JP6378088B2 - Urethane resin composition - Google Patents

Description

  The present invention relates to a urethane resin composition.

Concrete reinforced with reinforcing bars or the like is used for apartment houses such as condominiums, detached houses, various facilities of schools, and outer walls of commercial buildings.
Concrete has the advantage of maintaining strength over a long period of time as a structural material.
On the other hand, in hot weather such as summer, there is a disadvantage that heat is accumulated in concrete due to outside air or direct sunlight, and the inside of the building is heated by the accumulated heat.
In addition, the concrete is cooled not only in summer but also in cold periods such as winter. As a result, the interior of the building is cooled.
In this way, the outside temperature may affect the inside of the building for a long time through the concrete. In order to reduce this effect, heat insulation is usually applied to concrete.
For example, in the case of concrete reinforced with reinforcing bars used in apartment houses such as apartments, a hard urethane foam is sprayed on the concrete surface to form a heat insulating layer.
However, if only a hard urethane foam is sprayed as the heat insulating layer, the hard urethane foam may burn if a fire or the like occurs inside the building. In order to prevent the hard urethane foam from burning, a fire-resistant material called white cement, which is mainly composed of volcanic ash, cement or the like, is sprayed on the surface of the hard urethane foam.
By using the white cement, it is possible to prevent the hard urethane foam from burning.
However, after forming a heat insulation layer by spraying hard urethane foam on the surface of the concrete, when a white cement is sprayed on the surface of the hard urethane foam to form a fireproof layer, a spraying operation occurs in two stages. There was a problem that construction was not easy.
And after spraying the said rigid urethane foam, the next construction process cannot be advanced until the said rigid urethane foam fully reacts. Furthermore, after spraying the white cement on the surface of the rigid urethane foam, the next construction process cannot proceed until the curing of the white cement is completed, and there is a problem that it takes time for construction.

In order to cope with the above problem, it is convenient if the construction can be completed using only the urethane resin composition that does not require the spraying of white cement. At present, in order to simplify the construction, it is desired to develop a urethane resin composition capable of completing the construction by a one-step spraying method.
However, the known urethane resin composition has a problem of a large calorific value when burned. In order to complete construction by a one-step spraying method, it is necessary to reduce the amount of heat generated when the urethane resin composition burns.
As one of the techniques for solving this problem, a technique for improving the flame retardancy of a cured urethane resin composition by forming a nurate bond when the urethane resin composition is cured is disclosed (patent) Reference 1).
Moreover, the technique which improves the flame retardance of a urethane resin composition is disclosed by using ammonium polyphosphate and red phosphorus as a flame retardant (patent document 2).
Similarly, a technique for improving the flame retardancy of a urethane resin composition by using a catalyst that promotes trimerization of ammonium polyphosphate and isocyanate groups as a flame retardant is also disclosed (Patent Document 3).

JP 2002-047325 A JP 10-168150 A JP-A-11-140150

  An object of the present invention is to provide a urethane resin composition having a small calorific value when burned and excellent in flame retardancy.

  As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, it was found that a urethane resin composition containing a phosphate-containing flame retardant meets the object of the present invention, and the present invention has been completed. .

That is, the present invention
[1] A urethane resin composition comprising a urethane resin containing a polyisocyanate compound and a polyol compound, a flame retardant, and a trimerization catalyst for promoting a trimerization reaction of an isocyanate group contained in the polyisocyanate compound,
The flame retardant comprises red phosphorus and a phosphate-containing flame retardant;
The red phosphorus is in the range of 3.0 to 20 parts by weight and the phosphate-containing flame retardant is in the range of 1.0 to 18 parts by weight with respect to 100 parts by weight of the urethane resin. The present invention provides a urethane resin composition.

One of the present invention is
[2] The urethane resin composition according to the above [1], wherein the weight ratio of the red phosphorus and the phosphate-containing flame retardant is in the range of 1: 3 to 3: 1.

One of the present invention is
[3] The urethane resin composition according to the above [1] or [2], wherein the phosphate-containing flame retardant is a monophosphate.

One of the present invention is
[4] The urethane resin composition according to any one of [1] to [3], wherein the polyisocyanate compound and the polyol compound contained in the urethane resin have an index in the range of 150 to 700. is there.

One of the present invention is
[5] The urethane resin composition according to any one of [1] to [4], wherein the urethane resin composition contains at least one of a foam stabilizer and a foaming agent.

One of the present invention is
[6] The urethane resin composition according to any one of the above [1] to [5], wherein the density after curing is in the range of 0.020 to 0.080 kg / m ³ .

The present invention also provides
[7] A molded product obtained by molding the urethane resin composition according to any one of [1] to [6] is provided.

The present invention also provides
[8] The molded body according to the above [7], wherein the molded body is used for a building, an automobile, a railway vehicle, a ship, or an airplane.

  The urethane resin composition according to the present invention is excellent in handleability. Moreover, since the molded object obtained by the urethane resin composition which concerns on this invention has little calorific value at the time of combustion, it can exhibit the outstanding flame retardance.

The urethane resin composition according to the present invention will be described.
First, the urethane resin used for the 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 diphenylmethane diisocyanate 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 polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polymer polyol, and polyether polyol.

Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.
The polycarbonate polyol can be obtained, for example, by dealcoholization reaction of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with diethylene carbonate, dipropylene carbonate, and the like. 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 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. And a condensate of hydroxycarboxylic acid and the above polyhydric alcohol.

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

  Examples of the polymer polyol include a polymer obtained by graft polymerization of an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate on the aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, and the like. , Polybutadiene polyols, modified polyols of polyhydric alcohols, or 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, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, anthrol, 1,4,5 , 8-tetrahydroxyanthracene, phenols such as 1-hydroxypyrene,
Polybutadiene polyol,
Polyols made from castor oil,
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 and the like.
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. And the resulting polymer.
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.

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

Next, the blending ratio of the main component and the curing agent of the urethane resin will be described.
In the present invention, the index which is the ratio (NCO / OH) of the active hydrogen group (OH) of the polyol compound and water to the active isocyanate group (NCO) in the polyisocyanate compound is [equivalent number of isocyanate] × 100 ÷ [ The number of equivalents of polyol + the number of equivalents 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 isocyanate 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 index range is usually mixed so as to be in the range of 150-700. This range is preferably in the range of 200 to 700, more preferably in the range of 300 to 700, and still more preferably in the range of 350 to 650.
When the equivalent ratio is 150 or more, the amount of isocyanurate groups in the urethane resin composition can be prevented from decreasing, and thus the flame retardancy can be prevented from being decreased. When the equivalent ratio is 700 or less, the urethane resin composition can be prevented from becoming too brittle. be able to.

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 amino compounds, tin compounds, and acetylacetone metal salts.

Examples of the amino compound include pentamethyldiethylenetriamine, 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'N'-dimethylaminoethylpiperazine, imidazole substituted secondary amine functional group in imidazole ring with cyanoethyl group Compound, N, N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine, N-methylimidazole, trimethylaminoethylpiperazine, tripropylamine,
Examples thereof include tetramethylammonium salt, tetraethylammonium salt, and triphenylammonium salt.

  Examples of the tin compound include dibutyltin diacetate and dibutyltin dilaurate.

  Examples of the acetylacetone metal salt include acetylacetone aluminum, acetylacetone iron, acetylacetone copper, acetylacetone zinc, acetylacetone beryllium, acetylacetone chromium, acetylacetone indium, acetylacetone manganese, acetylacetone molybdenum, acetylacetone titanium, acetylacetone cobalt, acetylacetone vanadium, and acetylacetone zirconium. It is done.

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

The addition amount of the urethane resin curing catalyst used in the 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 to 8 parts by weight, still more preferably in the range of 0.01 to 6 parts by weight, and in the range of 0.01 to 1.5 parts by weight. Most preferably.
In the case of 0.01 parts by weight or more and 10 parts by weight or less, it is easy to handle and the reaction is easily controlled.

  As the polyurethane resin used in the present invention, there can be used those obtained by reacting an isocyanate group contained in a polyisocyanate compound, which is a main component of the polyurethane resin, to trimerize and promoting the formation of an isocyanurate ring.

  In order to promote the formation of an 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, potassium acetate, sodium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, quaternary ammonium compounds such as tertiary amine carboxylates, 2-ethylaziridine, etc. Amine compounds such as aziridines, lead compounds such as diazabicycloundecene, lead naphthenate and lead octylate, alcoholate compounds such as sodium methoxide, phenolate compounds such as potassium phenoxide, quaternary ammonium salts of carboxylic acids, etc. Use it.

The addition amount of the trimerization catalyst used in the flame retardant urethane resin composition according to the present invention is not particularly limited, but may be in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. Preferably, it is in the range of 0.01 to 8 parts by weight, more preferably in the range of 0.01 to 6 parts by weight, and 0.5 to 1.5 parts by weight. The range is most preferable.
When the amount is 0.01 parts by weight or more, the amount of isocyanurate groups in the urethane resin composition can be prevented from decreasing, so that the flame retardancy can be prevented. When the amount is 10 parts by weight or less, the urethane resin composition Can be prevented from becoming too brittle.

  One or two or more trimerization catalysts can be used.

In the present invention, a foaming agent is used in addition to the urethane resin.
In order to promote foaming of the urethane resin contained in the urethane resin composition according to the present invention, a foaming agent can be added to the urethane resin composition according to the present 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, trichlorotrifluoroethane, CHF ₃ , CH ₂ F ₂ , 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), HFC-365mfc (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, or water is used alone.

The amount of the foaming agent used in the urethane resin 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. More preferably, it is in the range of 1 to 18 parts by weight, more preferably in the range of 0.1 to 15 parts by weight, and in the range of 0.3 to 10 parts by weight. Most preferred.
When the water range is 0.1 parts by weight or more, formation of bubbles is promoted and a good foam is obtained, and when it is 20 parts by weight or less, the vaporization force is increased and the bubbles are prevented from becoming coarse. Can do.

A foam stabilizer can also be used in the 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, it is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 4 parts by weight, and still more preferably 1 to 3 parts by weight.

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

Next, red phosphorus used in the present invention will be described.
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 3.0 parts by weight to 20 parts by weight with respect to 100 parts by weight of the urethane resin.
This range is more preferably in the range of 3.0 parts by weight to 12 parts by weight.
When the range of the red phosphorus is 3.0 parts by weight or more, the self-extinguishing property of the urethane resin composition according to the present invention is maintained, and when it is 20 parts by weight or less, the urethane resin composition according to the present invention Foaming is not hindered.

Next, the phosphate-containing flame retardant used in the present invention will be described.
The phosphate-containing flame retardant used in the present invention contains phosphoric acid.
Examples of phosphoric acid used in the phosphate-containing flame retardant include various phosphoric acids such as monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid.

Examples of the phosphate-containing flame retardant include salts of the various phosphoric acids and at least one metal or compound selected from metals of Group IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. Can be mentioned.
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 pyridine, triazine, melamine, and ammonium.
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 and pyrophosphate.

The monophosphate is not particularly limited, and examples thereof include ammonium salts such as ammonium dihydrogen phosphate and 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.

  Among these, since the self-extinguishing property of the phosphate-containing flame retardant is improved, it is preferable to use a monophosphate, such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, primary aluminum phosphate, phosphoric acid It is more preferable to use at least one selected from the group consisting of monosodium and tertiary aluminum phosphate, and it is more preferable to use ammonium dihydrogen phosphate and diammonium hydrogen phosphate.

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

The amount of the phosphate-containing flame retardant used in the present invention is in the range of 1.0 to 18 parts by weight with respect to 100 parts by weight of the urethane resin.
When the range of the phosphate-containing flame retardant is 1.0 part by weight or more, the self-extinguishing property of the urethane resin composition according to the present invention is maintained, and when it is 18 parts by weight or less, the urethane according to the present invention is maintained. Foaming of the resin composition is not inhibited.

In the present invention, it is preferable to use the red phosphorus and the phosphate-containing flame retardant together because the total calorific value of the molded article of the urethane resin composition obtained is reduced.
When the red phosphorus and the phosphate-containing flame retardant are used in combination, the weight ratio of the red phosphorus and the phosphate-containing flame retardant is preferably in the range of 1: 3 to 3: 1. .

Moreover, the urethane resin composition according to the present invention can be used in combination with a flame retardant other than the red phosphorus and the phosphate-containing flame retardant.
Examples of such flame retardants include phosphate esters, bromine-containing flame retardants, boron-containing flame retardants, and antimony-containing flame retardants.

  Although there is no limitation in particular as said phosphate ester, It is preferable to use monophosphate ester, condensed phosphate ester, etc.

  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 0.1 weight part-200 weight part with respect to 100 weight part of said urethane resins. The addition amount of the phosphate ester is preferably in the range of 0.1 to 100 parts by weight, more preferably in the range of 0.1 to 50 parts by weight, and 5 to 15 parts by weight. If it is the range, it is still more preferable.
When the range of the phosphoric acid ester is 0.1 parts by weight or more, the molded body made of the urethane resin composition according to the present invention can be prevented from cracking the dense residue formed by the heat of fire, and 200 parts by weight or less. In this case, foaming of the urethane resin composition according to the present invention is not inhibited.

The bromine-containing flame retardant is not particularly limited as long as it is a compound containing bromine in the molecular structure, and examples thereof include aromatic brominated compounds.
Specific examples of the aromatic brominated compound include, for example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (penta Monomeric organic bromine compounds such as bromophenoxy) ethane, ethylene-bis (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, brominated polystyrene, 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 the bromine-containing flame retardant used in the present invention is not particularly limited, but is preferably in the range of 0.1 to 60 parts by weight with respect to 100 parts by weight of the urethane resin, and 0.1 parts by weight. It is more preferably in the range of ˜50 parts by weight, still more preferably in the range of 0.1 parts by weight to 40 parts by weight, and most preferably in the range of 2 parts by weight to 5 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 urethane resin composition according to the present invention is maintained, and when it is 60 parts by weight or less, the urethane resin composition according to the present invention. The foaming of objects is not hindered.

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 in the range of 0.1 to 60 parts by weight with respect to 100 parts by weight of the urethane resin. The amount of the boron-containing flame retardant added is preferably in the range of 0.1 to 50 parts by weight, more preferably in the range of 0.1 to 40 parts by weight, and 1 to 10 parts by weight. More preferably, it is in the range of parts.
When the range of the boron-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the urethane resin composition according to the present invention is maintained, and when it is 60 parts by weight or less, the urethane resin composition according to the present invention. The foaming of objects is not hindered.

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

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

The amount of the antimony-containing flame retardant added is not particularly limited, but is preferably in the range of 0.1 to 60 parts by weight, and 0.1 to 50 parts by weight with respect to 100 parts by weight of the urethane resin. Is more preferably in the range of 0.1 to 40 parts by weight, and most preferably in the range of 1 to 10 parts by weight.
When the range of the antimony-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the urethane resin composition according to the present invention is maintained, and when it is 60 parts by weight or less, the urethane resin composition according to the present invention. The foaming of objects is not hindered.

Further, the urethane resin 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 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 balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder, Seed metal powder, 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 fiber , Alumina fibers, silica fibers, zirconia fibers and the like.

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

  Further, the urethane resin composition according to the present invention is an antioxidant, such as phenol-containing, amine-containing, sulfur-containing, heat stabilizer, metal harm-preventing agent, as long as the object of the present invention is not impaired. An antistatic agent, a stabilizer, a crosslinking agent, a lubricant, a softener, a pigment, an additive such as a tackifier resin, and a tackifier such as polybutene and a petroleum resin can be included.

Since the urethane resin composition according to the present invention reacts and cures, the viscosity changes with time.
Therefore, before using the urethane resin composition according to the present invention, the urethane resin composition is divided into two or more to prevent the urethane resin composition from reacting and curing. And when using the urethane resin composition which concerns on this invention, the urethane resin composition which concerns on this invention is obtained by putting together the said urethane resin composition divided | segmented into two or more.
When the urethane resin composition is divided into two or more, curing does not start with each component of the urethane resin composition divided into two or more, and is cured after mixing the components of the urethane resin composition. What is necessary is just to divide each component so that reaction may start.

Next, the manufacturing method of the said urethane resin composition is demonstrated.
The method for producing the urethane resin composition is not particularly limited. For example, the method of mixing the components of the urethane resin composition, the urethane resin composition is suspended in an organic solvent, or heated and melted. Or a method of preparing a slurry by dispersing in a solvent, or a reaction curable resin component contained in the urethane resin composition contains a component that is solid at a temperature of 25 ° C. The urethane resin composition can be obtained by a method such as melting the 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 urethane resin composition excluding the catalyst and the catalyst can be kneaded in the same manner immediately before injection.

  The urethane resin composition according to the present invention can be obtained by the method described above.

Next, a method for curing the urethane resin composition according to the present invention will be described.
When the respective components of the urethane resin composition are mixed, the reaction starts, the viscosity increases with the passage of time, and the fluidity is lost.
For example, a molded body made of the urethane resin composition can be obtained by injecting the 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 urethane resin composition, heat can be applied or pressure can be applied.
Although there is no particular limitation on the density of the urethane resin composition after curing, it is preferably in the range of 0.020~0.080kg / ^{m 3,} in the range of 0.030~0.080kg / ^{m 3} More preferably, the range of 0.030 to 0.070 kg / m ³ is still more preferable, and the range of 0.030 to 0.060 kg / m ³ is most preferable.
The molded body made of the urethane resin composition after curing 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 in accordance with the test method of ISO-5660. it can.

  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 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-1: polyol 1
p-phthalic polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol R
FK-505, hydroxyl value: 250 mg KOH / g, number of functional groups: 2 [per molecule])
A-2: Polyol 2
o-Phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RDK-142, hydroxyl value: 400 mgKOH / g)
A-3: Polyol 3
p-phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RLK-035, hydroxyl value: 150 mgKOH / g)
A-4: Polyol 4
Polyether polyol (Mitsui Chemicals, product name: Actol T-400, hydroxyl value: 399 mgKOH / g, functional group number: 3 [per molecule])
A-5: Polyol 5
Polyether polyol (manufactured by Mitsui Chemicals, product name: Actol SOR-400, hydroxyl value: 397 mg KOH / g, number of functional groups: 6 [per molecule])
(B) Component: 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: Trimerization catalyst (product name: Kao Riser No. 14 manufactured by Kao Corporation)
B-4: Trimerization catalyst (product name: Kao Riser No. 410, manufactured by Kao Corporation)
B-5: Trimerization catalyst (product name: Kao Riser No. 420, manufactured by Kao Corporation)
B-6: Pentamethyldiethylenetriamine (manufactured by Tosoh Corporation, product name: TOYOCAT-DT)
Component (C): foam stabilizer, foaming agent [foam stabilizer]
Polyalkylene glycol foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193)
[Foaming agent]
C-1: Water C-2: HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Solvay Japan) using the following mixture
HFC-245fa (1,1,1,3,3-pentafluoropropane, manufactured by Central Glass Co., Ltd.)
Mixing ratio HFC-365mfc: HFC-245fa = 7: 3 (weight ratio; hereinafter referred to as “HFC”)

(D) Component: Additive D-1: Red phosphorus (Rin Chemical Industry Co., Ltd., product name: Nova Excel 140)
D-2: Ammonium dihydrogen phosphate (manufactured by Taihei Chemical Industrial Co., Ltd.)
D-3: Diammonium hydrogen phosphate (manufactured by Taihei Chemical Industrial Co., Ltd.)
D-4: Primary aluminum phosphate (manufactured by Taihei Chemical Industrial Co., Ltd.)
D-5: Trialuminum phosphate (manufactured by Taihei Chemical Industry Co., Ltd.)
D-6: Sodium monophosphate (manufactured by Taihei Chemical Industrial Co., Ltd.)

Component (X): polyisocyanate compound (hereinafter referred to as “polyisocyanate”)
MDI (manufactured by Nippon Polyurethane Industry Co., Ltd., product name: Millionate MR-200) Viscosity: 167 mPa · s, isocyanate content 30.5-32.0%

Next, according to the composition of the following Table 1, each component of a polyol compound, a catalyst, a flame retardant and a polyisocyanate is weighed in a 1000 ml polypropylene beaker, using a three-one motor (product name: BLW1200), 25 ° C., 400 rpm. The mixture was stirred for 2 minutes.
A foam stabilizer and a foaming agent were added to the above components 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.
In addition, each compounding component shown in Table 1 is a unit by weight, and the total value of the polyol compound and the polyisocyanate is expressed as 100 parts by weight.
The obtained urethane resin composition lost fluidity with the passage of time, and a cured product of the urethane resin composition was obtained. The cured product was evaluated according to the following criteria, and the results are shown in Table 1.
The density was 0.052. The results are also shown in Table 1 (unit: g / cm ³ ).

[Measurement of heat quantity and maximum heat generation rate]
A sample for corn calorimeter test was cut out from the cured product so as to be 10 cm × 10 cm × 5 cm, and when heated for 10 minutes at a radiant heat intensity of 50 kW / m ² according to ISO-5660, respectively when heated for 20 minutes The total calorific value and the maximum exothermic rate of were 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.
The total calorific value after 10 minutes from this test was 2.8 MJ / m ² , and the total calorific value after 20 minutes was 4.9 MJ / m ² . The maximum heat generation rate was 2.9 Kw / m ² . The results are shown in Table 1.

Compared to the case of Example 1, it was carried out except that the amount of foaming agent C-1 used was 0.6 parts by weight, and that D-3 was used in an amount of 3.0 parts by weight instead of flame retardant D-2. The experiment was conducted exactly as in Example 1.
The results are shown in Table 1.

Compared to the case of Example 1, it was carried out except that the amount of foaming agent C-1 used was 0.6 parts by weight, and that D-4 was used in an amount of 3.0 parts by weight instead of flame retardant D-2. The experiment was conducted exactly as in Example 1.
The results are shown in Table 1.

Compared to the case of Example 1, it was carried out except that the amount of foaming agent C-1 used was 0.6 parts by weight, and that D-5 was used in an amount of 3.0 parts by weight instead of flame retardant D-2. The experiment was conducted exactly as in Example 1.
The results are shown in Table 1.

Compared to the case of Example 1, it was carried out except that the amount of foaming agent C-1 used was 0.6 parts by weight, and that D-6 was used in an amount of 3.0 parts by weight instead of flame retardant D-2. The experiment was conducted exactly as in Example 1.
The results are shown in Table 1.

Compared to the case of Example 1, the amount of foaming agent C-1 used was 1.0 part by weight, the amount of foaming agent C-2 was not used, and the amount of polyol A-1 used was 11. The experiment was performed in the same manner as in Example 1 except that the amount was 9 parts by weight and that the amount of polyisocyanate used was 88.1 parts by weight.
The results are shown in Table 1.

The experiment was performed in the same manner as in Example 6 except that 6.0 parts by weight of flame retardant D-2 was used as compared with Example 6.
The results are shown in Table 1.

Compared to the case of Example 1, the amount of foaming agent C-1 used was 0.6 parts by weight, the amount of flame retardant D-2 used was 6.0 parts by weight, polyol compound A- The experiment was conducted in exactly the same manner as in Example 1 except that 15.4 parts by weight of polyol compound A-2 was used instead of 1, and the amount of polyisocyanate used was 84.6 parts by weight.
The results are shown in Table 1.

Compared to the case of Example 8, it was carried out except that 30.1 parts by weight of polyol compound A-3 was used instead of polyol compound A-2, and that the amount of polyisocyanate used was 69.9 parts by weight. The experiment was conducted exactly as in Example 8.
The results are shown in Table 1.

Compared with the case of Example 8, it replaced with polyol compound A-2, and it implemented except having used 15.5 weight part of polyol compound A-4, and having used 84.5 weight part of polyisocyanate. The experiment was conducted exactly as in Example 8.
The results are shown in Table 1.

Compared to the case of Example 8, it was carried out except that 16.7 parts by weight of polyol compound A-5 was used instead of polyol compound A-2 and that the amount of polyisocyanate used was 83.3 parts by weight. The experiment was conducted exactly as in Example 8.
The results are shown in Table 1.

Compared to the case of Example 1, 0.7 parts by weight of the trimerization catalyst B-3 was used instead of the trimerization catalyst B-2, and the use amount of the foaming agent C-1 was 0.6 parts by weight. The experiment was performed in exactly the same manner as in Example 1 except that.
The results are shown in Table 1.

As compared with the case of Example 12, the experiment was performed in the same manner as in Example 12 except that 0.7 parts by weight of the trimerization catalyst B-4 was used instead of the trimerization catalyst B-3.
The results are shown in Table 1.

As compared with the case of Example 12, the experiment was performed in exactly the same manner as in Example 12 except that 0.7 parts by weight of the trimerization catalyst B-5 was used instead of the trimerization catalyst B-3.
The results are shown in Table 1.

As compared with the case of Example 12, the experiment was performed in exactly the same manner as in Example 12 except that 0.7 parts by weight of the trimerization catalyst B-2 was used instead of the trimerization catalyst B-3.
The results are shown in Table 1.

In the case of Example 1 except that the amount of the flame retardant D-1 used is 12.0 parts by weight and the amount of the flame retardant D-2 used is 6.0 parts by weight compared to the case of Example 1. The experiment was carried out in exactly the same way.
The results are shown in Table 2.

In the case of Example 1 except that the amount of the flame retardant D-1 used is 3.0 parts by weight and the amount of the flame retardant D-2 used is 1.0 parts by weight compared to the case of Example 1. The experiment was carried out in exactly the same way.
The results are shown in Table 2.

Experiments were performed in exactly the same manner as in Example 1 except that the amount of flame retardant D-1 used was 9.0 parts by weight, compared with Example 1.
The results are shown in Table 2.

In the case of Example 1 except that the amount of the flame retardant D-1 used is 3.0 parts by weight and the amount of the flame retardant D-2 used is 9.0 parts by weight as compared with the case of Example 1. The experiment was carried out in exactly the same way.
The results are shown in Table 2.

In the case of Example 1 except that the amount of the flame retardant D-1 used is 18.0 parts by weight and the amount of the flame retardant D-2 used is 6.0 parts by weight compared to the case of Example 1. The experiment was carried out in exactly the same way.
The results are shown in Table 2.

The experiment was performed in exactly the same manner as in Example 1, except that the amount of flame retardant D-2 used was 18.0 parts by weight compared to Example 1.
The results are shown in Table 2.

Compared with the case of Example 1, the usage-amount of polyol compound A-1 was 10.0 weight part, and the usage-amount of polyisocyanate was 90.0 weight part. The experiment was performed in the same manner as in Example 1 except that the amount of flame retardant D-1 used was 3.0 parts by weight and the amount of flame retardant D-2 used was 1.0 parts by weight.
The results are shown in Table 2.

In the case of Example 22, except that the amount of the flame retardant D-1 used was 1.0 part by weight and the amount of the flame retardant D-2 used was 3.0 parts by weight, compared with the case of Example 22. The experiment was carried out in exactly the same way.
The results are shown in Table 2.

In the case of Example 22, except that the amount of the flame retardant D-1 used was 9.0 parts by weight and the amount of the flame retardant D-2 used was 3.0 parts by weight, compared to the case of Example 22. The experiment was carried out in exactly the same way.
The results are shown in Table 2.

The experiment was performed in exactly the same manner as in Example 22, except that the amount of flame retardant D-2 used was 9.0 parts by weight, compared with Example 22.
The results are shown in Table 2.

In the case of Example 22, except that the amount of flame retardant D-1 used was 18.0 parts by weight and the amount of flame retardant D-2 used was 6.0 parts by weight, compared to the case of Example 22. The experiment was carried out in exactly the same way.
The results are shown in Table 2.

As compared with the case of Example 22, the experiment was performed in the same manner as in Example 22 except that the amount of the flame retardant D-2 used was 18.0 parts by weight.
The results are shown in Table 2.
The results are shown in Table 2.

[Comparative Example 1]
According to the formulation shown in Table 3, 50.3 parts by weight of polyol compound A-1, 49.7 parts by weight of polyisocyanate, 0.1 part by weight of foam stabilizer, and 1.7 parts by weight of foaming agent C-1 Using 0.6 parts by weight of the foaming agent C-2 and 6.4 parts by weight of the flame retardant D-1, an experiment was conducted according to the same procedure as in Example 1.
The results are shown in Table 3.

[Comparative Example 2]
As compared with the case of Comparative Example 1, the experiment was performed in the same manner as in the case of Comparative Example 1 except that 6.0 parts by weight of the flame retardant D-2 was used.
The results are shown in Table 3.

[Comparative Example 3]
Compared to the case of Comparative Example 1, the experiment was performed in exactly the same manner as in Comparative Example 1 except that 6.0 parts by weight of flame retardant D-3 was used.
The results are shown in Table 3.

[Comparative Example 4]
As compared with the case of Comparative Example 1, the experiment was performed in the same manner as in Comparative Example 1 except that 6.0 parts by weight of each of the flame retardants D-2 and D-3 were used.
The results are shown in Table 3.

[Comparative Example 5]
As compared with the case of Example 12, the experiment was performed in the same manner as in Example 12 except that 3.2 parts by weight of the flame retardant D-1 was used and the flame retardant D-2 was not used. .
The results are shown in Table 3.

[Comparative Example 6]
Compared to the case of Comparative Example 5, the experiment was performed in exactly the same manner as in Comparative Example 5 except that 3.0 parts by weight of flame retardant D-2 was used.
The results are shown in Table 3.

[Comparative Example 7]
Compared to the case of Comparative Example 6, the experiment was performed in exactly the same manner as in Comparative Example 6 except that 6.0 parts by weight of flame retardant D-2 was used.
The results are shown in Table 3.

[Comparative Example 8]
The experiment was performed in exactly the same manner as in Comparative Example 6 except that 12.0 parts by weight of flame retardant D-2 was used as compared with Comparative Example 6.
The results are shown in Table 3.

[Comparative Example 9]
Compared to the case of Comparative Example 6, the experiment was performed in exactly the same manner as in Comparative Example 6 except that 24.0 parts by weight of flame retardant D-2 was used.
The results are shown in Table 3.

[Comparative Example 10]
As compared with the case of Comparative Example 6, the experiment was performed in exactly the same manner as in Comparative Example 6 except that 3.0 parts by weight of the flame retardant D-3 was used instead of the flame retardant D-2.
The results are shown in Table 3.

[Comparative Example 11]
Experiments were performed in exactly the same manner as in Comparative Example 10 except that 6.0 parts by weight of flame retardant D-3 was used as compared with Comparative Example 10.
The results are shown in Table 3.

[Comparative Example 12]
The experiment was performed in exactly the same manner as in Comparative Example 10 except that 15.0 parts by weight of flame retardant D-3 was used as compared with Comparative Example 10.
The results are shown in Table 3.

[Comparative Example 13]
The experiment was performed in exactly the same manner as in Comparative Example 10 except that 45.0 parts by weight of flame retardant D-3 was used as compared with Comparative Example 10.
The results are shown in Table 3.

[Comparative Example 14]
In the case of Example 1 except that the amount of the flame retardant D-1 used is 2.0 parts by weight and the amount of the flame retardant D-2 used is 1.0 parts by weight compared to the case of Example 1. The experiment was carried out in exactly the same way.
The results are shown in Table 3.

[Comparative Example 15]
In the case of Example 1 except that the amount of the flame retardant D-1 used is 24.0 parts by weight and the amount of the flame retardant D-2 used is 12.0 parts by weight compared to the case of Example 1. The experiment was carried out in exactly the same way.
The results are shown in Table 3.

[Comparative Example 16]
Experiments were performed in exactly the same manner as in Example 1 except that the amount of flame retardant D-1 used was 1.0 part by weight as compared with Example 1.
The results are shown in Table 3.

  Since the molded object obtained by the urethane resin composition according to the present invention has a small calorific value when combusted, it can exhibit excellent flame retardancy.

  The molded body is preferably used for a material used for at least one of a building, an automobile, a railway vehicle, a ship, an airplane, and the like.

  Since the molded product of the urethane resin composition according to the present invention is excellent in flame retardancy, it is suitable for structural materials such as buildings, wall materials, floor materials, ceiling materials, heat insulating materials, seat materials such as vehicles, bed materials, etc. The urethane resin composition of the invention can be widely applied.

Claims (7)

A urethane resin composition comprising a urethane resin containing a polyisocyanate compound and a polyol compound, a flame retardant, and a trimerization catalyst for promoting a trimerization reaction of an isocyanate group contained in the polyisocyanate compound,
The flame retardant comprises red phosphorus and monophosphate ;
The red phosphorus is in the range of 3.0 to 20 parts by weight and the monophosphate is in the range of 1.0 to 18 parts by weight with respect to 100 parts by weight of the urethane resin. A urethane resin composition. The urethane resin composition according to claim 1, wherein a weight ratio of the red phosphorus and the monophosphate is in a range of 1: 3 to 3: 1. The urethane resin composition of Claim 1 or 2 whose index of the polyisocyanate compound and polyol compound contained in the said urethane resin is the range of 150-700. The urethane resin composition according to any one of claims 1 to 3 , wherein the urethane resin composition contains at least one of a foam stabilizer and a foaming agent. The urethane resin composition according to any one of claims 1 to 4 , wherein a density after curing is in a range of 0.020 to 0.080 kg / m ³ . The molded object formed by shape | molding the urethane resin composition in any one of Claims 1-5 . The molded body according to claim 6 , wherein the molded body is used as a material for use in a building, an automobile, a railway vehicle, a ship, or an airplane.