JP5671591B2 - Fireproof urethane resin composition - Google Patents

Description

  The present invention relates to a fire resistant urethane resin composition.

Rigid polyurethane foam is used for applications such as heat insulating materials and lightweight structural materials. Such a rigid polyurethane foam can be obtained by mixing a polyol composition containing a polyol compound and a foaming agent and a polyisocyanate compound, and foaming and curing.
While this rigid polyurethane foam is lightweight and easy to use, there is a problem that it is easy to burn.
As one of technologies for making the rigid polyurethane foam difficult to burn, it is known to use a catalyst that promotes the formation of isocyanurate bonds when the polyol composition and the polyisocyanate compound are reacted (patent) References 1, 2).
By using a catalyst that promotes the formation of isocyanurate bonds, the formation of a heat-stable isocyanurate ring is promoted inside the rigid polyurethane foam, and the flame retardancy of the rigid polyurethane foam can be enhanced. .

Usually, water, pentane or the like is used as a foaming agent used in the production of the rigid polyurethane foam, but when water is used as a foaming agent used in the production of the rigid polyurethane foam, It is known that the ratio of urea bonds increases and the ratio of isocyanurate bonds decreases (Patent Documents 3 and 4).
When the proportion of isocyanurate bonds in the rigid polyurethane foam skeleton decreases, the nonflammability evaluation of the rigid polyurethane foam decreases.
Further, when a flammable substance such as pentane is used, the flammable substance is easily left in the hard polyurethane skeleton, and the nonflammability evaluation of the hard polyurethane foam may be further reduced.
As a result, there has been a problem that it is not easy to obtain a rigid polyurethane foam that can pass the nonflammability standard by the corn calorimeter test.

JP 2004-050495 A JP 2002-338651 A JP 2008-088355 A JP 2008-088356 A

  An object of the present invention is to provide a fire resistant urethane resin composition having excellent fire resistance.

  As a result of intensive studies by the present inventors to solve the above-mentioned problems, a fire-resistant urethane resin composition containing a catalyst and an additive, wherein the catalyst performs a trimerization reaction of an isocyanate group contained in the urethane resin. At least three selected from the group consisting of red phosphorus, phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant and antimony-containing flame retardant. It has been found that a fire-resistant urethane resin composition containing is suitable for the purpose of the present invention, and the present invention has been completed.

That is, the present invention
[1] A fire-resistant urethane resin composition containing a catalyst and an additive,
The catalyst includes a trimerization catalyst that promotes a trimerization reaction of an isocyanate group contained in the urethane resin,
The additive is
(A) Red phosphorus, phosphate-containing flame retardant and bromine-containing flame retardant
(B) Phosphoric acid ester, red phosphorus and bromine-containing flame retardant
(C) Phosphate ester, red phosphorus and phosphate-containing flame retardant
(E) Phosphate ester, boron-containing flame retardant and red phosphorus
(G) Phosphate ester, red phosphorus, phosphate-containing flame retardant and bromine-containing flame retardant
(H) Phosphate ester, boron-containing flame retardant, red phosphorus, phosphate-containing flame retardant, bromine-containing flame retardant and antimony-containing flame retardant
Or
(I) Boron-containing flame retardant, red phosphorus, phosphate-containing flame retardant, bromine-containing flame retardant and antimony-containing flame retardant
Consisting of any one of
The trimerization catalyst is in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the urethane resin,
The additive is in the range of 0.3 to 180 parts by weight with respect to 100 parts by weight of the urethane resin,
For 100 parts by weight of the urethane resin,
The red phosphorus is in the range of 3.2 to 20 parts by weight ;
The phosphate ester is in the range of 3.7 to 17.5 parts by weight ,
The phosphate-containing flame retardant ranges from 1.6 parts by weight to 10 parts by weight ,
The bromine-containing flame retardant ranges from 1.6 parts by weight to 10 parts by weight ,
The boron-containing flame retardant is 6.3 parts by weight ,
The antimony-containing flame retardant is 3.0 parts by weight ;
The polyol contained in the urethane resin is at least one selected from the group consisting of polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols and polyether polyols. And
The polyol contained in the urethane resin consists of an oxygen atom, a hydrogen atom and a carbon atom,
The boron-containing flame retardant is at least one selected from the group consisting of boron oxide, boric acid and boric acid metal salts, and provides a fire-resistant urethane resin composition.

One of the present invention is
[ 2 ] The refractory urethane resin composition according to [1] above, wherein the phosphate-containing flame retardant comprises at least one selected from the group consisting of monophosphate, pyrophosphate, and polyphosphate. It is to provide.

One of the present invention is
[ 3 ] The fire-resistant urethane resin composition according to the above [1] or [2] , wherein the phosphate ester is at least one of a monophosphate ester and a condensed phosphate ester.

One of the present invention is
[ 4 ] The fire-resistant urethane resin composition according to any one of [1] to [ 3 ], wherein the bromine-containing flame retardant contains a brominated aromatic ring-containing aromatic compound.

One of the present invention is
[ 5 ] The refractory urethane according to any one of [1] to [ 4 ], wherein the antimony-containing flame retardant is at least one selected from the group consisting of antimony oxide, antimonate, and pyroantimonate. A resin composition is provided.

One of the present invention is
[ 6 ] The fire-resistant urethane resin composition according to any one of [1] to [ 5 ], wherein the urethane resin includes an isocyanate compound and a polyol compound.

One of the present invention is
[ 7 ] The refractory urethane resin composition according to any one of [1] to [ 6 ], wherein the refractory urethane resin composition includes at least one selected from the group consisting of a foam stabilizer and a foaming agent. Is to provide.

One of the present invention is
[8] The above [1] to [1] , wherein the additive comprises any one of the following (a ), (b), (c), (e), (g), (h) or (i) : 7] is provided. The fire-resistant urethane resin composition according to any one of 7) is provided.
(A) Red phosphorus, phosphate-containing flame retardant and bromine-containing flame retardant (b) Phosphate ester, red phosphorus and bromine-containing flame retardant (c) Phosphate ester, red phosphorus and phosphate-containing flame retardant
(E) Phosphate ester, boron-containing flame retardant and red phosphorus
(G) Phosphate ester, red phosphorus, phosphate-containing flame retardant and bromine-containing flame retardant (h) Phosphate ester, boron-containing flame retardant, red phosphorus, phosphate-containing flame retardant, bromine-containing flame retardant and antimony-containing Flame Retardant (i) Boron-containing flame retardant, red phosphorus, phosphate-containing flame retardant, bromine-containing flame retardant and antimony-containing flame retardant

Further, one of the present invention is a fire-resistant urethane resin composition containing an [ 9 ] additive, wherein the additive contains red phosphorus as an essential component, and in addition to red phosphorus, phosphate esters and phosphates are difficult to contain. Including at least three selected from the group consisting of a flame retardant, a bromine-containing flame retardant, a boron-containing flame retardant and an antimony-containing flame retardant,
The additive is in the range of 0.3 to 180 parts by weight with respect to 100 parts by weight of the urethane resin,
A sample for testing a cone calorimeter having a specific gravity of 0.02 to 0.20 in a range of 0.02 to 0.20 obtained by molding the refractory urethane resin composition is compliant with the ISO-5660 test method. And Q ₁ (MJ / m ² ) as the total calorific value by the corn calorimeter test when heated at a radiant heat intensity of 50 kW / m ^{2 for} 20 minutes,
A corn calorimeter test sample having a length of 10 cm, a width of 10 cm and a thickness of 5 cm obtained by molding the urethane resin not containing the additive is radiant heat intensity 50 kW / m ² in accordance with the test method of ISO-5660. When the total calorific value by the corn calorimeter test when heated at 20 minutes is Q ₀ (MJ / m ² ),
The percentage X represented by (Q ₁ / Q ₀ ) × 100 is in the range of 5 to 65%, and the fire resistant urethane resin composition according to any one of the above [1] to [ 8 ] It provides things.

The present invention also provides
[ 10 ] A molded article obtained by molding the fire-resistant urethane resin composition according to any one of [1] to [ 9 ].

  Since the fire-resistant urethane resin composition according to the present invention provides a molded article having a small specific gravity, it is excellent in handleability. In addition, the molded product obtained from the fire-resistant urethane resin composition according to the present invention has a small calorific value when combusted, and the residue after combustion maintains a certain shape, so that it can exhibit excellent fire resistance. it can.

The fireproof urethane resin composition according to the present invention will be described.
First, the urethane resin used for the fireproof urethane resin composition will be described.
As said urethane resin, what contains the polyisocyanate compound as a main ingredient, the polyol compound as a hardening | curing agent, etc. are mentioned, for example.
Examples of the polyisocyanate compound that is the main component of the urethane resin include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.

Examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and the like.
Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.
The said polyisocyanate compound can use 1 type, or 2 or more types.
The main component of the urethane resin is preferably polymethylene polyphenyl polyisocyanate for reasons such as ease of use and availability.

  Examples of the polyol compound that is a curing agent for the urethane resin include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, polyether polyols, and the like. It is done.

Examples of the polylactone-based polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.
The polycarbonate polyol is obtained by, for example, a dealcoholization reaction of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, or nonanediol with diethylene carbonate, dipropylene carbonate, or the like. Polyol etc.

Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolak, 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-based polyol include a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, and a polymer obtained by ring-opening polymerization of a lactone such as ε-caprolactone and α-methyl-ε-caprolactone. Examples thereof include condensates, and condensates of hydroxycarboxylic acids with the above polyhydric alcohols.

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

As the polymer polyol, for example, the aromatic polyols, alicyclic polyols, aliphatic polyols, to polyester polyols, styrene, methyl acrylate, ethylenically unsaturated compound is graft polymerized polymers such as methacrylate, Examples thereof include polybutadiene polyols, modified polyols of polyhydric alcohols, and hydrogenated products thereof.

Examples of the modified polyol of the polyhydric alcohol include those modified by reacting a 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., tetra- to octavalent alcohols such as sucrose, glucose, mannose, fructose, methyl glucoside and derivatives thereof,
Phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F 1 , 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, anthrol, 1,4,5,8- Phenol polybutadiene polyols such as tetrahydroxyanthracene and 1-hydroxypyrene,
Castor oil-based polyol,
Examples include (co) polymers of hydroxyalkyl (meth) acrylates and polyfunctional (eg, 2 to 100 functional group) 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 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-propyloxide, 1,2 -Butylene oxide, 1, 4- butylene oxide, etc. are mentioned.
Among these, PO, EO, and 1,2-butylene oxide are preferable from the viewpoint of properties and reactivity, 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.

Examples of the polyether polyol include ring-opening polymerization of at least one alkylene oxide such as ethylene oxide, propylene oxide, and tetrahydrofuran in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogens. The polymer obtained by making it contain is mentioned.
Examples of the low molecular weight active hydrogen compound having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol,
Glycerin, triol such as trimethylol propane.

The polyol used in the present invention is preferably a polyester-based polyol or a polyether-based polyol because the effect of reducing the total calorific value upon combustion is great.
Among them, it is more preferable to use a polyester-based polyol having a molecular weight of 300 to 500.

The ratio of the active hydrogen group (OH) in the polyol compound and the active isocyanate group (NCO) in the polyisocyanate compound (NCO / OH) is determined by combining the polyisocyanate compound as the main component of the urethane resin and the polyol compound as the curing agent. The equivalent ratio is preferably in the range of 0.7 to 10, more preferably in the range of 1.5 to 7.0, still more preferably in the range of 2.0 to 6.0. Most preferably, it is in the range of 5 to 5.0.
If the equivalent ratio is 0.7 or more, the viscosity of the urethane resin can be prevented from becoming too high, and if it is 10 or less, good adhesive strength can be maintained.

Next, the trimerization catalyst used in the present invention will be described.
The fire-resistant urethane resin composition according to the present invention includes a trimerization catalyst that promotes a trimerization reaction of isocyanate groups contained in the urethane resin.
By using this trimerization catalyst, the isocyanate group contained in the polyisocyanate compound, which is the main component of the polyurethane resin used in the present invention, is allowed to react and trimerize to promote the formation of an isocyanurate ring.

  In order to promote the formation of the isocyanurate ring, for example, as a trimerization catalyst, tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) ) Aromatic compounds such as hexahydro-S-triazine, alkali metal salts of carboxylic acids such as potassium acetate and potassium 2-ethylhexanoate, quaternary ammonium salts of carboxylic acids and the like may be used.

The addition amount of the trimerization catalyst used in the fire-resistant urethane resin composition according to the present invention is not particularly limited, but is preferably in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. , More preferably in the range of 0.01 parts by weight to 8 parts, still more preferably in the range of 0.01 parts by weight to 6 parts, and in the range of 0.7 parts to 1.5 parts. Most preferred.
When the amount is 0.01 parts 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.

  Examples of the catalyst used in the present invention include triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N '-Trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl, N'-dimethylaminoethylpiperazine, imidazole compound in which secondary amine functional group in imidazole ring is substituted with cyanoethyl group, etc. And amino-based catalysts.

Although there is no limitation in particular in the addition amount of the catalyst used for the fireproof urethane resin composition which concerns on this invention, It is preferable that it is the range of 0.01 weight part-10 weight part with respect to 100 weight part of urethane resins, More preferably, it is in the range of 0.01 to 8 parts by weight, still more preferably in the range of 0.01 to 6 parts by weight, and in the range of 0.05 to 0.15 parts by weight. Most preferably it is.
When the amount is 0.01 parts by weight or more, the problem that the formation of urethane bonds is inhibited does not occur. When the amount is 10 parts by weight or less, the problem that the trimerization is inhibited can be reduced.

Moreover, in order to accelerate | stimulate foaming of the urethane resin contained in the fire resistant urethane resin composition which concerns on this invention, a foaming agent can be added with respect to the fire resistant urethane resin composition which concerns on this invention.
Examples of the foaming agent include water,
Low boiling point hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane,
Chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride,
Fluorine compounds such as trichloromonofluoromethane and trichlorotrifluoroethane,
Hydrofluorocarbons such as CHF ₃ , CH ₂ F ₂ and CH ₃ F;
Dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)), HFC-245fa (1,1 , 1,3,3-pentafluoropropane), hydrochlorofluorocarbon compounds such as HFC-365mfa (1,1,1,3,3-pentafluorobutane),
Examples include organic physical foaming agents such as ether compounds such as diisopropyl ether or mixtures of these compounds, and 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, or water, and more preferably hydrofluorocarbon and water are used in combination.

The amount of water used as the foaming agent in the fire-resistant urethane resin composition according to the present invention is not particularly limited, but is in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. It is preferably 0.1 to 18 parts by weight, more preferably 0.1 to 15 parts by weight, and 0.5 to 0.7 parts by weight. Most preferred is the range of parts.
When the water range is 0.1 parts by weight or more, foaming is promoted, and the density of the obtained molded body can be reduced. When the water content is 20 parts by weight or less, the foam does not break and foams. It is possible to prevent the body from being formed.

The addition amount of the foaming agent excluding water used in the fireproof urethane resin composition according to the present invention is not particularly limited, but is in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the urethane resin. Preferably, it is in the range of 0.1 to 40 parts by weight, more preferably in the range of 0.1 to 20 parts by weight, and 3.0 to 7.0 parts by weight. Most preferred is the range of parts.
Foaming is promoted when the amount of foaming accelerator other than water used is 0.1 parts by weight or more, and the density of the resulting molded product can be reduced. When the amount is 50 parts by weight or less, the urethane foam is broken. It is possible to prevent the foam from being formed without forming a foam.

A foam stabilizer can also be used in the fireproof urethane resin composition according to the present invention.
Examples of the foam stabilizer include surfactants such as polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ether, silicone foam stabilizers such as organopolysiloxane, and the like.
The amount of the foam stabilizer used for the urethane resin cured by the chemical reaction is appropriately set according to the urethane resin cured by the chemical reaction to be used. For example, for example, 100 parts by weight of the urethane resin On the other hand, a range of 0.01 to 5 parts by weight is preferable.

  The catalyst, the foaming agent, and the foam stabilizer may be used alone or in combination of two or more.

Next, the additive used for this invention is demonstrated.
The fireproof urethane resin composition according to the present invention includes an additive.
The additive includes at least three selected from the group consisting of red phosphorus, phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant and antimony-containing flame retardant.

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

Moreover, the addition amount of red phosphorus used for the fireproof urethane resin composition according to the present invention is in the range of 3.2 to 20 parts by weight with respect to 100 parts by weight of the urethane resin.
When the range of the red phosphorus is 0.1 parts by weight or more, the self-extinguishing property of the fire-resistant urethane resin composition according to the present invention is maintained, and when it is 60 parts by weight or less, the fire-resistant urethane according to the present invention. Foaming of the resin composition is not inhibited.

  Further, the phosphate ester used in the present invention is not particularly limited, but it is preferable to use a monophosphate ester, a condensed phosphate ester, or the like.

  The monophosphate ester is not particularly limited, and examples thereof include 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, 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, diphenyl methanephosphonate, phenylphosphonic acid Examples include diethyl, resilsinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, tris (β-chloropropyl) phosphate, and the like.

The condensed phosphate ester is not particularly limited, and examples thereof include 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 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 (manufactured by ADEKA, trade name ADK STAB PFR), bisphenol A polycresyl phosphate (trade names FP-600, FP-700), and the like.

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

  The said phosphate ester can use 1 type, or 2 or more types.

Moreover, the addition amount of the phosphate ester used for this invention is the range of 3.7 weight part-17.5 weight part with respect to 100 weight part of said urethane resins.
When the range of the phosphoric acid ester is 0.1 parts by weight or more, the compact made of the fire-resistant urethane resin composition according to the present invention can be prevented from cracking the dense residue formed by the heat of fire, and 60% by weight. In the case of less than the part, foaming of the refractory urethane resin composition according to the present invention is not inhibited.

The phosphate-containing flame retardant used in the present invention contains phosphoric acid.
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, pyrophosphoric acid, and polyphosphoric acid.

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

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

Although not particularly limited as the monophosphate, for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen 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, magnesium hypophosphite,
Calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite,
Zinc salts such as zinc phosphate, zinc phosphite, zinc hypophosphite,
Examples thereof include aluminum salts such as primary aluminum phosphate, secondary aluminum phosphate, tertiary aluminum phosphate, aluminum phosphite, and aluminum hypophosphite.

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

  Among these, in order to improve the self-extinguishing properties of the phosphate-containing flame retardant, it is preferable to use ammonium dihydrogen phosphate, diammonium hydrogen phosphate, primary aluminum phosphate, and ammonium dihydrogen phosphate. More preferably it is used.

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

The addition amount of the phosphate-containing flame retardant used in the present invention is in the range of 1.6 parts by weight to 10 parts by weight with respect to 100 parts by weight of the urethane resin.
When the range of the phosphate-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the fire-resistant urethane resin composition according to the present invention is maintained, and when it is 60 parts by weight or less, the present invention is applied. Foaming of such a refractory urethane resin composition is not inhibited.

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 brominated aromatic ring-containing aromatic compounds.
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.

The amount of bromine-containing flame retardant used in the present invention is in the range of 1.6 to 10 parts by weight .
When the range of the bromine-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the fire-resistant urethane resin composition according to the present invention is maintained, and when it is 60 parts by weight or less, the fire resistance according to the present invention is maintained. Foaming of the conductive urethane resin composition 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 the boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.
Examples of the borate include alkali metals, alkaline earth metals, elements of Group 4, Group 12, and Group 13 of the periodic table, and ammonium borate.
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, zinc borate, aluminum borate, and ammonium borate.

  The boron-containing flame retardant used in the present invention is preferably a borate, and more preferably zinc borate.

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

The addition amount of the boron-containing flame retardant used in the present invention is 6.3 parts by weight with respect to 100 parts by weight of the urethane resin.
When the range of the boron-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the refractory urethane resin composition according to the present invention is maintained, and when it is 60 parts by weight or less, the fire resistance according to the present invention is maintained. Foaming of the conductive urethane resin composition is not inhibited.

Examples of the antimony-containing flame retardant used in the present invention include antimony oxide, antimonate, pyroantimonate and the like.
Examples of the antimony oxide include antimony trioxide and antimony pentoxide.
Examples of the antimonate include sodium antimonate and potassium antimonate.
Examples of the pyroantimonate include sodium pyroantimonate and potassium pyroantimonate.

  The antimony-containing flame retardant used in the present invention is preferably antimony oxide.

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

The addition amount of the antimony-containing flame retardant used in the present invention is 3.0 parts by weight with respect to 100 parts by weight of the urethane resin.
When the range of the antimony-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the fire-resistant urethane resin composition according to the present invention is maintained, and when it is 60 parts by weight or less, the fire resistance according to the present invention is maintained. Foaming of the conductive urethane resin composition is not inhibited.

Moreover, the fireproof urethane resin composition which concerns on this invention can use an inorganic filler together.
The inorganic filler is not particularly limited. For example, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, Aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium silicate and other potassium salts, talc, clay, mica, Montmorillonite, bentonite, activated clay, ceviolite, imogolite, sericite, glass fiber, glass beads, silica-based balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder Various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, inorganic phosphorus compound, silica alumina Examples thereof include fibers, alumina fibers, silica fibers, and zirconia fibers.

  The said inorganic filler can use 1 type, or 2 or more types.

  Furthermore, the fire-resistant urethane resin composition according to the present invention is an antioxidant, phenolic, amine-based, sulfur-based antioxidant, heat stabilizer, and metal damage prevention, as long as the object of the present invention is not impaired. Additives such as agents, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, tackifying resins, and tackifiers such as polybutene and petroleum resins.

The additive used in the present invention contains at least three selected from the group consisting of red phosphorus, phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant and antimony-containing flame retardant.
The additive contains at least two selected from the group consisting of phosphate, a phosphate-containing flame retardant, a bromine-containing flame retardant, a boron-containing flame retardant, and an antimony-containing flame retardant in addition to red phosphorus, using red phosphorus as an essential component. It is more preferable that one be included.

Examples of preferable combinations of additives used in the present invention include any of the following (a) to (i).
(A) Red phosphorus, phosphate-containing flame retardant and bromine-containing flame retardant (b) Phosphate ester, red phosphorus and bromine-containing flame retardant (c) Phosphate ester, red phosphorus and phosphate-containing flame retardant (d) Phosphate ester, phosphate-containing flame retardant and bromine-containing flame retardant (e) Phosphate ester, boron-containing flame retardant and red phosphorus (f) phosphate ester, boron-containing flame retardant and phosphate-containing flame retardant (g) Phosphate ester, red phosphorus, phosphate containing flame retardant and bromine containing flame retardant (h) Phosphate ester, boron containing flame retardant, red phosphorus, phosphate containing flame retardant, bromine containing flame retardant and antimony containing flame retardant ( i) Boron-containing flame retardant, red phosphorus, phosphate-containing flame retardant, bromine-containing flame retardant and antimony-containing flame retardant Among them, the additive used in the present invention may contain the component (a) as a constituent element. preferable.

Moreover, the addition amount of the additive used for this invention is the range of 0.3 weight part-180 weight part with respect to 100 weight part of urethane resin, and the range of the total amount of additives other than urethane resin. This range is preferably in the range of 0.3 to 80 parts by weight, more preferably in the range of 0.3 to 50 parts by weight, and in the range of 0.3 to 40 parts by weight. More preferably.
When the range of the additive is 0.3 parts by weight or more, the compact made of the fire-resistant urethane resin composition according to the present invention can prevent the dense residue formed by the heat of fire from cracking, and 180 parts by weight. In the following cases, foaming of the refractory urethane resin composition according to the present invention is not inhibited.

Since the refractory urethane resin composition according to the present invention reacts and cures, its viscosity changes with time.
Therefore, before using the fire resistant urethane resin composition according to the present invention, the fire resistant urethane resin composition is divided into two or more to prevent the fire resistant urethane resin composition from reacting and curing. deep. And when using the fire-resistant urethane resin composition according to the present invention, the fire-resistant urethane resin composition according to the present invention is integrated by combining the fire-resistant urethane resin composition divided into two or more. Is obtained.
When dividing the refractory urethane resin composition into two or more, each component of the refractory urethane resin composition divided into two or more does not start to cure, and each of the refractory urethane resin compositions is divided into two or more. What is necessary is just to divide each component so that hardening reaction may start after mixing a component.

Next, the manufacturing method of the said fireproof urethane resin composition is demonstrated.
The method for producing the fire resistant urethane resin composition is not particularly limited. For example, a method in which the components of the fire resistant urethane resin composition are mixed, and the fire resistant urethane resin composition is suspended in an organic solvent to form a paint. In the case where a component that is solid at 25 ° C. is contained in the reaction curable resin component contained in the refractory urethane resin composition, a method such as preparing a slurry by dispersing in a solvent, The refractory urethane resin composition can be obtained by a method such as melting the refractory urethane resin composition under heating.

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 refractory urethane resin composition excluding the catalyst and the catalyst may be kneaded in the same manner immediately before injection.

  By the method described above, the fire-resistant urethane resin composition according to the present invention can be obtained.

Next, a method for curing the fireproof urethane resin composition according to the present invention will be described.
When the respective components of the refractory urethane resin composition are mixed, the reaction starts, the viscosity increases with the passage of time, and the fluidity is lost.
For example, the molded article made of the fire-resistant urethane resin composition can be obtained by injecting the fire-resistant urethane resin composition into a container such as a mold or a frame material and curing it.
When obtaining a molded body made of the fire-resistant urethane resin composition, heat can be applied or pressure can be applied.
Although there is no limitation in particular in the specific gravity of the molded object which consists of the said fireproof urethane resin composition, it is preferable that it is the range of 0.02-0.2, and it is more preferable that it is the range of 0.03-0.15. , 0.03 to 0.1 is more preferable, and 0.04 to 0.08 is most preferable.
Such a compact is easy to handle because of its low specific gravity.

Next, the fire resistance test implemented about the molded object which consists of the said urethane resin composition is demonstrated.
A molded body made of the urethane resin composition is cut into a length of 10 cm, a width of 10 cm and a thickness of 5 cm to prepare a sample for a corn calorimeter test.
Using the corn calorimeter test sample, the total calorific value of the corn calorimeter test when heated at a radiant heat intensity of 50 kW / m ^{2 for} 20 minutes can be measured according to the test method of ISO-5600. it can.

Let Q ₁ (MJ / m ² ) be the total calorific value obtained by a cone calorimeter test using a molded body made of the fire-resistant urethane resin composition.
A cone calorimeter test is performed on a molded body obtained from a composition obtained by removing the additive from the fire-resistant urethane resin composition by the same procedure. The total calorific value obtained by this corn calorimeter test is defined as Q ₀ (MJ / m ² ).

In the case of the refractory urethane resin composition according to the present invention, it is preferable that the percentage X value obtained by the following formula (1) from the total calorific value is in the range of 5 to 65%. This range is more preferably 5 to 55%.
(Q ₁ / Q ₀ ) × 100 = X (1)
The fire resistant urethane resin composition satisfying the above formula (1) is easy to handle and has excellent fire resistance.

  Hereinafter, the present invention will be described in detail by way of examples. In addition, this invention is not limited at all by the following examples.

  According to the formulation shown in Table 1, the fire-resistant urethane resin composition according to Example 1 was prepared by being divided into three components (A) to (C). The details of each component shown in Table 1 are as follows.

(A) component: polyol compound (a) polyol compound A-1: polyol 1
p-phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RFK-505, hydroxyl value = 250 mgKOH / g)
A-2: Polyol 2
o-Phthalic acid-based polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RDK-142, hydroxyl value: 400 mgKOH / g)
A-3: Polyol 3
o-Phthalic acid-based polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RDK-121, hydroxyl value: 260 mgKOH / g)
A-4: Polyol 4
p-phthalic acid-based polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RLK-062, hydroxyl value: 250 mgKOH / g)
A-5: Polyol 5
p-phthalic acid-based polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RLK-035, hydroxyl value: 150 mgKOH / g)
A-6: Polyol 6
Polyether polyol (Mitsui Chemicals, product name: Actol T-400, hydroxyl value: 399 mgKOH / g)
A-7: Polyol 7
Polyether polyol (Mitsui Chemicals, product name: Actol T-700, hydroxyl value: 250 mgKOH / g)
(B) Catalyst B-1: Potassium 2-ethylhexanoate (Tokyo Chemical Industry Co., Ltd., product code: P0048)
B-2: Trimerization catalyst (product name: TOYOCAT-TR20, manufactured by Tosoh Corporation)
B-3: Pentamethyldiethylenetriamine (manufactured by Tosoh Corporation, product name: TOYOCAT-DT)
(C) Foaming agent, foam stabilizer water HFC-365mfa (1,1,1,3,3-pentafluorobutane, manufactured by Central Glass Co., Ltd.)
HFC-245fa (1,1,1,3,3-pentafluoropropane, manufactured by Nippon Solvay)
Mixing ratio HFC-365fa: HFC-245fa = 7: 3 (hereinafter referred to as “HFC”)
Polyalkylene glycol-based foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193)

Component (B): Isocyanate (hereinafter referred to as “polyisocyanate”)
MDI (manufactured by Nippon Urethane Industry Co., Ltd., product name: Millionate MR-200) Viscosity: 167 mPa · s

(C) Component: Additive C-1: Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP, hereinafter referred to as “TMCPP”)
C-2: Zinc borate (product name: Firebrake ZB, manufactured by Hayakawa Shoji Co., Ltd.)
C-3: Red phosphorus (manufactured by Rin Chemical Industry Co., Ltd., product name: Nova Excel 140)
C-4: Ammonium dihydrogen phosphate (manufactured by Taihei Chemical Industrial Co., Ltd.)
C-5: Diammonium hydrogen phosphate (manufactured by Taihei Chemical Industry Co., Ltd.)
C-6: primary aluminum phosphate (manufactured by Taihei Chemical Industrial Co., Ltd.)
C-7: Hexabromobenzene (manac product, product name: HBB-B, hereinafter referred to as “HBB”)
C-8: Ethylene-bis (tetrabromophthalimide) (manufactured by Albemarle, product name: SAYTEXBT-93, hereinafter referred to as “EBTBPI”)
C-9: Ethylene bis (pentabromophenyl) (manufactured by Albemarle, product name: SAYTEX 8010, hereinafter referred to as “EBPBP”)
C-10: Antimony trioxide (Nippon Seiko Co., Ltd., product name: Patox C)

Next, according to the composition shown in Table 1 below, the components (A) and (C) are weighed in a 1000 ml polypropylene beaker, and a three-one motor (manufactured by HEIDON, product name: BLW1200) is used at 25 ° C. and 400 rpm. Stir for minutes.
A foam stabilizer and a foaming agent were added to the components (A) and (C) after stirring, and the mixture was stirred for about 10 seconds at 25 ° C. and 1200 rpm using a three-one motor to prepare a foam.
The obtained fire-resistant urethane resin composition lost fluidity over time, and a cured product of the fire-resistant urethane resin composition was obtained. The cured product was evaluated according to the following criteria, and the results are shown in Table 1.

[Measurement of calorific value]
A sample for corn calorimeter test was cut out from the cured product so as to be 10 cm × 10 cm × 5 cm, and the maximum heat generation rate and total heat generation when heated for 20 minutes at a radiant heat intensity of 50 kW / m ² in accordance with ISO-5660 Was measured.
This measurement method is a test method stipulated as corresponding to the standard according to the corn calorimeter method at the Building Comprehensive Testing Laboratory, which is a public institution stipulated in Article 108-2 of the Building Standards Act Enforcement Ordinance. It conforms to the test method of ISO-5660.

Compared to the case of Example 1, the amount of TMCPP used was reduced from 7.0 parts by weight to 3.7 parts by weight, and the amount of red phosphorus used was reduced from 6.0 parts by weight to 3.2 parts by weight. Except that the amount of ammonium dihydrogen phosphate used was reduced from 3.0 parts by weight to 1.6 parts by weight, and the amount of HBB used was reduced from 3.0 parts by weight to 1.6 parts by weight. The experiment was performed in exactly the same manner as in Example 1.
The results are shown in Table 1.

Compared to the case of Example 1, the amount of TMCPP used was increased from 7.0 parts by weight to 14.7 parts by weight, and the amount of red phosphorus used was increased from 6.0 parts by weight to 12.6 parts by weight. Except that the amount of ammonium dihydrogen phosphate used was increased from 3.0 parts by weight to 6.3 parts by weight, and the amount of HBB used was increased from 3.0 parts by weight to 6.3 parts by weight. The experiment was performed in exactly the same manner as in Example 1.
The results are shown in Table 1.

Compared to the case of Example 1, the amount of TMCPP used was increased from 7.0 parts by weight to 8.8 parts by weight, and the amount of red phosphorus used was increased from 6.0 parts by weight to 7.5 parts by weight. The experiment was carried out in exactly the same manner as in Example 1 except that the amount of ammonium dihydrogen phosphate used was increased from 3.0 parts by weight to 3.8 parts by weight and that HBB was not used. It was.
The results are shown in Table 1.

Compared to the case of Example 1, the amount of TMCPP used was reduced from 7.0 parts by weight to 4.4 parts by weight, and the amount of red phosphorus used was reduced from 6.0 parts by weight to 3.8 parts by weight. The experiment was carried out in the same manner as in Example 1 except that the amount of ammonium dihydrogen phosphate used was reduced from 3.0 parts by weight to 1.9 parts by weight and that HBB was not used. It was.
The results are shown in Table 1.

Compared to the case of Example 1, the amount of TMCPP used was increased from 7.0 parts by weight to 17.5 parts by weight, and the amount of red phosphorus used was increased from 6.0 parts by weight to 15.0 parts by weight. The experiment was carried out in exactly the same manner as in Example 1, except that the amount of ammonium dihydrogen phosphate used was increased from 3.0 parts by weight to 7.5 parts by weight and that HBB was not used. It was.
The results are shown in Table 1.

Compared to the case of Example 1, the amount of TMCPP used was increased from 7.0 parts by weight to 8.8 parts by weight, and the amount of red phosphorus used was increased from 6.0 parts by weight to 7.5 parts by weight. The same experiment as in Example 1 was conducted except that ammonium dihydrogen phosphate was not used and the amount of HBB was increased from 3.0 parts by weight to 3.8 parts by weight. It was.
The results are shown in Table 1.

Compared to the case of Example 1, the amount of TMCPP used was reduced from 7.0 parts by weight to 4.4 parts by weight, and the amount of red phosphorus used was reduced from 6.0 parts by weight to 3.8 parts by weight. The same experiment as in Example 1 was conducted except that ammonium dihydrogen phosphate was not used and the amount of HBB used was reduced from 3.0 parts by weight to 1.9 parts by weight. It was.
The results are shown in Table 1.

Compared to the case of Example 1, the amount of TMCPP used was increased from 7.0 parts by weight to 17.5 parts by weight, and the amount of red phosphorus used was increased from 6.0 parts by weight to 15.0 parts by weight. The same experiment as in Example 1 was conducted except that ammonium dihydrogen phosphate was not used and the amount of HBB was increased from 3.0 parts by weight to 7.5 parts by weight. It was.
The results are shown in Table 1.

Compared to the case of Example 1, TMCPP was not used, the amount of red phosphorus used was increased from 6.0 parts by weight to 10.0 parts by weight, and the amount of ammonium dihydrogen phosphate used was 3 The experiment was performed in exactly the same manner as in Example 1 except that the amount was increased from 0.0 parts by weight to 5.0 parts by weight and the amount of HBB used was increased from 3.0 parts by weight to 5.0 parts by weight. It was.
The results are shown in Table 1.

Compared to the case of Example 1, TMCPP was not used, the amount of red phosphorus used was reduced from 6.0 parts by weight to 5.0 parts by weight, and the amount of ammonium dihydrogen phosphate used was 3 The experiment was conducted in the same manner as in Example 1 except that the amount was reduced from 0.0 part by weight to 2.5 parts by weight and the amount of HBB used was reduced from 3.0 parts by weight to 2.5 parts by weight. It was.
The results are shown in Table 2.

Compared to the case of Example 1, TMCPP was not used, the amount of red phosphorus used was increased from 6.0 parts by weight to 20 parts by weight, and the amount of ammonium dihydrogen phosphate used was 3.0. The experiment was performed in exactly the same manner as in Example 1 except that the amount was increased from 10 parts by weight to 10 parts by weight and the amount of HBB used was increased from 3.0 parts by weight to 10 parts by weight.
The results are shown in Table 2.

Compared to the case of Example 1, the amount of TMCPP used was increased from 7.0 parts by weight to 7.4 parts by weight, that of 6.3 parts by weight of zinc borate, and the amount of red phosphorus used. The experiment was performed in exactly the same manner as in Example 1 except that the amount was increased from 6.0 parts by weight to 6.3 parts by weight and that ammonium dihydrogen phosphate and HBB were not used.
The results are shown in Table 2.

Compared with the case of Example 1, the usage-amount of polyol compound A-1 was increased from 21.8 weight part to 52.7 weight part, and the usage-amount of polyisocyanate was changed from 78.2 weight part to 47.3 weight part. The experiment was performed in the same manner as in Example 1 except that the amount was reduced to parts by weight.
The results are shown in Table 2.

Compared with the case of Example 1, the usage-amount of polyol compound A-1 was reduced from 21.8 weight part to 13.7 weight part, and the usage-amount of polyisocyanate was reduced from 78.2 weight part to 86.3 weight part. The experiment was performed in the same manner as in Example 1 except that the amount was increased to parts by weight.
The results are shown in Table 2.

Compared with the case of Example 1, the usage-amount of polyol compound A-1 was reduced from 21.8 weight part to 10.0 weight part, and the usage-amount of polyisocyanate was reduced from 78.2 weight part to 90.0 weight part. The experiment was performed in the same manner as in Example 1 except that the amount was increased to parts by weight.
The results are shown in Table 2.

Compared to the case of Example 1, instead of polyol compound A-1, 16.6 parts by weight of polyol compound A-2 was used, and the amount of polyisocyanate used was 78.2 parts by weight to 83.4 parts by weight. The experiment was performed in exactly the same manner as in Example 1 except that the amount was increased.
The results are shown in Table 2.

Compared to the case of Example 1, 21.4 parts by weight of polyol compound A-3 was used instead of polyol compound A-1, and the amount of polyisocyanate used was 78.2 parts by weight to 78.6 parts by weight. The experiment was performed in exactly the same manner as in Example 1 except that the amount was increased.
The results are shown in Table 2.

The experiment was performed in exactly the same manner as in Example 1 except that 21.8 parts by weight of polyol compound A-4 was used instead of polyol compound A-1 as compared with Example 1.
The results are shown in Table 3.

Compared to the case of Example 1, 27.6 parts by weight of polyol compound A-5 was used instead of polyol compound A-1, and the amount of polyisocyanate used was 78.2 parts by weight to 72.4 parts by weight. The experiment was performed in exactly the same manner as in Example 1 except that the amount was increased.
The results are shown in Table 3.

Compared to the case of Example 1, instead of polyol compound A-1, 16.6 parts by weight of polyol compound A-6 was used, and the amount of polyisocyanate used was 78.2 parts by weight to 83.4 parts by weight. The experiment was performed in exactly the same manner as in Example 1 except that the amount was increased.
The results are shown in Table 3.

The experiment was performed in exactly the same manner as in Example 1 except that 21.8 parts by weight of polyol compound A-7 was used instead of polyol compound A-1 as compared with Example 1.
The results are shown in Table 3.

As compared with the case of Example 1, the experiment was performed in the same manner as in Example 1 except that 3.0 parts by weight of diammonium hydrogen phosphate was used instead of ammonium dihydrogen phosphate.
The results are shown in Table 3.

The experiment was performed in exactly the same manner as in Example 1 except that 3.0 parts by weight of primary aluminum phosphate was used instead of ammonium dihydrogen phosphate as compared with Example 1.
The results are shown in Table 3.

Compared to the case of Example 1, the experiment was performed in the same manner as in Example 1 except that 3.0 parts by weight of EBTBPI was used instead of HBB.
The results are shown in Table 3.

As compared with the case of Example 1, the experiment was performed in the same manner as in Example 1 except that 3.0 parts by weight of EBPBP was used instead of HBB.
The results are shown in Table 3.

The experiment was performed in the same manner as in the case of Example 1 except that 6.0 parts by weight of zinc borate was additionally used as compared with the case of Example 1.
The results are shown in Table 3.

The experiment was performed in exactly the same manner as in Example 1, except that TMCPP was not used and that 6.0 parts by weight of zinc borate was additionally used as compared with Example 1.
The results are shown in Table 3.

[Comparative Example 1]
Compared with the case of Example 1, the usage-amount of polyol compound A-1 was increased from 21.8 weight part to 50.3 weight part, and the usage-amount of polyisocyanate was changed from 78.2 weight part to 49.7 weight part. The experiment was performed in the same manner as in Example 1 except that the amount was reduced to parts by weight and the additive was not used.
The results are shown in Table 4.

[Comparative Example 2]
As compared with the case of Example 1, the experiment was performed in the same manner as in Example 1 except that no additive was used.
The results are shown in Table 4.

[Comparative Example 3]
Compared to the case of Comparative Example 2, 19.4 parts by weight of polyol compound A-2 was used instead of polyol compound A-1, and polyisocyanate was increased from 78.2 parts by weight to 80.6 parts by weight. The experiment was performed in exactly the same manner as in Comparative Example 2 except for the above.
The results are shown in Table 4.

[Comparative Example 4]
Compared to the case of Comparative Example 2, in place of polyol compound A-1, 26.1 parts by weight of polyol compound A-3 was used, and polyisocyanate was reduced from 78.2 parts by weight to 73.9 parts by weight. The experiment was performed in exactly the same manner as in Comparative Example 2 except for the above.
The results are shown in Table 4.

[Comparative Example 5]
Compared to the case of Comparative Example 2, 16.6 parts by weight of polyol compound A-6 was used instead of polyol compound A-1, and the polyisocyanate was increased from 78.2 parts by weight to 83.4 parts by weight. The experiment was performed in exactly the same manner as in Comparative Example 2 except for the above.
The results are shown in Table 4.

[Comparative Example 6]
The experiment was performed in exactly the same manner as in Comparative Example 2 except that 10.0 parts by weight of TMCPP and 10.0 parts by weight of zinc borate were used as compared with Comparative Example 2.
The results are shown in Table 4.

[Comparative Example 7]
The experiment was performed in the same manner as in Comparative Example 2 except that 10.0 parts by weight of TMCPP and 10.0 parts by weight of HBB were used as compared with Comparative Example 2.
The results are shown in Table 4.

[Comparative Example 8]
The experiment was conducted in the same manner as in Comparative Example 2 except that 10.0 parts by weight of zinc borate and 10.0 parts by weight of ammonium dihydrogen phosphate were used as compared with Comparative Example 2. It was.
The results are shown in Table 4.

[Comparative Example 9]
The experiment was performed in the same manner as in Comparative Example 2 except that 10.0 parts by weight of zinc borate and 10.0 parts by weight of HBB were used as compared with Comparative Example 2.
The results are shown in Table 4.

The values (%) of the percentage X represented by (Q ₁ / Q ₀ ) × 100 are entered in Tables 1 to 3, respectively.
The molded product obtained from the fire-resistant urethane resin composition according to the present invention has a small calorific value when combusted, and the residue after combustion maintains a certain shape, and thus can exhibit excellent fire resistance.

  Since the molded product of the fire-resistant urethane resin composition according to the present invention is excellent in fire resistance, the fire-resistant urethane resin composition of the present invention can be widely applied to structural materials such as buildings.

Claims (7)

A fire resistant urethane resin composition comprising a catalyst and an additive,
The catalyst includes a trimerization catalyst that promotes a trimerization reaction of an isocyanate group contained in the urethane resin,
The additive is
(A) Red phosphorus, phosphate-containing flame retardant and bromine-containing flame retardant
(B) Phosphoric acid ester, red phosphorus and bromine-containing flame retardant
(C) Phosphate ester, red phosphorus and phosphate-containing flame retardant
(E) Phosphate ester, boron-containing flame retardant and red phosphorus
(G) Phosphate ester, red phosphorus, phosphate-containing flame retardant and bromine-containing flame retardant
(H) Phosphate ester, boron-containing flame retardant, red phosphorus, phosphate-containing flame retardant, bromine-containing flame retardant and antimony-containing flame retardant
Or
(I) Boron-containing flame retardant, red phosphorus, phosphate-containing flame retardant, bromine-containing flame retardant and antimony-containing flame retardant
Consisting of any one of
The trimerization catalyst is in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the urethane resin,
The additive is in the range of 0.3 to 180 parts by weight with respect to 100 parts by weight of the urethane resin,
For 100 parts by weight of the urethane resin,
The red phosphorus is in the range of 3.2 to 20 parts by weight ;
The phosphate ester is in the range of 3.7 to 17.5 parts by weight ,
The phosphate-containing flame retardant ranges from 1.6 parts by weight to 10 parts by weight ,
The bromine-containing flame retardant ranges from 1.6 parts by weight to 10 parts by weight ,
The boron-containing flame retardant is 6.3 parts by weight ,
The antimony-containing flame retardant is 3.0 parts by weight ;
The polyol contained in the urethane resin is at least one selected from the group consisting of 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. And
The polyol contained in the urethane resin consists of an oxygen atom, a hydrogen atom and a carbon atom,
The fire-resistant urethane resin composition, wherein the boron-containing flame retardant is at least one selected from the group consisting of boron oxide, boric acid and a boric acid metal salt.   The refractory urethane resin composition according to claim 1, wherein the phosphate-containing flame retardant comprises at least one selected from the group consisting of monophosphate, pyrophosphate, and polyphosphate.   The refractory urethane resin composition according to claim 1 or 2, wherein the phosphate ester is at least one of a monophosphate ester and a condensed phosphate ester.   The fire-resistant urethane resin composition according to any one of claims 1 to 3, wherein the bromine-containing flame retardant contains a brominated aromatic ring-containing aromatic compound.   The fireproof urethane resin composition according to any one of claims 1 to 4, wherein the antimony-containing flame retardant is at least one selected from the group consisting of antimony oxide, antimonate, and pyroantimonate.   The fire-resistant urethane resin composition according to any one of claims 1 to 5, wherein the urethane resin contains an isocyanate compound and a polyol compound.   The refractory urethane resin composition according to any one of claims 1 to 6, wherein the refractory urethane resin composition contains at least one selected from the group consisting of a foam stabilizer and a foaming agent.