JP2017226831A - Flame-retardant urethane resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant urethane resin composition that prevents the occurrence of carbon monoxide and has high flame retardancy.SOLUTION: A flame-retardant urethane resin composition contains a polyisocyanate compound, a polyol compound, a catalyst, a foamer, a foam stabilizer, and an additive, the additive containing red phosphorus and at least one of clay mineral, layered polysilicic acid and a molybdenum compound.SELECTED DRAWING: None

Description

  The present invention relates to a flame retardant urethane resin composition.

  Rigid polyurethane foam with flame resistance to fire is used for heat insulation of buildings such as apartment houses, detached houses, various school facilities, and commercial buildings.

  Patent Document 1 is a refractory urethane resin composition containing a catalyst and an additive, wherein the catalyst contains a trimerization catalyst that promotes a trimerization reaction of isocyanate groups contained in the urethane resin, and the additive is red phosphorus. , Phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, and antimony-containing flame retardant, and the trimerization catalyst is 100 parts by weight of urethane resin The fire-resistant urethane resin composition is characterized by being in the range of 0.01 to 10 parts by weight, and 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. Is described.

JP 2014-193995

  Patent Document 1 includes red phosphorus and at least two selected from the group consisting of phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant and antimony-containing flame retardant in addition to red phosphorus. However, the fire-resistant urethane resin composition exhibits high flame retardancy, but if there is a large amount of red phosphorus used, there is a tendency for carbon monoxide to be generated violently. There was a problem of shortage.

  An object of the present invention is to provide a flame retardant urethane resin composition that suppresses generation of carbon monoxide and has high flame retardancy.

  In order to achieve the above object, the present inventors use red phosphorus as an additive and at least one of clay mineral, layered polysilicic acid, and molybdenum compound, while exhibiting flame retardancy. The inventors have found that the generation of carbon oxide can be suppressed, and have completed the present invention.

  According to one aspect of the present invention, a flame retardant urethane resin composition comprising a polyisocyanate compound, a polyol compound, a catalyst, a foaming agent, a foam stabilizer, and an additive, the additive being red phosphorus; and a clay mineral And a flame retardant urethane resin composition comprising at least one of layered polysilicic acid and molybdenum compound.

  ADVANTAGE OF THE INVENTION According to this invention, the flame-retardant urethane resin composition with high flame retardance in which generation | occurrence | production of carbon monoxide was suppressed, and its molded object are provided.

  Hereinafter, the flame-retardant urethane resin composition according to the present invention will be described.

  The urethane resin is composed of a polyisocyanate compound as a main agent and a polyol compound as a curing agent.

  As a polyisocyanate compound, aromatic polyisocyanate, alicyclic polyisocyanate, aliphatic polyisocyanate etc. are mentioned, for example.

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

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

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

  One or more polyisocyanate compounds can be used. The main component of the urethane resin is preferably diphenylmethane diisocyanate for reasons such as ease of use and availability.

  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.

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

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

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

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

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

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

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

  Examples of the polymer polyol include a polymer obtained by graft polymerization of an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate on an aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, or the like, polybutadiene Examples thereof include polyols, modified polyols of polyhydric alcohols, and hydrogenated products thereof.

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

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

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

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

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

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

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

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

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

  The isocyanate index is a percentage of the equivalent ratio of the isocyanate group of the polyisocyanate compound to the hydroxyl group of the polyol compound. When the value exceeds 100, the isocyanate group is in excess of the hydroxyl group. .

  The range of the isocyanate index of the urethane resin used in the present invention is preferably in the range of 100 to 1000, more preferably in the range of 250 to 1000, and even more preferably in the range of 250 to 800, 300 to A range of 700 is most preferred. The isocyanate index (INDEX) is calculated by the following method.

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

  The flame retardant urethane resin composition contains a catalyst, a foaming agent, a foam stabilizer, and an additive.

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

  The addition amount of the trimerization catalyst used in the flame retardant urethane resin composition is preferably in the range of 0.05 to 10 parts by weight and in the range of 0.2 to 8 parts by weight with respect to 100 parts by weight of the urethane resin. More preferably, it is in the range of 0.6 to 6 parts by weight, and most preferably in the range of 0.6 to 3.0 parts by weight.

  Preferable catalysts include a trimerization catalyst that causes the isocyanate group contained in the polyisocyanate compound, which is the main component of the polyurethane resin, to react and trimerize to promote the formation of an isocyanurate ring.

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

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

  The addition amount of the trimerization catalyst used in the flame retardant urethane resin composition is preferably in the range of 0.005 to 10 parts by weight and in the range of 0.01 to 8 parts by weight with respect to 100 parts by weight of the urethane resin. It is more preferable that it is 0.02 to 1.0 part by weight, and it is most preferable that it is 0.05 to 0.8 part by weight. When the amount is 0.005 parts by weight or more, there is no problem that the trimerization of isocyanate is inhibited. When the amount is 10 parts by weight or less, an appropriate foaming rate can be maintained, and handling is easy.

  The flame retardant urethane resin composition may contain a urethanization catalyst as a catalyst.

  The urethanization catalyst is a catalyst that causes a polymerization reaction simultaneously with the curing and urethanization reaction.

  Urethane catalysts include tertiary amine catalysts such as alkylated polyalkylene polyamines, triethylamine, triethylenediamine, N-ethylmorpholine, diethylethanolamine, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N′-trimethyl. Aminoethyl-ethanolamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, diaminobicyclooctane, 1,2-dimethyl Imidazole, 1-methylimidazole, 1-isobutyl-2-methylimidazole, bis (dimethylaminoethyl) ether, 1,8-diazabicyclo- [5,4,0] -undecene-7; metal catalysts such as octylic acid Stannous, dibutylstannic dilaurate, octylic acid ; And combinations thereof.

  The addition amount of the urethanization catalyst used in the flame retardant urethane resin composition is not limited, but is preferably in the range of 0 to 10 parts by weight, and 0.005 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. Is more preferable, and the range of 0.01 to 7 parts by weight is still more preferable.

  The foaming agent used for the flame retardant urethane resin composition promotes foaming of the urethane resin.

Specific examples of the blowing agent include, for example, water; hydrocarbons having a low boiling point such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane; dichloroethane, propyl chloride, isopropyl chloride, Chlorinated aliphatic hydrocarbon compounds such as butyl chloride, isobutyl chloride, pentyl chloride and isopentyl chloride; Fluorine compounds such as CHF ₃ , CH ₂ F ₂ and CH ₃ F; Trichloromonofluoromethane, trichlorotrifluoroethane, dichloromono Fluoroethane, (
For example, hydrochlorofluorocarbon compounds such as HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)); HFC-245fa (1,1 , 1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane) and other hydrofluorocarbons; ether compounds such as diisopropyl ether, HFO-1233zd (E) (trans -1-chloro-3,3,3-trifluoropropene), hydrofluoroolefins such as HFO-1234yf (2,3,3,3-tetrafluoro-1-propene); or organic compounds such as mixtures of these compounds System physical blowing agent, nitrogen gas, oxygen gas, argon gas, Inorganic physical foaming agents such as carbon oxide gas.

  The range of the blowing agent is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the urethane resin. The foaming agent is more preferably in the range of 0.1 to 18 parts by weight, still more preferably in the range of 0.5 to 18 parts by weight, with respect to 100 parts by weight of the urethane resin. Most preferred is in the range of parts by weight.

When the range of the foaming agent is 0.1 parts by weight or more, the formation of bubbles is promoted and a good foam is obtained. When the range is 30 parts by weight or less, the vaporization power is increased and the bubbles are prevented from becoming coarse. Can do.
Since the foaming agent can suppress the calorific value, it is preferable to use water, pentane, cyclopentane, hydrofluorocarbon, hydrofluoroolefin, more preferably water, hydrofluorocarbon, hydrofluoroolefin, and use water and hydrofluoroolefin in combination. It is preferable to do.

  Examples of the foam stabilizer used in the flame-retardant urethane resin composition 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 with respect to the urethane resin cured by the chemical reaction is appropriately set depending on the urethane resin cured by the chemical reaction to be used. For example, with respect to 100 parts by weight of the urethane resin, the amount of foam stabilizer is 0. It is preferable if it is in the range of 1 to 10 parts by weight.

  One or two or more of the catalyst, the foaming agent and the foam stabilizer can be used.

  Next, the additive used for the flame-retardant urethane resin composition of the present invention will be described.

  According to the invention, the additive comprises red phosphorus; and at least one of clay minerals, layered polysilicic acid and molybdenum compounds as essential components. In addition, the additive is red phosphorus; and at least one of clay mineral, layered polysilicic acid and molybdenum compound; boron-containing flame retardant, needle filler, phosphate ester, phosphate-containing flame retardant, bromine-containing It may contain at least one additive selected from the group consisting of a flame retardant, an antimony-containing flame retardant, and a metal hydroxide.

  In one embodiment, the additive is red phosphorus; and at least one of clay minerals, layered polysilicic acid, and molybdenum compounds; and phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, antimony-containing A flame retardant and at least one additive selected from the group consisting of metal hydroxides.

  In another embodiment, the additive is red phosphorus; and at least one of clay minerals, layered polysilicic acid and molybdenum compounds; and at least one of boron-containing flame retardants and needle fillers; and phosphate esters And at least one additive selected from the group consisting of a phosphate-containing flame retardant, a bromine-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide.

  The total amount of additives used in the present invention is preferably in the range of 6 to 70 parts by weight, more preferably in the range of 6 to 60 parts by weight, with respect to 100 parts by weight of the urethane resin, and 8.5. More preferably, it is in the range of ˜40 parts by weight.

  When the range of the additive is 6 parts by weight or more, flame retardancy can be exhibited, and when it is 70 parts by weight or less, foaming of the flame retardant urethane resin composition is not inhibited.

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

  The amount of red phosphorus used in the flame retardant urethane resin composition according to the present invention is not particularly limited, and is preferably in the range of usually 0.1 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. The range is more preferably in the range of 10 to 10 parts by weight, still more preferably in the range of 1.5 to 8 parts by weight, and most preferably in the range of 2 to 6 parts by weight. When the range of red phosphorus is 0.5 parts by weight or more, flame retardancy is exhibited, and when it is 20 parts by weight or less, toxicity and generation of carbon monoxide can be suppressed.

  Examples of the clay mineral include hydrotalcite, hydrotalcite-type layered double hydroxide, kaolinite, halloysite, sericite, montmorillonite, smectite, hectorite, saponite, vermiculite, talc and the like.

Hydrotalcite is a kind of carbonate mineral, for example, the composition formula Mg ₆ Al ₂ (CO ₃ ) (OH) ₁₆ · 4 (H ₂ O), Mg _3.5 Zn _0.5 Al ₂ (OH) ₁₂ (CO ₃ ) · 3H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ (CO ₃ ) · Clay mineral represented by 3.5H ₂ O. By adding hydrotalcite to the flame retardant urethane resin composition of the present invention, the generation of carbon monoxide is suppressed.

  Examples of the layered polysilicic acid include known polysilicic acids such as Kenyanite, Macatite, Kanemite, Magadiite, and Ilarite.

  The addition amount of each of the clay mineral and the layered polysilicic acid is preferably in the range of 0.1 to 20 parts by weight, and preferably in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. More preferably, it is still more preferably in the range of 1 to 5 parts by weight. When the hydrotalcite is 0.1 parts by weight or more, the generation of carbon monoxide is effectively suppressed. When the hydrotalcite is 20 parts by weight or less, the heat generation of the flame retardant urethane resin composition during heating is good.

  By adding the molybdenum compound to the flame retardant urethane resin composition of the present invention, the amount of carbon monoxide generated is suppressed. Examples of the molybdenum compound include ammonium molybdate and molybdenum trioxide.

  The addition amount of the molybdenum compound is preferably in the range of 0.1 to 20 parts by weight, more preferably in the range of 0.5 to 10 parts by weight, with respect to 100 parts by weight of the urethane resin. More preferably, it is in the range of parts by weight. When the molybdenum compound is 0.1 parts by weight or more, the generation of carbon monoxide is effectively suppressed, and when it is 20 parts by weight or less, the heat generation of the flame retardant urethane resin composition during heating is good.

  Examples of the boron-containing flame retardant used in the present invention include borax, boron oxide, boric acid, and borate. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.

  Examples of borates include alkali metals, alkaline earth metals, Group 4 elements, Group 12 elements, Group 13 elements, and ammonium borates. Specifically, as borate, alkali borate such as lithium borate, sodium borate, potassium borate, cesium borate, alkali borate such as magnesium borate, calcium borate, barium borate, etc. Examples include earth metal salts, zirconium borate, 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 two or more boron-containing flame retardants can be used.

  The amount of the boron-containing flame retardant used in the flame retardant urethane resin composition according to the present invention is not particularly limited, and is preferably in the range of 0.1 to 60 parts by weight with respect to 100 parts by weight of the urethane resin. The range is more preferably 0.1 to 40 parts by weight, and still more preferably 1 to 10 parts by weight.

  When the range of the boron-containing flame retardant is 0.1 parts by weight or more, the generation of carbon monoxide at the time of combustion of the flame retardant urethane resin composition according to the present invention is suppressed, and in the case of 60 parts by weight or less Manufacturing costs can be reduced.

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

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

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

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

  Examples of the plate-like inorganic filler include layered minerals such as flaky graphite, plate-like calcium carbonate, plate-like aluminum hydroxide, glass flakes, plate-like iron oxide, and metal plate-like materials.

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

  The addition amount of the acicular filler is preferably in the range of 3 to 30 parts by weight, more preferably in the range of 3 to 25 parts by weight, with respect to 100 parts by weight of the urethane resin. More preferably, it is in the range. When the acicular filler is 3 parts by weight or more and 30 parts by weight or less, the shape retention of the flame retardant urethane resin composition is good.

  In one embodiment, 3-30 parts by weight of acicular filler per 6-70 parts by weight of additive, preferably 3-25 parts by weight of acicular filler per 6-60 parts by weight of additive, more preferably 8. It is 3-18 parts by weight of acicular filler with respect to 5-40 parts by weight.

  The flame retardant urethane resin composition may further include at least one additive selected from the group consisting of a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide. Good. The amount of the at least one additive is preferably in the range of 0.1 to 60 parts by weight, more preferably in the range of 0.1 to 40 parts by weight with respect to 100 parts by weight of the urethane resin. More preferably, it is in the range of 1 to 10 parts by weight.

  Although the phosphate ester used for this invention is not specifically limited, It is preferable to use a 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, trixylyl phosphate, Tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, di- Phenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, Resorcinol 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-200, manufactured by Daihachi Chemical Industry Co., Ltd.). ), Hydroquinone poly (2,6-xylyl) phosphate and condensates thereof, resorcinol polyphenyl phosphate (trade name CR-733S, PFR), bisphenol A polycresyl phosphate (trade name CR-741, trade name FP-600) FP-700), aromatic condensed phosphate ester (trade name CR747), and the like.

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

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

  The amount of the phosphate ester added is preferably in the range of 2.5 to 50 parts by weight, more preferably in the range of 2.5 to 40 parts by weight, with respect to 100 parts by weight of the urethane resin. More preferably, it is in the range of 5 to 30 parts by weight.

  When the phosphoric ester range is 2.5 parts by weight or more, flame retardancy is imparted to the flame retardant urethane resin composition, and when it is 50 parts by weight or less, the viscosity of the flame retardant urethane resin composition is maintained. Is done.

  The phosphate-containing flame retardant contains phosphoric acid. The phosphoric acid used in 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.

  Examples of the phosphate-containing flame retardant include at least one selected from 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. The phosphate which consists of a salt with these metals or compounds can be mentioned.

  Examples of the metals of Group IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.

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

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

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

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

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

  Although not particularly limited as the monophosphate, for example, ammonium salts such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, Sodium salts such as disodium phosphite and sodium hypophosphite, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, potassium hypophosphite, etc. Potassium salts, lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, lithium hypophosphite, etc., barium dihydrogen phosphate, barium hydrogen phosphate , Barium salts such as tribarium phosphate and barium hypophosphite, magnesium monohydrogen phosphate, magnesium hydrogen phosphate, lithium Magnesium salts such as trimagnesium phosphate, magnesium hypophosphite, calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite, zinc phosphate, zinc phosphite, hypophosphorous acid Examples thereof include zinc salts such as zinc acid, aluminum salts such as primary aluminum phosphate, secondary aluminum phosphate, tertiary aluminum phosphate, aluminum phosphite, and aluminum hypophosphite.

  Among these, primary aluminum phosphate, secondary aluminum phosphate, and tertiary aluminum phosphate are preferable, and primary aluminum phosphate is more preferable.

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

  Although there is no limitation in particular in the addition amount of the phosphate containing flame retardant used for this invention, it is preferable that it is the range of 0.1-60 weight part with respect to 100 weight part of urethane resins, and 0.1-20 The range is more preferably in the range of parts by weight, still more preferably in the range of 0.1 to 10 parts by weight, and most preferably in the range of 1.0 to 5 parts by weight.

  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 a brominated aromatic ring-containing aromatic compound.

Specific examples of the brominated aromatic ring-containing aromatic compound include, for example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis Monomeric organic bromine compounds such as (pentabromophenoxy) ethane, ethylenebis (pentabromophenyl), ethylenebis (tetrabromophthalimide), tetrabromobisphenol A,
Brominated polycarbonate such as polycarbonate oligomer produced from brominated bisphenol A as a raw material, copolymer of 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 more bromine-containing flame retardants can be used.

  Although there is no limitation in particular in the addition amount of the bromine containing flame retardant used for this invention, it is preferable that it is the range of 0.1-60 weight part with respect to 100 weight part of urethane resins, 0.1-50 weight part Is more preferable, and it is still more preferable that it is the range of 0.1-40 weight part.

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

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

  Although there is no limitation in particular in the addition amount of the antimony containing flame retardant used for this invention, it is preferable that it is the range of 0.1-60 weight part with respect to 100 weight part of urethane resins, 0.1-50 weight part 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.

  Furthermore, the flame retardant urethane resin composition is a range that does not impair the object of the present invention, and if necessary, one or more inorganic fillers other than the above-mentioned needle-like filler, phenol-based, amine-based , Sulfur-based antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, tackifier resins and other auxiliary components, polybutenes, petroleum resins, etc. An imparting agent can be included.

  Since the flame retardant urethane resin composition reacts and cures, its viscosity changes over time. Therefore, before using the flame retardant urethane resin composition, the flame retardant urethane resin composition is divided into two or more to prevent the flame retardant urethane resin composition from reacting and curing. And when using a flame-retardant urethane resin composition, a flame-retardant urethane resin composition is obtained by putting together the flame-retardant urethane resin composition divided | segmented into two or more.

  In addition, when dividing the flame retardant urethane resin composition into two or more, each component of the flame retardant urethane resin composition divided into two or more does not start to cure, and each of the flame retardant urethane resin composition Each component may be divided so that the curing reaction starts after the components are mixed.

  In one embodiment, the flame retardant urethane resin composition has a catalyst in the range of 0.6 to 10 parts by weight (particularly 0.6 to 10 parts by weight based on 100 parts by weight of a urethane resin composed of a polyisocyanate compound and a polyol compound. Trimerization catalyst in the range of parts by weight), 0.1 to 30 parts by weight of blowing agent, foam stabilizer in the range of 0.1 to 10 parts by weight, and additive in the range of 6 to 70 parts by weight. In the additive, red phosphorus is 1 to 10 parts by weight, boron-containing flame retardant is 0.1 to 60 parts by weight, and filler is 3 to 30 parts by weight.

  The method for producing the flame retardant urethane resin composition is not particularly limited. For example, the method of mixing the components of the flame retardant urethane resin composition, the flame retardant urethane resin composition suspended in an organic solvent, A method of heating and melting to form a paint, a method of preparing a slurry by dispersing in a solvent, and the reaction curable resin component contained in the flame retardant urethane resin composition at room temperature (about 25 ° C.) When a component that is solid at the temperature is contained, the flame retardant urethane resin composition can be obtained by a method such as melting the flame retardant urethane resin composition under heating.

  The flame retardant urethane resin composition is a single-screw extruder, twin-screw extruder, Banbury mixer, kneader mixer, kneading roll, lykai machine, planetary agitator, high-pressure foaming. It can be obtained by kneading using a known apparatus such as a machine or a low pressure foaming machine.

  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 flame retardant urethane resin composition excluding the catalyst and the catalyst can be kneaded in the same manner immediately before injection. A flame-retardant urethane resin composition can be obtained by the method described above.

  Next, the curing method of the flame retardant urethane resin composition according to the present invention will be described.

  When each component of the flame retardant urethane resin composition is mixed, the reaction starts, the viscosity increases with the passage of time, and fluidity is lost.

  For example, a molded body made of a flame retardant urethane resin composition can be obtained as a foam by injecting the flame retardant urethane resin composition into a container such as a mold or a frame material and curing it. Or the molded object which consists of a flame-retardant urethane resin composition can be obtained as a foam by spraying and curing a flame-retardant urethane resin composition to a to-be-coated structure.

  When obtaining the molded object which consists of a flame-retardant urethane resin composition, heat can be added or a pressure can be applied.

The thickness of the molded product of the present invention is not particularly limited, but is preferably 1 to 200 mm, more preferably 20 to 200 mm, still more preferably 20 to 100 mm, and further preferably 20 to 50 mm. Most preferred.
When used in a place where low toxicity is required, the total calorific value when heated for 5 minutes using a corn calorimeter is 8 MJ / m in accordance with the test method of ISO-5660 from the safety in case of fire. ² or less and the carbon monoxide concentration peak top are required to be 150 ppm or less.

  Next, application examples of the flame retardant urethane resin composition according to the present invention will be described.

  The flame retardant urethane resin composition can be molded into a thin panel and placed on structures such as buildings, furniture, automobiles, trains, and ships. Or the foam layer which consists of a flame-retardant urethane resin composition can be formed in the surface of a structure by spraying a flame-retardant urethane resin composition on the said structure.

  Next, a fire resistance test performed on the molded body of the present invention will be described.

A molded body made of the flame-retardant urethane resin composition of the present invention is cut into a length of 100 mm, a width of 100 mm and a thickness of 25 mm to prepare a sample for corn calorimeter test. Using this corn calorimeter test sample, the total calorific value by the corn calorimeter test when heated at a radiant heat intensity of 50 kW / m ^{2 for} 5 minutes in accordance with the test method of ISO-5660 is 8 MJ / m ² or less. is there. In addition, the standard that the total calorific value at the time of heating for 5 minutes is 8 MJ / m ² or less is the flame resistance standard of flame retardancy in Japan.

  Similarly, the carbon monoxide concentration is measured according to the test method of ISO-5660.

Moreover, the molded object which consists of a flame-retardant urethane resin composition of this invention is a 100 mm x 100 mm x 25 mm (length direction x width direction x thickness direction) molded object according to the ISO-5660 test method, radiant heat intensity 50kW / m < ² >. When heated for 5 minutes, cracking and harmful shrinkage do not occur in the molded body after heating.

  Hereinafter, although an example is described, the present invention is not limited to these.

Test Example 1 Production of Foam Molded Body Composed of Flame Retardant Urethane Resin Composition Production of Foam Molded Body Composed of Flame Retardant Urethane Resin Composition According to the formulation shown in Table 1, flame retardant urethane resin compositions according to Examples 1 to 12 and Comparative Examples 1 to 4 were prepared. Details of each component in the table are as follows.

(1) Polyol compound (A-1) p-phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RFK-505, hydroxyl value = 250 mgKOH / g)
(2) Catalyst (B-1) Trimerization catalyst (potassium octylate, manufactured by Momentive Performance Materials, product name: K-Zero G)
(B-2) Trimerization catalyst (manufactured by Tosoh Corporation, product name: TOYOCAT-TR20)
(B-3) Urethane catalyst (pentamethyldiethylenetriamine, manufactured by Tosoh Corporation, product name: TOYOCAT-DT)
(3) Foam stabilizer Polyalkylene glycol foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193)
(4) Foaming agent (C-1) pure water (C-2) HFC HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Nippon Solvay) and HFC-245fa (1,1, 1,3,3-pentafluoropropane (manufactured by Central Glass Co., Ltd.), mixing ratio HFC-365mfc: HFC-245fa = 7: 3, hereinafter referred to as “HFC”)
(C-3) Cyclopentane (manufactured by Tokyo Chemical Industry Co., Ltd.)
(C-4) HFO (trans-1-chloro-3,3,3-trifluoropropene, manufactured by Honeywell, product name: Solstice LBA)
(5) Isocyanate compound (hereinafter referred to as “polyisocyanate compound”)
MDI (manufactured by Tosoh Corporation, product name: Millionate MR-200) Viscosity: 167 mPa · s, NCO content = 32.1%
(6) Additive (D-1) Red phosphorus (Rin Chemical Industry Co., Ltd., product name: Nova Excel 140)
(D-2) Acicular filler wollastonite (SiO ₂ · CaO) (manufactured by Kinsei Matec Co., Ltd., product name: SH-1250) aspect ratio 10-16, average particle size 4.5-6.5 μm
(D-3) Zinc borate (product name: Firebrake ZB, manufactured by Hayakawa Shoji Co., Ltd.)
(D-4) Hydrotalcite (manufactured by Sakai Chemical Co., Ltd., product name: HT-1)
(D-5) Primary aluminum phosphate (product name: 100P, manufactured by Taki Chemical Co., Ltd.)
(D-6) Montmorillonite (Kunimine Industries, product name: Kunipia F)
(D-7) Talc (Product name: P-2, manufactured by Nippon Talc Co., Ltd.)
(D-8) Ammonium molybdate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd., product name: TF-2000)
(D-9) Cresyl diphenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name: CDP)
(D-10) Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)
According to the composition of Table 1 below, the polyol compound of (1), excluding the polyisocyanate compound of (5) and the HFC, HFO or cyclopentane component of (C-2) to (C-4), Various catalysts, (3) foam stabilizer, (4) foaming agent, and (6) additive were weighed into a 1000 mL polypropylene beaker and stirred with a hand mixer at 25 ° C. for 10 seconds. Add the polyisocyanate compound (5) and the HFC, HFO or cyclopentane component (C-2) to (C-4) to the kneaded product after stirring and worship for about 10 seconds with a hand mixer. A foam was created. The obtained flame-retardant urethane resin composition lost fluidity with the passage of time, and foamed molded articles of the flame-retardant urethane resin compositions of Examples 1 to 12 and Comparative Examples 1 to 4 were obtained.

Test Example 2 Evaluation of Molded Body The foam molded body of the flame retardant urethane resin composition produced in Test Example 1 was evaluated for the following items.

(1) Measurement of density Cut out from the cured product to be 100 mm x 100 mm x 25 mm (length direction x width direction x thickness direction), measure the dimensions using calipers, measure the mass with an electronic balance, and measure the density. It was measured. The results are shown in Table 1.

(2) Measurement of total calorific value A molded body cut out from a cured product so as to be 100 mm × 100 mm × 25 mm (length direction × width direction × thickness direction) is used as a corn calorimeter test sample, and conforms to ISO-5660. The mixture was heated at a radiant heat intensity of 50 kW / m ^{2 for} 5 minutes. The results are shown in Table 1.

The total calorific value of the corn calorimeter when heated for 5 minutes was 8 MJ / m ² or less in all of Examples 1 to 12, and the molded product of the present invention was excellent in flame retardancy.

The sample of Example 2 was also measured for the total calorific value of the corn calorimeter when heated for 10 minutes and heated for 20 minutes, and the total calorific value of each sample was 8 MJ / m ² or less.

(3) CO concentration measurement Based on the test method of ISO-5660, the peak value of the carbon monoxide concentration at the time of combustion of the sample of said (2) was measured.

  While the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to the above-described embodiments, and various modifications based on the technical idea of the present invention are possible.

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

The configurations, methods, steps, shapes, materials, numerical values, and the like of the above-described embodiments can be combined with each other without departing from the gist of the present invention.
The present invention can also employ the following configurations.
[Item 1] A flame retardant urethane resin composition comprising a polyisocyanate compound, a polyol compound, a catalyst, a foaming agent, a foam stabilizer, and an additive, the additive being red phosphorus; and clay minerals, layered polysilicic acid, and A flame retardant urethane resin composition comprising at least one of molybdenum compounds.
[Item 2] The flame-retardant urethane resin composition according to [Item 1], wherein the catalyst contains a trimerization catalyst.
[Item 3] The flame-retardant urethane resin composition according to [Item 1], wherein the amount of red phosphorus is in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the urethane resin.
[Item 4] The flame-retardant urethane resin composition according to [Item 1], wherein the amount of red phosphorus is in the range of 1.5 to 8 parts by weight with respect to 100 parts by weight of the urethane resin.
[Claim 5] The flame retardant urethane resin composition according to any one of [Claim 1] to [Claim 4], wherein the additive further contains at least one of a boron-containing flame retardant and an acicular filler.
[Claim 6] The flame-retardant urethane resin composition according to any one of [Claim 1] to [Claim 5], wherein the amount of the boron-containing flame retardant is in the range of 0.1 to 60 parts by weight.
[Claim 7] The flame-retardant urethane resin composition according to any one of [Claim 1] to [Claim 5], wherein the amount of the boron-containing flame retardant is in the range of 1 to 10 parts by weight.
[Item 8] The flame-retardant urethane resin composition according to any one of items [1] to [7], wherein the boron-containing flame retardant is a borate.
[Item 9] The flame-retardant urethane resin composition according to [Item 8], wherein the boron-containing flame retardant is a borate.
[Claim 10] The flame-retardant urethane resin composition according to any one of [Claim 1] to [Claim 9], wherein the amount of the acicular filler is in the range of 3 to 30 parts by weight with respect to 100 parts by weight of the urethane resin.
[Item 11] The flame-retardant urethane resin composition according to any one of items [1] to [9], wherein the amount of the needle filler is in the range of 3 to 25 parts by weight with respect to 100 parts by weight of the urethane resin.
[Item 12] The flame-retardant urethane resin composition according to any one of [Item 1] to [Item 9], wherein the amount of the needle-like filler is in the range of 3 to 18 parts by weight with respect to 100 parts by weight of the urethane resin.
[Claim 13] The flame retardant urethane resin composition according to any one of [Claim 1] to [Claim 12], wherein the additive is in the range of 0.1 to 60 parts by weight with respect to 100 parts by weight of the urethane resin. object.
[Item 14] The flame-retardant urethane resin composition according to any one of items [1] to [13], which is 3 to 30 parts by weight of an acicular filler with respect to 6 to 70 parts by weight of the additive.
[Item 15] The flame-retardant urethane resin composition according to any one of items [1] to [13], which is 3 to 25 parts by weight of an acicular filler with respect to 6 to 60 parts by weight of the additive.
[Item 16] The flame-retardant urethane resin composition according to any one of items [1] to [13], which is 3 to 18 parts by weight of an acicular filler with respect to 8.5 to 40 parts by weight of the additive.
[Item 17] The flame-retardant urethane resin composition according to any one of items [1] to [16], wherein the additive includes a boron-containing flame retardant and an acicular filler.
[Item 18] The flame-retardant urethane resin composition according to any one of items [1] to [17], wherein the additive contains a clay mineral.
[Item 19] The flame-retardant urethane resin composition according to any one of items [1] to [18], wherein the clay mineral is hydrotalcite or montmorillonite.
[Item 20] The flame-retardant urethane resin composition according to any one of [Item 1] to [Item 19], wherein the amount of the clay mineral is in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. object.
[Claim 21] The flame-retardant urethane resin composition according to any one of [Claim 1] to [Claim 19], wherein the amount of the clay mineral is in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. object.
[Item 22] The flame-retardant urethane resin composition according to any one of [Item 1] to [Item 19], wherein the amount of the clay mineral is in the range of 1 to 5 parts by weight with respect to 100 parts by weight of the urethane resin.
[Item 23] The additive further includes at least one additive selected from the group consisting of phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, antimony-containing flame retardants, and metal hydroxides. ] The flame-retardant urethane resin composition in any one of [Item 22].
[Item 24] The additive further comprises a phosphate ester and at least one additive selected from the group consisting of a phosphate-containing flame retardant, a bromine-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide. The flame retardant urethane resin composition according to any one of [Item 1] to [Item 22].
[Item 25] The flame-retardant urethane resin composition according to Item 21 or Item 24, wherein the amount of the phosphate ester is in the range of 2.5 to 50 parts by weight with respect to 100 parts by weight of the urethane resin.
[Claim 26] The flame retardant urethane resin composition according to [Claim 22] or [Claim 24], wherein the at least one additive is in the range of 0.1 to 60 parts by weight with respect to 100 parts by weight of the urethane resin. object.
[Item 27] The flame-retardant urethane resin composition according to any one of items [1] to [26], wherein the molybdenum compound is selected from ammonium molybdate and molybdenum trioxide.
[Item 28] The flame-retardant urethane resin composition according to any one of items [1] to [27], wherein the amount of the molybdenum compound is in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. .
[Item 29] The flame-retardant urethane resin composition according to any one of items [1] to [27], wherein the amount of the molybdenum compound is in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. .
[Item 30] The flame-retardant urethane resin composition according to any one of items [1] to [27], wherein the amount of the molybdenum compound is in the range of 1 to 5 parts by weight with respect to 100 parts by weight of the urethane resin.
[Item 31] A molded article comprising the flame-retardant urethane resin composition according to any one of [Item 1] to [Item 30].

Claims (6)

  A flame retardant urethane resin composition comprising a polyisocyanate compound, a polyol compound, a catalyst, a foaming agent, a foam stabilizer, and an additive, the additive being red phosphorus; and among clay minerals, layered polysilicic acid and molybdenum compounds A flame retardant urethane resin composition comprising:   The flame retardant urethane resin composition according to claim 1, wherein the catalyst contains a trimerization catalyst.   The flame-retardant urethane resin composition according to claim 1 or 2, wherein the additive further contains at least one of a boron-containing flame retardant and an acicular filler.   The flame retardant urethane resin composition according to claim 1, wherein the boron-containing flame retardant is a borate.   Based on 100 parts by weight of a urethane resin composed of a polyisocyanate compound and a polyol compound, red phosphorus is in the range of 0.1 to 20 parts by weight, boron-containing flame retardant is in the range of 0.1 to 20 parts by weight, and the needle filler is 3 The flame retardant urethane resin composition according to claim 3 or 4, wherein at least one of -30 parts by weight, clay mineral, layered polysilicic acid, and molybdenum compound is 0.1-20 parts by weight.   The molded object which consists of a flame-retardant urethane resin composition as described in any one of Claims 1-5.