the polyurethane foam.
The rigid polyurethane spray foam has a property that it is difficult to ignite while having excellent heat insulating properties.

Next, a first embodiment of the flame-retardant heat insulating material composition for use in the spray according to the present invention will be described.
First polyol compound, a catalyst, a foam stabilizer, polyol solution, prepare (X) containing a blowing agent and a flame retardant.
Similarly, prepare isocyanate solution (Y) containing a polyisocyanate compound.

FIG. 1 is a schematic configuration diagram illustrating the configuration of a spray device 100 that sprays the flame-retardant heat-insulating material composition according to the first embodiment.
The polyol liquid (X) is charged into the container 1. The isocyanate liquid (Y) is charged into the container 2.

A pipe 10 is connected to each of the vessels 1 and 2, and the contents of the vessels 1 and 2 can be transferred to the reaction vessel 20 through the pipes 10 and 10.
The containers 1 and 2 are provided with open / close valves 3 and 3, respectively.

  By introducing a gas such as nitrogen into the containers 1 and 2, the contents of the containers 1 and 2 can be transferred to the reaction container 20 through the pipe 10. It is also possible to interrupt the transfer by interrupting the introduction of the gas and closing the on-off valve 3.

The reaction vessel 20 is provided with a stirring blade 21 so that the contents of the reaction vessel 20 can be stirred.
The polyol liquid (X) and the isocyanate liquid (Y) introduced into the reaction vessel 20 are mixed inside the reaction vessel 20 and pass through the pipe 22 together with the compressed air supplied by the air compressor 30. Is discharged from the spray nozzle 23 to the outside.

The flame-retardant thermal insulation composition comprising the polyol liquid (X) and the isocyanate liquid (Y) cures to form a rigid polyurethane spray foam.
The resulting rigid polyurethane spray foam has a low specific gravity, a small amount of heat at the time of combustion, and a property of being difficult to burn.

By spraying the flame-retardant heat-insulating material composition on a structural material, the heat-insulating properties and fire resistance of the structural material can be easily increased.
As the structural material, for example, building materials such as walls, floors, ceilings, doors, beams,
Passenger cars, buses, trucks, tractors and other four-wheeled vehicles, two-wheeled vehicles, bicycles, trains, land vehicles such as freight locomotives, etc. Vehicles such as boats such as patrol boats can be cited.
It is to be noted that a rigid polyurethane spray foam having similarly excellent heat insulation and fire resistance can be obtained by using the formulations of any of the examples.

Next, a second embodiment of the flame-retardant insulating material composition for use in the spray according to the present invention will be described.
In the case of the first embodiment, the polyol liquid (X) and the isocyanate liquid (Y) were mixed and sprayed before use.
On the other hand, in the case of the second embodiment, the polyol liquid (X) and the isocyanate liquid (Y) are sprayed independently, and the polyol liquid (X) and the isocyanate liquid (Y) are sprayed during spraying. The point of mixing is different.
In the case of the second embodiment, as in the first embodiment, the polyol compound, a catalyst, a foam stabilizer, and a polyol solution containing a flame retardant (X) and made tone.
And, it prepares isocyanate solution (Y) containing a polyisocyanate compound in the same manner.

FIG. 2 is a schematic configuration diagram illustrating the configuration of a spray device 110 that sprays the flame-retardant heat-insulating material composition according to the second embodiment.
Pipes 22 are installed in the containers 1 and 2, respectively, and together with the compressed air supplied by the air compressor 30, the above-mentioned polyol liquid (X
) And the isocyanate liquid (Y) is discharged.

The flame-retardant thermal insulation composition comprising the polyol liquid (X) and the isocyanate liquid (Y) cures to form a rigid polyurethane spray foam.
The resulting rigid polyurethane spray foam has a low specific gravity, a small amount of heat at the time of combustion, and a property of being difficult to burn.

By spraying the flame-retardant heat-insulating material composition on the structural material, the flame-retardant heat-insulating material composition can be easily cured on the structural material. Can be enhanced.
It should be noted that a rigid polyurethane spray foam having similarly excellent heat insulation and fire resistance can be obtained by using any of the formulations of Reference Examples.

  Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited at all by the following examples.

  According to the composition shown in Table 1, the flame-retardant heat-insulating material composition according to Example 1 was prepared. The details of each component shown in Table 1 are as follows.

(A) Polyol compound A-1: p-phthalic acid-based polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RFK-505, hydroxyl value: 250 mgKOH / g, number of functional groups: 2 [per molecule])
A-2: p-phthalic acid-based polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: RLK-087, hydroxyl value: 200 mgKOH / g, number of functional groups: 2 [per molecule])
(B) Catalyst B-1: potassium octylate (K-zero G, manufactured by Momentive Performance Materials)
B-2: trimerization catalyst (manufactured by Tosoh Corporation, product name: TOYOCAT-TR20)
B-3: Pentamethyldiethylenetriamine (Tosoh Corporation, product name: TOYOCAT-DT)
(C) Foam stabilizer Polyalkylene glycol-based foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193, foam stabilizer in Table 1)
(D) Blowing agent D-1: water D-2: HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Nippon Solvay)
HFC-245fa (1,1,1,3,3-pentafluoropropane, manufactured by Central Glass)
Mixing ratio HFC-365mfc: HFC-245fa = 7: 3 (described as "HFC" in Table 1)
D-3: HFO (trans-1-chloro-3,3,3-trifluoropropene, manufactured by Honeywell, product name: Solstice LBA)
(E) Polyisocyanate compound MDI (manufactured by Nippon Polyurethane Industry Co., Ltd., product name: Millionate MR-200) Isocyanate content 30.5 to 32.0%
(F) Flame retardant F-1: Red phosphorus (manufactured by Rin Kagaku Kogyo KK, product name: Nova Excel 140)
F-2: Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCP)
P, hereinafter referred to as “TMCPP”. )
(G) Flame retardant aid G-1: ammonium dihydrogen phosphate (manufactured by Taihei Chemical Industry Co., Ltd.)
G-2: Hexabromobenzene (manac, product name: HBB-B, hereinafter referred to as "HBB")
G-3: Aluminum hydroxide (manufactured by Armorix, product name: B-325)
G-4: Needle-like filler (manufactured by Kinsei Matech Co., Ltd., product name: SH-1250)

Next, according to the composition shown in Table 1 below, the polyisocyanate as the component (E) and the components other than the polyisocyanate are each kept at a predetermined temperature, and a foaming machine (product name: REACTOR E-10, manufactured by GRACO) is used. And spray-foamed.
During spray spray foaming, the primary heater temperature of the foaming machine was in the range of 30-50 ° C, and the hose heater temperature was in the range of 30-50 ° C.
The sprayed flame retardant insulation composition loses its fluidity over time, yielding a rigid polyurethane spray foam.
The rigid polyurethane spray foam was evaluated according to the following criteria, and the results are shown in Table 1.
The density was 51 (kg / m ³ ). Also shown in Table 1.

[Measurement of total calorific value]
A rectangular parallelepiped cone calorimeter test sample was cut out from a rigid polyurethane spray foam so as to have a size of 10 cm (length) × 10 cm (width) × 2 cm (thickness), and a radiant heat intensity of 50 kW / m ² was obtained in accordance with ISO-5660. The total heating value when heated for 20 minutes was measured.
This measurement method is a test method specified by the Building Comprehensive Laboratory, which is a public organization specified in Article 108-2 of the Building Standards Law Enforcement Order, as corresponding to the standard based on the cone calorimeter method. It is based on the test method of ISO-5660.
The total calorific value by this test was 7.1 (MJ / m ² ). Table 1 shows the results.

[Measurement of residue state]
As a result of the above measurement of the total calorific value, the magnitude of the longitudinal and lateral shrinkage of the test sample changed in the horizontal direction by 5 mm or more in each of the vertical and horizontal directions, and when the thickness changed by 10 mm or more, the result was evaluated as x, and the others were evaluated as ○. did. Table 1 shows the results.

[Measurement of thermal conductivity]
It was measured by QTM-500 manufactured by Kyoto Electronics Industry Co., Ltd. The unit of thermal conductivity is W / mk. Table 1 shows the results.

[Measurement of adhesive strength]
FIG. 3 and FIG. 4 are schematic diagrams for explaining a method of measuring the adhesive force of the rigid polyurethane spray foam.
The flame-retardant heat insulating material composition according to Example 1 was cured on a commercially available concrete substrate 40 to obtain a rigid polyurethane spray foam 41. Next, the surface of the rigid polyurethane spray foam 41 was polished to adjust the thickness of the rigid polyurethane spray foam to 50 mm. An anchor pull-out tester 60 was used for the experiment (Pull-out tester Technostar RT-3000LD manufactured by Sanko Techno Co., Ltd.).
FIG. 3 illustrates a state in which the rigid polyurethane spray foam 41 is viewed from above. The hard polyurethane spray foam 41 has cuts 42 and 43 cut by 40 mm in length and width, and the cuts 42 and 43 reach the concrete base material 40. 40 mm in length and width from the molded product of the rigid polyurethane spray foam 41,
The rectangular parallelepiped portion 44 having a thickness of 50 mm can be pulled out.
As shown in FIG. 4, an adherend 50 is bonded to the upper surface of the rectangular parallelepiped portion 44 with an adhesive.
A rod 51 is fixed to the adherend 50, and when the handle 52 is turned, the rod 51 is lifted up together with the adherend 50. The value obtained by dividing the maximum stress Fmax (N) required for pulling out the rectangular parallelepiped portion 44 from the rigid polyurethane spray foam 41 by the bonding area (cm ² ) of the adherend 50 was defined as the bonding force (N / cm ² ). .
The experiment was repeated six times. Table 1 shows the average value.

[Density measurement]
It was measured according to JIS A 9526. The unit is kg / m ³ . Table 1 shows the results.

[Measurement of dimensional stability]
A rectangular parallelepiped sample of 10 cm (length) × 10 cm (width) × 5 cm (thickness) was prepared, and the test sample had a shrinkage of 2% when allowed to stand at 80 ° C. and 85% RH for one month. The following were evaluated as 、, and the others as ×. Table 1 shows the results.

Compared with the case of Example 1, 3.2 parts by weight of the flame retardant F-1 and 3.6 parts by weight of F-2 were used. The experiment was carried out in exactly the same manner as in Example 1 except that 1.6 parts by weight of the flame retardant aid G-1 and 1.6 parts by weight of G-2 were used.
Table 1 shows the results.

Compared with the case of Example 1, 7.9 parts by weight of the foaming agent D-2, 15.8 parts by weight of the flame retardant F-1 and 18.4 parts by weight of F-2 were used. The experiment was carried out in exactly the same manner as in Example 1 except that 7.9 parts by weight of the flame retardant aid G-1 and 7.9 parts by weight of G-2 were used.
Table 1 shows the results.

The experiment was performed in exactly the same manner as in Example 1 except that 35.8 parts by weight of the polyol compound A-1 was used and 64.2 parts by weight of the polyisocyanate compound E were used, as compared with the case of Example 1. Was.
Table 1 shows the results.

The experiment was performed in exactly the same manner as in Example 1 except that 10 parts by weight of the polyol compound A-1 and 90 parts by weight of the polyisocyanate compound E were used, as compared with the case of Example 1.
Table 1 shows the results.

The experiment was performed in exactly the same manner as in Example 1 except that 8.2 parts by weight of the blowing agent D-2 was used.
Table 1 shows the results.

As compared with the case of Example 1, except that 10.9 parts by weight of the polyol compound A-1 was used, 12.6 parts by weight of A-2 was used, and 76.5 parts by weight of the polyisocyanate compound E were used. The experiment was performed in exactly the same manner as in Example 1.
Table 1 shows the results.

As compared with the case of Example 1, except that 25.3 parts by weight of A-2 was used instead of the polyol compound A-1 and 74.7 parts by weight of the polyisocyanate compound E were used. The experiment was performed in exactly the same way.
Table 1 shows the results.

The experiment was performed in exactly the same manner as in Example 1, except that G-4 was used in an amount of 9.0 parts by weight instead of the flame retardant aid G-2.
Table 1 shows the results.

Compared with the case of Example 9, 9.0 parts by weight of the flame retardant F-1 was used, 3.0% by weight of G-4 was not used, and the flame retardant auxiliary G-2 was not used. Except for this, the experiment was performed in exactly the same manner as in Example 9.
Table 1 shows the results.

The experiment was performed in exactly the same manner as in Example 9 except that 9.0 parts by weight of the flame retardant F-1 was used and that the flame retardant aid G-1 was not used. Was done.
Table 1 shows the results.

Compared to the case of Example 7, 9.0 parts by weight of the flame retardant F-1 was used, G-1 and G-2 were not used, and G-4 was 9.0. The experiment was conducted in exactly the same manner as in Example 7 except that parts by weight were used.
Table 2 shows the results.

Compared to the case of Example 8, 9.0 parts by weight of the flame retardant F-1 was used, G-1 and G-2 were not used, and G-4 was 9.0. The experiment was conducted in exactly the same manner as in Example 8 except that parts by weight were used.
Table 2 shows the results.

Compared with Example 1, 9.0 parts by weight of the flame retardant F-1 and 15 parts by weight of F-2 were used. The experiment was performed in exactly the same manner as in Example 1 except that the flame retardant aids G-1 and G-2 were not used, and that G-4 was used in an amount of 9.0 parts by weight.
Table 2 shows the results.

The experiment was performed in exactly the same manner as in Example 14, except that 30 parts by weight of the flame retardant F-2 was used.
Table 2 shows the results.

The experiment was performed in exactly the same manner as in Example 15 except that 18 parts by weight of the flame retardant aid G-4 was used.
Table 2 shows the results.

The experiment was carried out in exactly the same manner as in Example 11 except that 18 parts by weight of the flame retardant F-1 was used.
Table 2 shows the results.

Compared with Example 17, 6.0 parts by weight of the flame retardant F-1 was used. The experiment was carried out in exactly the same manner as in Example 17 except that 3.0 parts by weight of G-1 was used instead of the flame retardant aid G-4.
Table 2 shows the results.

The experiment was performed in exactly the same manner as in Example 18, except that 3.0 parts by weight of G-2 was used instead of the flame retardant aid G-1.
Table 2 shows the results.

The experiment was carried out in exactly the same manner as in Example 19, except that 6.0 parts by weight of G-3 was used in place of the flame-retardant aid G-2 as compared with Example 19.
Table 2 shows the results.

The experiment was performed in exactly the same manner as in Example 1 except that 5.7 parts by weight of D-3 was used instead of the blowing agent D-2 in comparison with the case of Example 1.
Table 3 shows the results.

The experiment was performed in exactly the same manner as in Example 11 except that 5.7 parts by weight of D-3 was used instead of the blowing agent D-2 in comparison with the case of Example 11.
Table 3 shows the results.

[Comparative Example 1]
Compared with Example 11, 54.7 parts by weight of polyol compound A-1 was used, catalysts B-1 and B-2 were not used, and 45.3 parts by weight of polyisocyanate compound E was used. The experiment was performed in exactly the same manner as in Example 11 except that it was used.
Table 3 shows the results.

[Comparative Example 2]
Compared with Example 11, 3.0 parts by weight of the flame retardant F-1 was used, 2.3 parts by weight of F-2 was used, and 3.0 parts by weight of the flame retardant auxiliary G-4 was used. An experiment was performed in exactly the same manner as in Example 11 except for the above.
Table 3 shows the results.

[Comparative Example 3]
Compared with Comparative Example 2, except that 6.0 parts by weight of the flame retardant F-1 was used, 7.0 parts by weight of F-2 was used, and the flame retardant auxiliary G-4 was not used. Was conducted in the same manner as in Comparative Example 2.
Table 3 shows the results.

[Comparative Example 4]
Comparative Example 3 was different from Comparative Example 3 except that 25.3 parts by weight of A-2 and 74.7 parts by weight of polyisocyanate compound E were used instead of polyol compound A-1. The experiment was performed in exactly the same way as in the case of.
Table 3 shows the results.

  The fire-resistant heat-insulating layer obtained by the flame-retardant heat-insulating material composition used in the present invention is very hard to ignite and can exhibit excellent fire resistance.

  The rigid polyurethane spray foam obtained from the flame-retardant heat-insulating composition for use in the spray according to the present invention has excellent heat insulating properties and fire resistance. Therefore, the present invention is applicable to applications such as structural materials requiring heat insulating properties and fire resistance. The flame-retardant heat insulating material composition for use in the spray according to the present invention can be widely applied.

1, 2 container 3 opening and closing valve 10 pipe 20 reaction vessel 21 stirring blade 22 pipe 23 spray nozzle 30 air compressor 40 concrete base material 41 hard polyurethane spray foam 42, 43 cut 44 rectangular parallelepiped part 50 adherend 51 rod 52 handle 60 anchor Pull-out tester 100,110 Spray device

Claims (7)

Having at least a polyol liquid (X) containing a polyol compound, a flame retardant, a flame retardant auxiliary, a foam stabilizer, a foaming agent and a trimerization catalyst, and an isocyanate liquid (Y) containing a polyisocyanate compound;
The trimerization catalyst is a catalyst for a trimerization reaction of an isocyanate group of a polyisocyanate compound contained in the isocyanate liquid (Y),
The flame retardant contains at least red phosphorus and a phosphate,
The flame retardant aid comprises at least one selected from the group consisting of phosphate-containing flame retardants, bromine-containing flame retardants, metal hydroxides and needle fillers,
With respect to the polyol compound and the polyisocyanate compound and the urethane resin 100 parts by weight consisting of the flame retardant, and wherein the area by der of 5.5 to 80 parts by weight, the flame for use in spray Combustion insulation composition.   At least one selected from the group consisting of a phosphate-containing flame retardant, a bromine-containing flame retardant, a metal hydroxide, and an acicular filler contained in the flame-retardant auxiliary, each based on 100 parts by weight of the urethane resin, The flame retardant insulation composition for use in a spray according to claim 1, wherein the composition ranges from 3.0 to 90 parts by weight.   The flame-retardant heat insulating material composition for use in a spray according to claim 1 or 2, wherein the trimerization catalyst is in a range of 0.01 to 10 parts by weight based on 100 parts by weight of the urethane resin. A method for using a flame-retardant heat insulating material composition for use in a spray according to any one of claims 1 to 3,
Spraying the polyol liquid (X) and the isocyanate liquid (Y) after mixing (1);
Or
Mixing the polyol liquid (X) and the isocyanate liquid (Y) after spraying (2);
The use of the flame-retardant insulation composition for use in spraying, comprising:   The method for using a flame-retardant heat-insulating composition for use in a spray according to claim 4, comprising spraying a flame-retardant heat-insulating composition for use in the spray on a structural material.   The method of using a flame retardant insulation composition for use in a spray according to claim 5, comprising curing the flame retardant insulation composition for use in the spray on the structural material.   A rigid polyurethane spray foam obtained by curing the flame-retardant heat-insulating composition for use in the spray according to the method for using the flame-retardant heat-insulating composition according to any one of claims 4 to 6.

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