URETHANE RESIN COMPOSITION

Abstract

For achieving a predetermined flame retardancy, a urethane resin composition comprises a polyisocyanate compound, a polyol compound, a catalyst, a foaming agent, ammonium polyphosphate, and phosphoric ester, and is free from red phosphorus.

Claims

1. A urethane resin composition for forming a foam body serving as a thermal insulation material for a building as a result of being sprayed on the building, the urethane resin composition comprising: a polyisocyanate compound, a polyol compound, a catalyst, a foaming agent, ammonium polyphosphate, and phosphoric ester, the urethane resin composition being free from red phosphorus, wherein the foaming agent includes water, wherein the foam body is equivalent to a quasi-uninflammable material defined in a heat release test in conformity with ISO-5660, and wherein the ammonium polyphosphate and the phosphoric ester are set in amount, respectively, in any one of the following ranges: range (A) where an amount of the ammonium polyphosphate is 20 parts by weight or more and 75 parts by weight or less, and an amount of the phosphoric ester is 40 parts by weight or more and 80 parts by weight or less, per 100 parts by weight of the polyol compound; range (B) where an amount of the ammonium polyphosphate is 20 parts by weight or more and 100 parts by weight or less, and an amount of the phosphoric ester is 60 parts by weight or more and 80 parts by weight or less, per 100 parts by weight of the polyol compound; range (C) where an amount of the ammonium polyphosphate is 40 parts by weight or more and 75 parts by weight or less, and an amount of the phosphoric ester is 40 parts by weight or more and 140 parts by weight or less, per 100 parts by weight of the polyol compound; range (D) where an amount of the ammonium polyphosphate is 40 parts by weight or more and 100 parts by weight or less, and an amount of the phosphoric ester is 60 parts by weight or more and 140 parts by weight or less, per 100 parts by weight of the polyol compound; and range (E) where an amount of the ammonium polyphosphate is 40 parts by weight or more and 125 parts by weight or less, and an amount of the phosphoric ester is 140 parts by weight, per 100 parts by weight of the polyol compound.

2. The urethane resin composition according to claim 1, further comprising kaolinite.

3. The urethane resin composition according to claim 2, wherein the kaolinite is fired kaolin.

4. The urethane resin composition according to claim 1, further comprising at least one selected from the group consisting of foam stabilizer, surface conditioner, and compatibilizer.

5. The urethane resin composition according to claim 1, further comprising a trimerization catalyst as the catalyst.

6. A urethane resin composition for forming a foam body serving as a thermal insulation material for a building as a result of being sprayed on the building, the urethane resin composition comprising: a polyisocyanate compound, a polyol compound, a catalyst, a foaming agent, ammonium polyphosphate, and phosphoric ester, the urethane resin composition being free from red phosphorus, wherein the foaming agent includes water, wherein the foam body is equivalent to an uninflammable material defined in a heat release test in conformity with ISO-5660, and wherein the ammonium polyphosphate and the phosphoric ester are set in amount, respectively, in any one of the following ranges: range (F) where an amount of the ammonium polyphosphate is 20 parts by weight or more and 75 parts by weight or less, and an amount of the phosphoric ester is 40 parts by weight or more and 80 parts by weight or less, per 100 parts by weight of the polyol compound; range (G) where an amount of the ammonium polyphosphate is 40 parts by weight or more and 75 parts by weight or less, and an amount of the phosphoric ester is 40 parts by weight or more and 120 parts by weight or less, per 100 parts by weight of the polyol compound; range (H) where an amount of the ammonium polyphosphate is 40 parts by weight or more and 100 parts by weight or less, and an amount of the phosphoric ester is 60 parts by weight or more and 120 parts by weight or less, per 100 parts by weight of the polyol compound; and range (I) where an amount of the ammonium polyphosphate is 75 parts by weight or more and 100 parts by weight or less, and an amount of the phosphoric ester is 60 parts by weight or more and 140 parts by weight or less, per 100 parts by weight of the polyol compound.

7. The urethane resin composition according to claim 6, further comprising kaolinite.

8. The urethane resin composition according to claim 7, wherein the kaolinite is fired kaolin.

9. The urethane resin composition according to claim 6, further comprising at least one selected from the group consisting of foam stabilizer, surface conditioner, and compatibilizer.

10. The urethane resin composition according to claim 6, further comprising a trimerization catalyst as the catalyst.

Description

BRIEF DESCRIPTIONS OF THE DRAWINGS

[0038] FIG. 1 depicts a view of photographs for comparison in foam body hue among Experimental EXAMPLES 53, 54.

[0039] FIG. 2 depicts a view of photographs for comparison in foam body hue among Experimental EXAMPLES 55 to 57.

DESCRIPTIONS OF EMBODIMENTS OF THE INVENTION

<1> Entire Composition Of Components

[0040] A urethane resin composition according to an embodiment of the present invention is a composition for forming a foam body having a thermal insulation material for a building and at least including a polyisocyanate compound, a polyol compound, a catalyst, a foaming agent, and a flame retardant.

[0041] The urethane resin composition according to an embodiment of the present invention can include a mineral-derived material such as clay mineral.

[0042] A thermal insulation layer may be formed in a building, for example, by: a method in which a polyisocyanate compound (first liquid) and other components (second liquid) are separately prepared and the first and second liquids are mixed while being atomized, and then sprayed; or a method in which the first and second liquids are sprayed while being mixed together.

<2> Properties

[0043] The urethane resin composition according to an embodiment of the present invention may have the following properties achieved by adjusting the formulation of materials.

<2.1> Incombustibility (Non-Combustibility)

[0044] The urethane resin composition according to an embodiment of the present invention can serve as uninflammable material or as a quasi-uninflammable material in conformity with ISO-5660.

<2.2> ISO-5660 Test

[0045] In a heat release test in conformity with ISO-5660, test equipment called a cone calorimeter is used.

[0046] The cone calorimeter includes a cone heater disposed above a specimen cut into a predetermine size, and a spark rod provided between the specimen and the cone heater. The specimen is heated by the cone heater to produce a flammable gas, and the flammable gas is ignited by sparks from the spark rod to cause combustion. The gross calorific value or the like obtained from the combustion is measured by a predetermined measuring method so that the flame retardancy is evaluated in light of the performance requirements shown in Table 1 below.

TABLE-US-00001 TABLE 1 Type Performance requirements Uninflammable (1) Gross calorific value is 8 MJ/m.sup.2 or less for 20 min material after heat starts. (2) There is no crack or through-hole up to rear surface harmful to fire prevention for 20 min after heat starts. (3) Heat release rate does not consecutively exceed 200 kW/m.sup.2 for duration of time exceeding 10 sec for 20 min after heat starts. Quasi- (1) Gross calorific value is 8 MJ/m.sup.2 or less for 10 min uninflammable after heat starts. material (2) There is no crack or through-hole up to rear surface harmful to fire prevention for 10 min after heat starts. (3) Heat release rate does not consecutively exceed 200 kW/m.sup.2 for duration of time exceeding 10 sec for 10 min after heat starts. Flame-retardant (1) Gross calorific value is 8 MJ/m.sup.2 or less for 5 min material after heat starts. (2) There is no crack or through-hole up to rear surface harmful to fire prevention for 5 min after heat starts. (3) Heat release rate does not consecutively exceed 200 kW/m.sup.2 for duration of time exceeding 10 sec for 5 min after heat starts. [0047] Japan Testing Center for Construction Material Fire resistance qualification test-evaluation operation method report Excerpt-version from Fire resistance qualification evaluation stipulated on: Jun. 1, 2000 (Hei-12); latest updated on: Jul. 1, 2021 https://www.jtccm.or.jp/Portals/0/resources/library/jtccm/seino/siryo/bassui/boukazairy ou.pdf

<2.3> Density

[0048] The foam body of the urethane resin composition according to an embodiment of the present invention can have a density of 30 kg/m.sup.3 or more.

[0049] When the foam body has a density of 30 kg/m.sup.3 or more, the effect of sufficiently suppressing deformation against external impact can be obtained when used as a thermal insulation material for a building.

<3> Polyisocyanate Compound

[0050] The polyisocyanate compound is a material to be used as a main agent in the urethane resin composition according to an embodiment of the present invention.

[0051] Examples of the polyisocyanate compound include aromatic polyisocyanate, alicyclic polyisocyanate, aliphatic polyisocyanate, modified polyisocyanate, and the like.

[0052] 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.

[0053] Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, dimethyldicyclohexylmethane diisocyanate, and the like.

[0054] Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and the like.

[0055] Examples of the modified polyisocyanate include isocyanate-terminated prepolymers in which a polyol component is reacted with a polyisocyanate compound. Examples include urethane modified products, carbodiimide modified products, urea modified products, biuret modified products, and allophanate modified products.

[0056] The polyisocyanate compounds may be used alone or in combination of two or more.

[0057] Especially, polymethylene polyphenyl polyisocyanate (polymeric MDI, crude MDI) is preferred because it is liquid at room temperature and easily available.

[0058] Examples of the polymethylene polyphenyl polyisocyanate include Millionate MR-200, MR-100, and MR-400 available from Tosoh Corporation, Sumidur 44 V20L and Desmodur 44 V20L available from Covestro AG, PM-200 and PM-400 available from Wanhua Chemical Group Co., Ltd., and PAPI27 and PAPI135 available from Dow Inc.

[0059] It is preferable that the polyisocyanate is contained in the urethane resin composition in such an amount that the isocyanate index is 150 to 1000. When the isocyanate index is 150 or more, the flame retardancy is even better. When the isocyanate index is 1000 or less, the adhesion to a building structure or the like is good.

[0060] In particular, in an embodiment of the present invention, the isocyanate index is most preferably within a range of 400 to 800.

[0061] The isocyanate index is calculated as the equivalent ratio of isocyanate groups contained in the isocyanate component to active hydrogen contained in the polyol component, water of the foaming agent, and the like.

[00001]$\left[\mathrm{Isocyanate}\mathrm{group}\right]/\left[\mathrm{OH}\mathrm{group}\right]\left(\mathrm{mol}\mathrm{ratio}\right)100$

<4> Polyol Compound

[0062] The polyol compound is a material to be used as a curing agent in the urethane resin composition according to an embodiment of the present invention.

[0063] The polyol compound includes an ester-based polyol compound or an ether-based polyol compound, and a combination thereof.

<4.1> Ester-Based Polyol Compound

[0064] Examples of the ester-based polyol compound include a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, a polymer obtained by ring-opening polymerization of lactone such as -caprolactone or -methyl--caprolactone, and a condensate of a hydroxycarboxylic acid and the polyhydric alcohol.

[0065] More specifically, examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, succinic acid, and the like. Terephthalic acid modification is preferred in terms of flame retardancy.

<4.2> Other Polyol Compounds

[0066] Examples of other polyol compounds include polylactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polymer polyol, polyether polyol, and the like.

[0067] Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, polyvalerolactone glycol, and the like.

[0068] Examples of the polycarbonate polyol include polyols obtained by a dealcoholization reaction between: a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, or nonanediol; and diethylene carbonate, dipropylene carbonate or the like.

[0069] Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, cresol novolac, and the like.

[0070] Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, dimethyldicyclohexylmethanediol, and the like.

[0071] Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, and the like.

[0072] Examples of the polyfunctional polyether polyol include: low molecular weight polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A, bis (B-hydroxyethyl)benzene, xylene glycol, glycerin, trimethylolpropane, pentaerythritol, and sucrose; or polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and the like with compounds having 2 or more, preferably 3 to 8 active hydrogen groups, as initiators having aromatic and aliphatic polyamines such as ethylenediamine, propylenediamine, toluene diamine, metaphenylenediamine, diphenylmethane diamine, xylylenediamine, triethanolamine; or polyether polyols obtained by ring-opening polymerization of alkyl glycidyl ethers such as methyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether, and cyclic ether monomers such as tetrahydrofuran. In addition, polyether polyols containing bromine, phosphorus, and the like may be used.

<5> Mineral-Derived Material

[0073] The mineral-derived material is a material for improving the flame retardancy and realizing a higher density.

[0074] A silicate compound is preferred as the mineral-derived material. For example, montmorillonite, saponite, hectorite, vermiculite, kaolinite, mica, talc, and the like may be used as the mineral-derived material.

[0075] An example including the kaolinite as a main component is kaolin.

[0076] The kaolin includes fired kaolin obtained by subjecting kaolin to high temperature treatment. The fired kaolin is preferred in that it has a low water content and a small particle diameter distribution.

[0077] The amount of the mineral-derived material is preferably, but not limited to, 3 to 85 parts by weight per 100 parts by weight of the polyol compound.

<6> Catalyst

[0078] The catalyst to be used to form a urethane foam is a material for promoting a reaction between isocyanate and active hydrogen in polyol and a reaction between isocyanate and water.

[0079] Hereinafter, an example of the catalyst will be explained.

<6.1> Trimerization Catalyst

[0080] The trimerization catalyst is a material for causing a reaction to occur among isocyanate groups included in the polyisocyanate compounds so as to trimerize the isocyanate groups thereby promoting the formation of an isocyanurate ring.

[0081] For such a trimerization catalyst, for example, nitrogen-containing aromatic compounds such as tris (dimethylaminomethyl) phenol, 2,4-bis(dimethylaminomethyl) phenol, and 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine; carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate, and potassium octylate; and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, and tetraphenylammonium salt may be used as the catalyst.

[0082] A combination of carboxylic acid alkyl metal salts and quaternary ammonium salts is preferred in terms of adhesion and flame retardancy at low temperatures.

[0083] Examples of the trimerization catalyst include Toyocat-TRX, Toyocat-TRV, and Toyocat-TR20 available from Tosoh Corporation, DABCO TMR, DABCO TMR-2, DABCO TMR-7, DABCO K-15, UCAT 18X, and POLYCAT 46 available from Evonik, and KAOLIZER NO. 410 and KAOLIZER NO. 420 available from Kao Corporation.

[0084] The amount of the trimerization catalyst may be set appropriately within such a range that a predetermined flame retardancy can be obtained, and is preferably, but not limited to, 1 to 20 parts by weight per 100 parts by weight of the polyol compound. When the amount of the trimerization catalyst is 1 part by weight or more, the flame retardancy is even better. When the amount of the trimerization catalyst is 20 parts by weight or less, any inconvenience such as clogging in a mixing part of a spray gun because of too fast reaction can be prevented.

<6.2> Other Catalysts

[0085] As other catalysts, there may be adopted catalyst having amino groups and catalyst containing organic metals.

[0086] Examples of catalysts having amino groups include N-alkyl polyalkylene polyamines such as triethylenediamine, N,N,N,N,N-pentamethyldiethylenetriamine, N,N,N,N-tetramethyl-1,6-hexanediamine, and N,N,N,N-tetramethylethylenediamine, N-(2-hydroxyethyl)-N,N,N-trimethylethylenediamine, 1-(2-dimethylaminoethyl)-4-methylpiperazine, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, N-methylmorpholine, N-ethylmorpholine, N,N-dimethylaminoethylmorpholine, dimethylcyclocyclohexylamine dimethylethanolamine, dimethylaminohexanol, dimethylaminoethoxyethanol, and diazabicycloundecene.

[0087] Product examples of the amine catalysts include TEDA-L33, TOYOCAT-ET, TOYOCAT-MR, TOYOCAT-TE, TOYOCAT-DT, TOYOCAT-NP, RX-5, RX-10, and TOYOCAT-DM70 available from Tosoh Corporation, DABCO 33LV, DABCO BL-19, DABCO BL-11, DABCO DMEA, DABCO T, DABCO N-MM, DABCO N-EM, DABCO XDM, DABCO NC-IM, POLYCAT 201, and POLYCAT 204 available from Evonik, and KAOLIZER NO. 1, KAOLIZER NO. 3, KAOLIZER NO. 10, KAOLIZER NO. 31, KAOLIZER NO. 21, KAOLIZER NO. 22, KAOLIZER NO. 25, KAOLIZER NO. 26, KAOLIZER NO. 120, KAOLIZER NO. 300, KAOLIZER NO. 350, and KAOLIZER NO. 390 available from Kao Corporation.

[0088] Further, examples of catalysts containing organometallics include bismuth octylate, lead octylate, tin (II) 2-ethylhexanoate, dibutyl bis [(1-oxooctyl)oxy] stannane, dibutyltin diacetate, and dibutyltin dilaurate.

[0089] Product examples of organometallic catalysts include BiCAT 8210 available from The Shepherd Chemical Company and the like.

[0090] These catalysts may be used alone or in combination of two or more.

<7> Foaming Agent

[0091] The foaming agent is a material for promoting density reduction of a formed product, because gas is produced in the resin when the polyisocyanate compound (first liquid) and other components (second liquid) are mixed.

[0092] The foaming agent is, for example, water. Water reacts with Isocyanate reacts with to produce carbon dioxide, which is trapped in the foam body, thereby promoting density reduction of the formed product.

[0093] Other examples of the foaming agent include what is called physical foaming agents as listed below. The physical foaming agent is liquid at room temperature and is gasified in the resin due to a heat release reaction between isocyanate and polyol to promote density reduction of the formed product.

[1] Hydrocarbon Compound

[0094] Propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, methyl formate, etc.

[2] Chlorinated Aliphatic Hydrocarbon Compound

[0095] Dichloroethane, propylchloride, isopropylchloride, butylchloride, isobutylchloride, pentylchloride, isopentylchloride, etc.

[3] Fluorine Compound

[0096] CHF.sub.3, CH.sub.2F.sub.2, CH.sub.3F, etc.

[4] Hydrochlorofluorocarbon Compound

[0097] Trichlormonofluoromethane, trichlortrifluoroethane, dichloromonofluoroethane, (e.g., HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)), etc.

[5] Hydrofluorocarbon

[0098] HFC-245fa available from Central Glass Co., Ltd. (1,1,1,3,3-pentafluoropropane), HFC-365mfc available from Honeywell International Inc. (1,1,1,3,3-pentafluorobutane), etc.

[6] Hydrofluoroolefin

[0099] Solstice LBA available from Honeywell International Inc. (HFO-1233zd, (E)-1-chloro-3,3,3-trifluoropropene, Opteon 1100 available from The Chemours Company (HFO-1336mzz (Z), (Z)-1,1,1,4,4,4-hexafluoro-2-butene), Opteon 1150 available from The Chemours Company (HFO-1336mzz (E), (E)-1,1,1,4,4,4-hexafluoro-2-butene), Amorea 1224 yd available from AGC Inc. ((Z)-1-chloro-2,3,3,3-tetrafluoropropene), etc.

[7] Organic Compound

[0100] Methyl formate, diisopropyl ether, etc.

[0101] As other examples of the foaming agent, nitrogen gas, oxygen gas, argon gas, carbon dioxide gas, and the like, which can be dispersed or dissolved in the polyol component or the isocyanate component, may be used.

[0102] The amount of the foaming agent is preferably, but not limited to, 1 part by weight to 100 parts by weight per 100 parts by weight of polyol. As the parts by weight of the foaming agent increase, the foam density decreases, but the dimension stability and the compression strength decrease simultaneously. The parts by weight of the foaming agent therefore may be set to match the density design.

[0103] In an embodiment of the present invention, the foaming agents may be used alone or in combination of two or more.

<8> Flame Retardant

[0104] The flame retardant is a material for imparting flame retardancy to the urethane resin composition according to an embodiment of the present invention. For the flame retardant in an embodiment of the present invention, there are used ammonium polyphosphate and phosphoric ester are used; however, no red phosphorus is used.

[0105] The ammonium polyphosphate (APP) is a chain inorganic phosphate compound containing ammonium cations with a molecular formula as NH.sub.4O(NH.sub.4PO.sub.3).sub.nNH.sub.4, where n denotes a degree of polymerization. The ammonium polyphosphate is such a compound in a tasteless and odorless white powdered form, and the compound of a high degree of polymerization, in particular, is in a crystalline form. A structural formula indicative of the molecular structure of the ammonium polyphosphate is shown below:

##STR00001##

[0106] Product examples containing the ammonium polyphosphate include: Taien CII available from TAIHEI CHEMICAL INDUSTRIAL CO., LTD.; NNA21 available from Ameda Corporation; AP766, AP750, AP422 available from Clariant Japan Co. Ltd., and the like.

[0107] The Phosphoric ester (Organophosphate) is an ester obtained as a result of causing phosphoric acid and alcohol to undergo dehydration and condensation together out of organophosphorus compounds.

[0108] The phosphoric ester has a structure obtained as a result of substituting one or more organic groups for a part or the entirety of three atomic hydrogens (H) of a phosphoric acid (OP(OH).sub.3). The esters on the order of 1, 2, 3 in a substitution number, there are called a phosphoric mono-ester, phosphoric di-ester, and phosphoric tri-ester, collectively called phosphoric ester. A structural formula indicative of the molecular structure of the phosphoric ester is shown below:

##STR00002##

[0109] Product examples containing the phosphoric ester include tris (-chloro-propyl) phosphate (TCPP) available from Wansheng, tri-cresyl phosphate (TCP) available from Zhangjiagang Fortune Chemical Co., Ltd., Tris (dimethyl-phenyl) phosphate (TXP) available from Zhangjiagang Fortune Chemical Co., Ltd., Triethyl phosphate (TEP) available from Wansheng, and the like.

<9> Others

[0110] The urethane resin composition according to an embodiment of the present invention may contain other materials listed below as appropriate. For example, a composition containing at least one selected from the group consisting of foam stabilizer, surface conditioner, and compatibilizer may be a preferred embodiment of the urethane resin composition according to the present invention.

<9.1> Foam Stabilizer

[0111] The foam stabilizer is, for example, an organosiloxane-polyoxyalkylene copolymer used in production of polyurethane foam.

[0112] Examples of the foam stabilizer include L-6900 available from Momentive and SH-193 available from Toray Dow Corning.

<9.2> Surface Conditioner

[0113] The surface conditioner is an additive that serves as a defoaming agent, a leveling agent, and an anti-popping agent by controlling surface tension and forms a good coating. Examples of the surface conditioner include acrylic polymers such as SEI-W01 and SEI-1501 available from Kusumoto Chemicals, Ltd.

<9.3> Compatibilizer

[0114] The compatibilizer is an element for suppressing phase separation.

[0115] There are some cases where liquid obtained as a result of mixing polyol, catalyst, foaming agent, aid, and the like, collectively called polyol premix, is frequently subjected to phase separation.

[0116] Due to the fact that the physical property of sprayed hard urethane foam using such a polyol premix subjected to the phase separation becomes worse, the compatibilizer suppresses such a worsening.

[0117] Examples of the compatibilizer includes polyoxyalkylene-alkylether, nonylphenol-ethoxylate, and the like.

EXAMPLES

<1> Test Materials

[0118] The following test was performed on a foam body made from the urethane resin composition according to an embodiment of the present invention. Details of each material are as follows.

(1) Polyol Compound

[0119] A: Terephthalic acid polyester polyol (available from KAWASAKI KASEI CHEMICALS LTD. INC., product name: MAXIMOL RFK-509, hydroxyl value=200 mg KOH/g)

(2) Catalyst

[0120] B1: Organometallic catalyst (available from The Shepherd Chemical Company, product name: BiCAT 8210)

(3) Trimerization Catalyst

[0121] B2: Quaternary ammonium salt (available from Evonik, product name: TMR-7) B3: Potassium acetate catalyst (available from Evonik, product name: POLYCAT 46)

(4) Flame Retardant

[1] Ammonium Polyphosphate

[0122] C1: Ammonium polyphosphate (available from TAIHEI CHEMICAL INDUSTRIAL CO., LTD., product name: Taien CII) in a white powdered form containing phosphorus having an amount within a range of 29.0 to 34.0% and nitrogen having an amount within a range of 12.0 to 16.0%, whose degree of polymerization is 79.6.

[0123] C1-1: Ammonium polyphosphate (available from Ameda Corporation, product name: NNA21) in a white powdered form containing 31.6% (31% or more)-phosphorus and 14.3% (14% or more)-nitrogen, whose degree of polymerization is 1561 (1000 or more), where the number placed in the parenthesis denotes a specification value.

[0124] C1-2: Ammonium polyphosphate (available from Clariant Japan Co. Ltd., product name: AP766) in a white powdered form (no information).

[0125] C1-3: Ammonium polyphosphate (available from Clariant Japan Co. Ltd., product name: AP750) in a white powdered form containing 21%-phosphorus and 12%-nitrogen.

[0126] C1-4: Ammonium polyphosphate (available from Clariant Japan Co. Ltd., product name: AP422) in a white powdered form containing phosphorus having an amount within a range of 31.0 to 32.0% and nitrogen having an amount within a range of 14.0 to 15.0%.

[2] Phosphoric Ester

[0127] C2: Phosphoric ester (available from Wansheng, product name: TCPP)

[0128] C2-1: Phosphoric ester (available from Wansheng, product name: TEP)

[0129] C2-2: Phosphoric ester (available from Zhangjiagang Fortune Chemical Co., Ltd., Product name: TXP)

[0130] C2-3: Phosphoric ester (available from Zhangjiagang Fortune Chemical Co., Ltd., Product name: TCP)

(5) Foaming Agent

[0131] D1: HFO-1233zd (available from Honeywell International Inc., product name: Solstice LBA)

[0132] D2: HFO-1336mzz (available from The Chemours Company, product name: Opteon 1100)

[0133] D3: Water (hydroxyl value=6234 mg KOH/g)

(6) Foam Stabilizer

[0134] E: Silicone foam stabilizer (available from Dow Tray Co. Ltd., product name: SH-193)

(7) Surface Conditioner

[0135] F: Acrylic polymer (available from Kusumoto Chemicals, Ltd., product name: SEI-W01)

(8) Compatibilizer

[0136] G1: Polyoxyalkylene-alkylether (available from Kao Corporation, product name: EMULGEN LS-106)

[0137] G2: Nonylphenol-ethoxylate (available from Dow Inc., product name: NP-9)

(9) Mineral-Derived Material

[0138] H: Fired kaolin (available from IMERYS Minerals, product name: Glomax LL) white powdered form

(10) Polyisocyanate

[0139] I: Polymeric MDI (available from Wanhua Chemical Group Co., Ltd. Corporation, product name: PM-200, NCO content=31%)

<2> Specimen Preparation Method

[0140] In accordance with the formulations in the tables, every components such as polyol and the like were weighed and stirred in a 1000 mL polypropylene beaker.

[0141] Hereinafter, this stirred product is referred to as polyol premix.

[0142] The temperature of the polyol premix and isocyanate was regulated to 20 C.

[0143] The isocyanate component was added to the temperature-regulated polyol premix component in accordance with the formulations in the tables. The mixture was stirred with an electric mixer for about three seconds and then quickly poured into a 200200200 mm.sup.3 wood box having a temperature regulated to 20 C. to obtain a foam body. (The polyol premix component contained powder, which was dispersed by stirring in advance immediately before addition of the isocyanate component.)

[0144] The foam body cured for 24 hours after foaming was cut into a size of 99 mm99 mm50 mm, and the mass of the cut foam body was measured (the foam density was calculated from the obtained mass and the size). A cone calorimeter specimen was thus prepared. (This specimen was cut into a height of 50 mm relative to the foaming direction.)

<3> Test Details

[0145] In a heat release test in conformity with the ISO-5660 test method, each specimen was heated at the intensity of radiant heat of 50 kW/m.sup.2 for 20 minutes, and the gross calorific value (when heated for 10 minutes and heated for 20 minutes), the maximum heat release rate, the duration of time in which 200 kW/m.sup.2 is exceeded (the duration of time in which the maximum heat release rate consecutively exceeds 200 kW/m.sup.2), and the like were evaluated.

[0146] Details of test equipment used in the present test are as follows. [0147] Product name: cone calorimeter type: C4 available from Toyo Seiki Seisaku-sho, Ltd. [0148] Distance between specimen and spark plug: 12.5 mm

<4> Test Results

[0149] Experimental examples to be compared, which are extracted from all the test results, will be described with reference to the tables. It is to be noted that there was no crack or through-hole up to the rear surface harmful to the fire prevention in any specimens under the test.

(1) Experimental Examples 1 and 2 (Table 2)

[0150] Initially, Table 2 shows Experimental EXAMPLES 1 and 2 in a case where only the ammonium polyphosphate is contained and a case where only the phosphoric ester is contained, as the flame retardant, respectively.

TABLE-US-00002 TABLE 2 Product OH value/ EXAM- EXAM- name Composition NCO content PLE 1 PLE 2 MAXIMOL A Terephthalic acid 200 100 100 RFK-509 polyester polyol TMR-7 B2 Trimerization 5 5 catalyst BiCAT B1 Catalyst 2 2 8210 POLYCAT B3 Trimerization 5 5 46 catalyst Taien CII C1 Flame retardant 0 50 ammonium polyphosphate TCPP C2 Flame retardant 80 0 phosphoric ester Solstice D1 Foaming agent 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 252.50 222.50 PM-200 I Polyisocyanate 31 252.50 222.50 polymeric MDI Polyol premix hydroxyl value 91.55 103.90 NCO Index 452 399 CCM Result EXAMPLE 1 EXAMPLE 2 Foam density kg/m.sup.3 42.1 28.6 Gross calorific 10 min Undetected 23.4 value MJ/m.sup.2 20 min Undetected 26.3 MJ/m.sup.2 Maximum heat kW/m.sup.2 Undetected 126.1 release rate

[0151] In Experimental EXAMPLE 1, cells (bubbles) had inhomogeneity in size within the specimen, which resulted in a quick determination that such a specimen is equivalent to neither uninflammable material nor quasi-uninflammable material, and for this reason, no heat release test was carried out.

[0152] Experimental EXAMPLE 2 resulted in the conclusion that the specimen is equivalent to neither uninflammable material nor quasi-uninflammable material.

(2) Experimental Examples 3 to 45 (Tables 3 to 10)

[0153] Subsequently, there are shown Experimental EXAMPLES where the ammonium polyphosphate and the phosphoric ester were set in amount per 100 parts by weight of the polyol compound, respectively, in the following ranges.

[0154] [Ammonium polyphosphate/parts by weight]: 20, 40, 50, 75, 100, and 125 [0155] [Phosphoric ester/parts by weight]: 20, 40, 60, 80, 100, 120, and 140

[0156] Table 3 shows Experimental EXAMPLES dependent upon their respective amounts of the phosphoric ester within a range of 20 parts by weight to 140 parts by weight while the amount of the ammonium polyphosphate being fixed to be 20 parts by weight, per 100 parts by weight of the polyol compound.

[0157] In Experimental EXAMPLES 7 to 9 among them, each specimen having rough cells occurring therewithin was unsuitable as a thermal insulation material, no heat release test was carried out.

TABLE-US-00003 TABLE 3 Product OH value/ EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- name Composition NCO content PLE 3 PLE 4 PLE 5 PLE 6 PLE 7 PLE 8 PLE 9 MAXIMOL A Terephthalic 200 100 100 100 100 100 100 100 RFK-509 acid polyester polyol TMR-7 B2 Trimerization 5 5 5 5 5 5 5 catalyst BiCAT B1 Catalyst 2 2 2 2 2 2 2 8210 POLYCAT B3 Trimerization 5 5 5 5 5 5 5 46 catalyst Taien CII C1 Flame retardant 20 20 20 20 20 20 20 ammonium polyphosphate TCPP C2 Flame retardant 20 40 60 80 100 120 140 phosphoric ester Solstice D1 Foaming agent 40 40 40 40 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 20 20 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 212.50 232.50 252.50 272.50 292.50 312.50 332.50 PM-200 I Polyisocyanate 31 212.50 232.50 252.50 272.50 292.50 312.50 332.50 polymeric MDI Polyol premix hydroxyl value 108.79 99.43 91.55 84.83 79.03 73.97 69.52 NCO Index 381 417 452 488 524 560 596 EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- CCM Result PLE 3 PLE 4 PLE 5 PLE 6 PLE 7 PLE 8 PLE 9 Foam density kg/m.sup.3 23.6 26.5 26.9 29.7 38.0 44.8 43.7 Gross calorific 10 min 9.4 4.5 4.0 5.1 Undetected Undetected Undetected value MJ/m.sup.2 20 min 13.4 7.1 5.6 7.1 Undetected Undetected Undetected MJ/m.sup.2 Maximum heat kW/m.sup.2 73.1 55.4 53.3 54.8 Undetected Undetected Undetected release rate

[0158] Table 4 shows Experimental EXAMPLES dependent upon their respective amounts of the phosphoric ester within a range of 20 parts by weight to 140 parts by weight while the amount of the ammonium polyphosphate being fixed to be 40 parts by weight, per 100 parts by weight of the polyol compound.

TABLE-US-00004 TABLE 4 Product OH value/ EXAMPLE EXAMPLE EXAMPLE EXAMPLE name Composition NCO content 10 11 12 13 MAXIMOL A Terephthalic acid 200 100 100 100 100 RFK-509 polyester polyol TMR-7 B2 Trimerization 5 5 5 5 catalyst BiCAT B1 Catalyst 2 2 2 2 8210 POLYCAT B3 Trimerization 5 5 5 5 46 catalyst Taien CII C1 Flame retardant 40 40 40 40 ammonium polyphosphate TCPP C2 Flame retardant 20 40 60 80 phosphoric ester Solstice D1 Foaming agent 40 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 232.50 252.50 272.50 292.50 PM-200 I Polyisocyanate 31 232.50 252.50 272.50 292.50 polymeric MDI Polyol premix hydroxyl value 99.43 91.55 84.83 79.03 NCO Index 417 452 488 524 Product OH value/ EXAMPLE EXAMPLE EXAMPLE name Composition NCO content 14 15 16 MAXIMOL A Terephthalic acid 200 100 100 100 RFK-509 polyester polyol TMR-7 B2 Trimerization 5 5 5 catalyst BiCAT B1 Catalyst 2 2 2 8210 POLYCAT B3 Trimerization 5 5 5 46 catalyst Taien CII C1 Flame retardant 40 40 40 ammonium polyphosphate TCPP C2 Flame retardant 100 120 140 phosphoric ester Solstice D1 Foaming agent 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 312.50 332.50 352.50 PM-200 I Polyisocyanate 31 312.50 332.50 352.50 polymeric MDI Polyol premix hydroxyl value 73.97 69.52 65.58 NCO Index 560 596 632 EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE CCM Result 10 11 12 13 14 15 16 Foam density kg/m.sup.3 25.6 27.2 27.8 31.7 32.7 35.2 40.4 Gross calorific 10 min 13.5 5.2 5.2 4.7 4.7 5.6 7.1 value MJ/m.sup.2 20 min 19.6 7.7 8.0 6.4 7.1 7.4 9.7 MJ/m.sup.2 Maximum heat kW/m.sup.2 96.7 46.5 36.8 48.1 44.5 41.3 46.8 release rate

[0159] Table 5 shows Experimental EXAMPLES dependent upon their respective amounts of the phosphoric ester within a range of 20 parts by weight to 140 parts by weight while the amount of the ammonium polyphosphate being fixed to be 50 parts by weight, per 100 parts by weight of the polyol compound.

TABLE-US-00005 TABLE 5 Product OH value/ EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- name Composition NCO content PLE 17 PLE 18 PLE 19 PLE 20 PLE 21 PLE 22 PLE 23 MAXIMOL A Terephthalic 200 100 100 100 100 100 100 100 RFK-509 acid polyester polyol TMR-7 B2 Trimerization 5 5 5 5 5 5 5 catalyst BiCAT B1 Catalyst 2 2 2 2 2 2 2 8210 POLYCAT B3 Trimerization 5 5 5 5 5 5 5 46 catalyst Taien CII C1 Flame retardant 50 50 50 50 50 50 50 ammonium polyphosphate TCPP C2 Flame retardant 20 40 60 80 100 120 140 phosphoric ester Solstice D1 Foaming agent 40 40 40 40 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 20 20 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 242.50 262.50 282.50 302.50 322.50 342.50 362.50 PM-200 I Polyisocyanate 31 242.50 262.50 282.50 302.50 322.50 342.50 362.50 polymeric MDI Polyol premix hydroxyl value 95.33 88.06 81.83 76.42 71.68 67.49 63.77 NCO Index 434 470 506 542 578 614 649 EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- CCM Result PLE 17 PLE 18 PLE 19 PLE 20 PLE 21 PLE 22 PLE 23 Foam density kg/m.sup.3 27.2 28.6 29.8 33.9 35.2 38.2 38.4 Gross calorific 10 min 16.4 4.9 4.1 4.6 5.8 4.9 6.9 value MJ/m.sup.2 20 min 22.4 7.4 5.3 6.2 8.0 6.4 11.7 MJ/m.sup.2 Maximum heat kW/m.sup.2 103.1 48.1 43.0 26.6 47.9 44.9 49.5 release rate

[0160] Table 6 shows Experimental EXAMPLES dependent upon their respective amounts of the phosphoric ester within a range of 20 parts by weight to 140 parts by weight while the amount of the ammonium polyphosphate being fixed to be 75 parts by weight, per 100 parts by weight of the polyol compound.

TABLE-US-00006 TABLE 6 Product OH value/ EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- name Composition NCO content PLE 24 PLE 25 PLE 26 PLE 27 PLE 28 PLE 29 PLE 30 MAXIMOL A Terephthalic 200 100 100 100 100 100 100 100 RFK-509 acid polyester polyol TMR-7 B2 Trimerization 5 5 5 5 5 5 5 catalyst BiCAT B1 Catalyst 2 2 2 2 2 2 2 8210 POLYCAT B3 Trimerization 5 5 5 5 5 5 5 46 catalyst Taien CII C1 Flame retardant 75 75 75 75 75 75 75 ammonium polyphosphate TCPP C2 Flame retardant 20 40 60 80 100 120 140 phosphoric ester Solstice D1 Foaming agent 40 40 40 40 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 20 20 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 267.50 287.50 307.50 327.50 347.50 367.50 387.50 PM-200 I Polyisocyanate 31 267.50 287.50 307.50 327.50 347.50 367.50 387.50 polymeric MDI Polyol premix hydroxyl value 86.42 80.41 75.13 70.59 66.52 62.90 59.66 NCO Index 479 515 551 587 623 658 694 EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- CCM Result PLE 24 PLE 25 PLE 26 PLE 27 PLE 28 PLE 29 PLE 30 Foam density kg/m.sup.3 32.1 30.6 33.3 35.0 36.5 39.2 44.5 Gross calorific 10 min 14.7 5.9 5.0 4.7 4.7 4.3 3.9 value MJ/m.sup.2 20 min 17.9 8.7 7.8 6.7 6.9 5.5 6.3 MJ/m.sup.2 Maximum heat kW/m.sup.2 84.7 65.3 52.5 53.4 44.1 44.9 42.3 release rate

[0161] Table 7 shows Experimental EXAMPLES dependent upon their respective amounts of the phosphoric ester within a range of 20 parts by weight to 140 parts by weight while the amount of the ammonium polyphosphate being fixed to be 100 parts by weight, per 100 parts by weight of the polyol compound.

TABLE-US-00007 TABLE 7 OH value/ Product NCO EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE name Composition content 31 32 33 34 35 36 37 MAXIMOL A Terephthalic acid 200 100 100 100 100 100 100 100 RFK-509 polyester polyol TMR-7 B2 Trimerization 5 5 5 5 5 5 5 catalyst BiCAT B1 Catalyst 2 2 2 2 2 2 2 8210 POLYCAT B3 Trimerization 5 5 5 5 5 5 5 46 catalyst Taien CII C1 Flame retardant 100 100 100 100 100 100 100 ammonium polyphosphate TCPP C2 Flame retardant 20 40 60 80 100 120 140 phosphoric ester Solstice D1 Foaming agent 40 40 40 40 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 20 20 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 292.50 312.50 332.50 352.50 372.50 392.50 412.50 PM-200 I Polyisocyanate 31 292.50 312.50 332.50 352.50 372.50 392.50 412.50 polymeric MDI Polyol premix hydroxyl value 79.03 73.97 69.52 65.58 62.06 58.90 56.04 NCO Index 524 560 596 632 667 703 739 EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE CCM Result 31 32 33 34 35 36 37 Foam density kg/m.sup.3 34.3 34.5 37.2 38.2 38.7 42.2 50.2 Gross calorific 10 min 16.8 11.6 5.3 4.1 5.0 4.8 4.7 value MJ/m.sup.2 20 min 24.0 14.2 7.6 6.2 7.1 7.7 7.1 MJ/m.sup.2 Maximum heat kW/m.sup.2 96.0 92.8 58.0 47.6 59.4 49.0 46.9 release rate

[0162] Table 8 shows Experimental EXAMPLES dependent upon their respective amounts of the phosphoric ester within a range of 20 parts by weight to 140 parts by weight while the amount of the ammonium polyphosphate being fixed to be 125 parts by weight, per 100 parts by weight of the polyol compound.

TABLE-US-00008 TABLE 8 OH value/ EX- EX- EX- EX- EX- EX- EX- Product NCO AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE name Composition content 38 39 40 41 42 43 44 MAXIMOL A Terephthalic acid 200 100 100 100 100 100 100 100 RFK-509 polyester polyol TMR-7 B2 Trimerization 5 5 5 5 5 5 5 catalyst BiCAT B1 Catalyst 2 2 2 2 2 2 2 8210 POLYCAT B3 Trimerization 5 5 5 5 5 5 5 46 catalyst Taien CII C1 Flame retardant 125 125 125 125 125 125 125 ammonium polyphosphate TCPP C2 Flame retardant 20 40 60 80 100 120 140 phosphoric ester Solstice D1 Foaming agent 40 40 40 40 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 20 20 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 317.50 337.50 357.50 377.50 397.50 417.50 437.50 PM-200 I Polyisocyanate 31 317.50 337.50 357.50 377.50 397.50 417.50 437.50 polymeric MDI Polyol premix hydroxyl value 72.81 68.49 64.66 61.24 58.16 55.37 52.84 NCO Index 569 605 640 676 712 748 784 EX- EX- EX- EX- EX- EX- EX- AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE CCM Result 38 39 40 41 42 43 44 Foam density kg/m.sup.3 37.8 38.8 40.0 42.5 43.2 47.2 54.1 Gross calorific 10 min 20.2 15.6 16.0 15.6 11.6 8.3 5.7 value MJ/m.sup.2 20 min 29.6 21.5 21.7 20.9 15.6 11.6 10.3 MJ/m.sup.2 Maximum heat kW/m.sup.2 110.1 121.0 97.5 98.0 84.1 66.4 62.2 release rate

(2.1) Isocyanate Index

[0163] Table 9 shows the isocyanate index (NCO Index) in each of Experimental EXAMPLES 3 to 44 in a matrix form.

TABLE-US-00009 TABLE 9 NCO Index (Isocyanate index) Ammonium Polyphosphate 20 40 50 75 100 125 Phosphoric 20 381 417 434 479 524 569 ester 40 417 452 470 515 560 605 60 452 488 506 551 596 640 80 488 524 542 587 632 676 100 524 560 578 623 667 712 120 560 596 614 658 703 748 140 596 632 649 694 739 784

[0164] As shown in Table 9, the isocyanate index of each foam body falls within a range of 381 to 784, that is a range of approximately 400 to approximately 800.

(2.2) Quasi-Uninflammability Evaluated by Heat Release Test

[0165] Table 10 shows the gross calorific value of the specimen when heated for 10 minutes in the heat release test in each of Experimental EXAMPLES 3 to 44 in a matrix form.

TABLE-US-00010 TABLE 10 10-min Gross Calorific Value Ammonium Polyphosphate 20 40 50 75 100 125 Phosphoric 20 9.4 13.5 16.4 14.7 16.8 20.2 ester 40 4.5 5.2 4.9 5.9 11.6 15.6 60 4.0 5.2 4.1 5.0 5.3 16.0 80 5.1 4.7 4.6 4.7 4.1 15.6 100 Undetected 4.7 5.8 4.7 5.0 11.6 120 Undetected 5.6 4.9 4.3 4.8 8.3 140 Undetected 7.1 6.9 3.9 4.7 5.7

[0166] According to Table 10, it was found that the specimen containing the ammonium polyphosphate and the phosphoric ester having their respective amounts per 100 parts by weight of the polyol compound falling within the following ranges was equivalent to the quasi-uninflammable material:

Range (1) of Amount

[0167] Ammonium polyphosphate/parts by weight: 20 or more and 75 or less [0168] Phosphoric ester/parts by weight: 40 or more and 80 or less

Range (2) of Amount

[0169] Ammonium polyphosphate/parts by weight: 20 or more and 100 or less [0170] Phosphoric ester/parts by weight: 60 or more and 80 or less

Range (3) of Amount

[0171] Ammonium polyphosphate/parts by weight: 40 or more and 75 or less [0172] Phosphoric ester/parts by weight: 40 or more and 140 or less

Range (4) of Amount

[0173] Ammonium polyphosphate/parts by weight: 40 or more and 100 or less [0174] Phosphoric ester/parts by weight: 60 or more and 140 or less

Range (5) of Amount

[0175] Ammonium polyphosphate/parts by weight: 40 or more and 125 or less [0176] Phosphoric ester/parts by weight: 140

(2.3) Uninflammability Evaluated by Heat Release Test

[0177] Table 11 shows the gross calorific value of the specimen when heated for 20 minutes in the heat release test in each of Experimental EXAMPLES 3 to 44 in a matrix form.

TABLE-US-00011 TABLE 11 20-min Gross Calorific Value Ammonium Polyphosphate 20 40 50 75 100 125 Phosphoric 20 13.4 19.6 22.4 17.9 24.0 29.6 ester 40 7.1 7.7 7.4 8.7 14.2 21.5 60 5.6 8.0 5.3 7.8 7.6 21.7 80 7.1 6.4 6.2 6.7 6.2 20.9 100 Undetected 7.1 8.0 6.9 7.1 15.6 120 Undetected 7.4 6.4 5.5 7.7 11.6 140 Undetected 9.7 11.7 6.3 7.1 10.3

[0178] According to Table 11, it was found that the specimen containing the ammonium polyphosphate and the phosphoric ester having their respective amounts per 100 parts by weight of the polyol compound falling within the following ranges was equivalent to the uninflammable material:

Range (6) of Amount

[0179] Ammonium polyphosphate/parts by weight: 20 or more and 50 or less [0180] Phosphoric ester/parts by weight: 40 or more and 80 or less

Range (7) of Amount

[0181] Ammonium polyphosphate/parts by weight: 20 or more and 100 or less [0182] Phosphoric ester/parts by weight: 60 or more and 80 or less

Range (8) of Amount

[0183] Ammonium polyphosphate/parts by weight: 40 or more and 50 or less [0184] Phosphoric ester/parts by weight: 40 or more and 120 or less

Range (9) of Amount

[0185] Ammonium polyphosphate/parts by weight: 40 or more and 100 or less [0186] Phosphoric ester/parts by weight: 60 or more and 120 or less

Range (10) of Amount

[0187] Ammonium polyphosphate/parts by weight: 75 or more and 100 or less [0188] Phosphoric ester/parts by weight: 60 or more and 140 or less

(3) Experimental Examples 20, 45 to 48 (Table 12)

[0189] Further subsequently, Table 12 shows Experimental EXAMPLES 20, 45 to 48 where each specimen containing the ammonium polyphosphate of 50 parts by weight and the phosphoric ester of 80 parts by weight per 100 parts, by weight of the polyol compound, further contains the fired kaolin as the mineral-derived material.

TABLE-US-00012 TABLE 12 Product OH value/ EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE name Composition NCO content 20 45 46 47 48 MAXIMOL A Terephthalic acid 200 100 100 100 100 100 RFK-509 polyester polyol SH-193 E Silicone-based foam stabilizer SEI-W01 F Surface conditioner LS-106 G1 Compatibilizer NP-9 G2 Compatibilizer BiCAT B1 Catalyst 2 2 2 2 2 8210 TMR-7 B2 Trimerization 5 5 5 5 5 catalyst POLYCAT B3 Trimerization 5 5 5 5 5 46 catalyst Glomax H Fired kaolin 3 25 50 75 LL Taien CII C1 Flame retardant 50 50 50 50 50 ammonium polyphosphate TCPP C2 Flame retardant 80 80 80 80 80 phosphoric ester Solstice D1 Foaming agent 40 40 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 302.50 305.50 327.50 352.50 377.50 PM-200 I Polyisocyanate 31 302.50 305.50 327.50 352.50 377.50 polymeric MDI Polyol premix hydroxyl value 76.42 75.67 70.59 65.58 61.24 NCO Index 542 547 587 632 676 EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE CCM Result 20 45 46 47 48 Foam density kg/m.sup.3 32.4 32.3 36.3 39.6 44.1 Gross calorific 10 min 4.8 4.5 5.0 5.0 6.8 value MJ/m.sup.2 20 min 6.7 6.3 7.3 7.5 10.7 MJ/m.sup.2 Maximum heat kW/m.sup.2 49.0 49.6 43.8 42.5 45.5 release rate

[0190] According to Table 12, it was found that each specimen in Experimental EXAMPLES 45 to 47, in the same manner as that in Experimental EXAMPLE 20, was equivalent to the uninflammable material, and the specimen in Experimental EXAMPLE 48 was equivalent to the quasi-uninflammable material.

[0191] For this reason, it was considered that the addition of fired kaolin does not have any large effect on the reduction of flame retardancy.

(4) Experimental Examples 20, 49 to 52 (Table 13)

[0192] Further subsequently, Table 13 shows Experimental EXAMPLES 20, 49 to 52 where each specimen containing the ammonium polyphosphate of 50 parts by weight and the phosphoric ester of 80 parts by weight per 100 parts, by weight of the polyol compound, further contains any of the foam stabilizer, surface conditioner, and compatibilizer.

TABLE-US-00013 TABLE 13 Product OH value/ EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE name Composition NCO content 20 49 50 51 52 MAXIMOL A Terephthalic acid 200 100 100 100 100 100 RFK-509 polyester polyol SH-193 E Silicone-based 3 foam stabilizer SEI-W01 F Surface conditioner 3 LS-106 G1 Compatibilizer 3 NP-9 G2 Compatibilizer 3 BiCAT B1 Catalyst 2 2 2 2 2 8210 TMR-7 B2 Trimerization 5 5 5 5 5 catalyst POLYCAT B3 Trimerization 5 5 5 5 5 46 catalyst Glomax H Fired kaolin LL Taien CII C1 Flame retardant 50 50 50 50 50 ammonium polyphosphate TCPP C2 Flame retardant 80 80 80 80 80 phosphoric ester Solstice D1 Foaming agent 40 40 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 302.50 305.50 305.50 305.50 305.50 PM-200 I Polyisocyanate 31 302.50 305.50 305.50 305.50 305.50 polymeric MDI Polyol premix hydroxyl value 76.42 75.67 75.67 75.67 75.67 NCO Index 542 547 547 547 547 EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE CCM Result 20 49 50 51 52 Foam density kg/m.sup.3 32.4 33.1 33.8 33.2 32.6 Gross calorific 10 min 4.8 5.8 3.7 4.9 5.6 value MJ/m.sup.2 20 min 6.7 7.4 5.7 6.7 6.8 MJ/m.sup.2 Maximum heat kW/m.sup.2 49.0 46.5 31.1 49.3 43.2 release rate

[0193] According to Table 13, it was found that each specimen in Experimental EXAMPLES 49 to 52, in the same manner as that in Experimental EXAMPLE 20, was equivalent to the uninflammable material.

[0194] For this reason, it was considered that the addition of foam stabilizer, surface conditioner, and compatibilizer does not have any large effect on the reduction of flame retardancy.

(5) Experimental Examples 53 to 55 (Table 14, FIGS. 1, 2)

[0195] Further subsequently, a comparison in hue of foam body was made among the specimens containing the fired kaolin (the same material as the above-described (H)) and the red phosphorus (C3: available from RIN KAGAKU KOGYO Co., Ltd., product name: Nova Excel 140) having their respective amounts, per 100 parts by weight of the polyol compound, combinations of which are shown in Table 14 below:

TABLE-US-00014 TABLE 14 Product OH value/ EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE name Composition NCO content 20 48 53 54 55 MAXIMOL A Terephthalic acid 200 100 100 100 100 100 RFK-509 polyester polyol BiCAT B1 Catalyst 2 2 2 2 2 8210 TMR-7 B2 Trimerization 5 5 5 5 5 catalyst POLYCAT B3 Trimerization 5 5 5 5 5 46 catalyst Glomax H Fired kaolin 75 75 LL Nova C3 Red phosphorus 25 50 50 Excel 140 Taien CII C1 Flame retardant 50 50 25 ammonium polyphosphate TCPP C2 Flame retardant 80 80 80 80 80 phosphoric ester Solstice D1 Foaming agent 40 40 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 302.50 377.50 302.50 302.50 377.50 PM-200 I Polyisocyanate 31 302.50 377.50 302.50 302.50 377.50 polymeric MDI Polyol premix hydroxyl value 76.42 61.24 76.42 76.42 61.24 NCO Index 542 676 542 542 676 EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE CCM Result 20 48 53 54 55 Foam density kg/m.sup.3 33.9 44.1 31.4 31.8 40.6 Gross calorific 10 min 4.6 6.8 3.8 4.3 4.3 value MJ/m.sup.2 20 min 6.2 10.7 5.9 5.1 6.4 MJ/m.sup.2 Maximum heat kW/m.sup.2 26.6 45.5 48.7 76.6 58.7 release rate

[0196] FIGS. 1, 2 depict views of photographs for comparison in hue of foam body among Experimental EXAMPLES 20, 48, 53 to 55. Each view is obtained by having taken a photograph of each foam body arranged in a white background.

[0197] The foam body according to an embodiment of the present invention as shown in FIG. 1 (foam bodies in Experimental EXAMPLES 20, 48, respectively) takes on white-based or beige-based hue substantially close to a background hue, and is therefore allowed to be colored such that it can take on any sorts of hue.

[0198] On the other hand, it was found in FIG. 2 that the foam body in Experimental EXAMPLES 53 to 55 containing the red phosphorus takes on reddish-brown-based hue distinct from a background hue, and for this reason, has a restricted degree of freedom in coloring in contrast to that according to an embodiment of the present invention.

(6) Experimental Examples 56 to 59 (Table 15)

[0199] Further subsequently, Table 15 shows Experimental EXAMPLES 56 to 59 dependent upon various products containing the ammonium polyphosphate while the amounts of the ammonium polyphosphate and the phosphoric ester being fixed to be 50 parts by weight and 80 parts by weight, respectively, per 100 parts by weight of the polyol compound.

TABLE-US-00015 TABLE 15 Product OH value/ EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE name Composition NCO content 20 56 57 58 59 MAXIMOL A Terephthalic acid 200 100 100 100 100 100 RFK-509 polyester polyol BiCAT B1 Catalyst 2 2 2 2 2 8210 TMR-7 B2 Trimerization 5 5 5 5 5 catalyst POLYCAT B3 Trimerization 5 5 5 5 5 46 catalyst Taien CII C1 Flame retardant 50 NNA21 C1-1 ammonium 50 AP766 C1-2 polyphosphate 50 AP750 C1-3 50 AP422 C1-4 50 TCPP C2 Flame retardant 80 80 80 80 80 phosphoric ester Solstice D1 Foaming agent 40 40 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 302.50 302.50 302.50 302.50 302.50 PM-200 I Polyisocyanate 31 302.50 302.50 302.50 302.50 302.50 polymeric MDI Polyol premix hydroxyl value 76.42 76.42 76.42 76.42 76.42 NCO Index 542 542 542 542 542 EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE CCM Result 20 56 57 58 59 Foam density kg/m.sup.3 32.4 32.4 32.7 30.2 30.6 Gross calorific 10 min 4.8 5.5 5.0 5.4 5.3 value MJ/m.sup.2 20 min 6.7 7.1 6.8 7.3 7.1 MJ/m.sup.2 Maximum heat kW/m.sup.2 49.0 52.6 49.1 40.0 45.2 release rate

[0200] According to Table 15, it was found that each specimen in Experimental EXAMPLES 56 to 59, in the same manner as that in Experimental EXAMPLE 20, was equivalent to the uninflammable material.

(7) Experimental Examples 60 to 63 (Table 16)

[0201] Further subsequently, Table 16 shows Experimental EXAMPLES 60 to 63 dependent upon various products containing the polyphosphoric ester while the amounts of the ammonium polyphosphate and the phosphoric ester being fixed to be 50 parts by weight and 80 parts by weight, respectively, per 100 parts by weight of the polyol compound.

TABLE-US-00016 TABLE 16 Product OH value/ EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE name Composition NCO content 20 60 61 62 63 MAXIMOL A Terephthalic acid 200 100 100 100 100 100 RFK-509 polyester polyol BiCAT B1 Catalyst 2 2 2 2 2 8210 TMR-7 B2 Trimerization 5 5 5 5 5 catalyst POLYCAT B3 Trimerization 5 5 5 5 5 46 catalyst Taien CII C1 Flame retardant 50 50 50 50 50 ammonium polyphosphate TCPP C2 Flame retardant 80 TCP C2-1 phosphoric ester 80 TEP C2-2 80 TXP C2-3 80 TCP C2-4 80 Solstice D1 Foaming agent 40 40 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 302.50 302.50 302.50 302.50 302.50 PM-200 I Polyisocyanate 31 302.50 302.50 302.50 302.50 302.50 polymeric MDI Polyol premix hydroxyl value 76.42 76.42 76.42 76.42 76.42 NCO Index 542 542 542 542 542 EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE CCM Result 20 60 61 62 63 Foam density kg/m.sup.3 32.4 34.5 30.1 34.7 34.6 Gross calorific 10 min 4.8 3.2 5.4 3.5 3.8 value MJ/m.sup.2 20 min 6.7 4.2 7.1 4.5 5.7 MJ/m.sup.2 Maximum heat kW/m.sup.2 49.0 53.8 68.9 52.1 32.6 release rate

[0202] According to Table 16, it was found that each specimen in Experimental EXAMPLES 60 to 63, in the same manner as that in Experimental EXAMPLE 20, was equivalent to the uninflammable material.

(8) Experimental Examples 64 to 72 (Table 17)

[0203] Still further subsequently, Table 17 shows Experimental EXAMPLES 64 to 72 having the averaged results of larger sample number (N=3) than the above dependent upon various amounts of the ammonium polyphosphate and the phosphoric ester per 100 parts by weight of the polyol compound.

TABLE-US-00017 TABLE 17 OH value/ EX- EX- EX- EX- EX- EX- EX- EX- EX- Product NCO AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE name Composition content 64 65 66 67 68 69 70 71 72 MAXIMOL A Terephthalic 200 100 100 100 100 100 100 100 100 100 RFK-509 acid poly- ester polyol BiCAT B1 Catalyst 2 2 2 2 2 2 2 2 2 8210 TMR-7 B2 Trimerization 5 5 5 5 5 5 5 5 5 catalyst POLYCAT B3 Trimerization 5 5 5 5 5 5 5 5 5 46 catalyst Taien CII C1 Flame 40 50 75 40 50 75 40 50 75 AP422 C1- retardant 4 ammonium polyphosphate TCPP C2 Flame 40 40 40 60 60 60 80 80 80 TCP C2- retardant 1 phosphoric ester Solstice D1 Foaming agent 40 40 40 40 40 40 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 20 20 20 20 20 20 1100 HFO- 1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (H20) water (H.sub.2O) Polyol premix total 252.50 262.50 287.50 272.50 282.50 307.50 292.50 302.50 327.50 PM-200 I Polyisocyanate 31 252.50 262.50 287.50 272.50 282.50 307.50 292.50 302.50 327.50 polymeric MDI Polyol premix hydroxyl value 91.55 88.06 80.41 84.83 81.83 75.18 79.03 76.42 70.59 NCO Index 452 470 515 488 506 551 524 542 587 EX- EX- EX- EX- EX- EX- EX- EX- EX- AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE CCM Result 64 65 66 67 68 69 70 71 72 Foam density kg/m.sup.3 26.8 28.4 32.0 28.4 29.9 35.0 30.7 32.0 36.2 Gross calorific 10 min 5.2 4.7 6.3 4.7 4.1 4.8 4.7 4.5 4.8 value MJ/m.sup.2 20 min 6.9 6.5 7.9 6.9 5.3 6.6 6.0 6.0 6.9 MJ/m.sup.2 Maximum heat kW/m.sup.2 62.0 53.8 93.0 54.8 52.7 64.9 49.8 56.7 55.2 release rate

(8.1) Quasi-Uninflammability Evaluated by Heat Release Test

[0204] Table 18 shows results obtained by replacing a part of the 10-min gross calorific values in the heat release test shown in a matrix form in Table 10 with those in Experimental EXAMPLES 64 to 72 in Table 17. It is to be noted that the numbers indicative of replaced values are emphasized by the underlined bold type.

TABLE-US-00018 TABLE 18 10-min Gross Calorific Value Ammonium Polyphosphate 20 40 50 75 100 125 Phosphoric 20 9.4 13.5 16.4 14.7 16.8 20.2 ester 40 4.5 5.2 4.7 6.3 11.6 15.6 60 4.0 4.7 4.1 4.8 5.3 16.0 80 5.1 4.7 4.5 4.8 4.1 15.6 100 Undetected 4.7 5.8 4.7 5.0 11.6 120 Undetected 5.6 4.9 4.3 4.8 8.3 140 Undetected 7.1 6.9 3.9 4.7 5.7

[0205] According to Table 18, it was found that the specimen falling within the following ranges was equivalent to the quasi-uninflammable material:

Range (A) of Amount Per 100 Parts by Weight of the Polyol Compound

[0206] Ammonium polyphosphate/parts by weight: 20 or more and 75 or less [0207] Phosphoric ester/parts by weight: 40 or more and 80 or less

Range (B) of Amount Per 100 Parts by Weight of the Polyol Compound

[0208] Ammonium polyphosphate/parts by weight: 20 or more and 100 or less [0209] Phosphoric ester/parts by weight: 60 or more and 80 or less

Range (C) of Amount Per 100 Parts by Weight of the Polyol Compound

[0210] Ammonium polyphosphate/parts by weight: 40 or more and 75 or less [0211] Phosphoric ester/parts by weight: 40 or more and 140 or less

Range (D) of Amount Per 100 Parts by Weight of the Polyol Compound

[0212] Ammonium polyphosphate/parts by weight: 40 or more and 100 or less [0213] Phosphoric ester/parts by weight: 60 or more and 140 or less

Range (E) of Amount Per 100 Parts by Weight of the Polyol Compound

[0214] Ammonium polyphosphate/parts by weight: 40 or more and 125 or less [0215] Phosphoric ester/parts by weight: 140

(8.2) Uninflammability Evaluated by Heat Release Test

[0216] Table 19 shows results obtained by replacing a part of the 20-min gross calorific values in the heat release test shown in a matrix form in Table 11 with those in Experimental EXAMPLES 64 to 72 in Table 17. It is to be noted that the numbers indicative of replaced values are emphasized by the underlined bold type.

TABLE-US-00019 TABLE 19 20-min Gross Calorific Value Ammonium Polyphosphate 20 40 50 75 100 125 Phosphoric 20 13.4 19.6 22.4 17.9 24.0 29.6 ester 40 7.1 6.9 6.5 7.9 14.2 21.5 60 5.6 6.9 5.3 6.6 7.6 21.7 80 7.1 6.0 6.0 6.9 6.2 20.9 100 Undetected 7.1 8.0 6.9 7.1 15.6 120 Undetected 7.4 6.4 5.5 7.7 11.6 140 Undetected 9.7 11.7 6.3 7.1 10.3

[0217] According to Table 19, it was found that the specimen falling within the following ranges was equivalent to the uninflammable material:

Range (F) of Amount Per 100 Parts by Weight of the Polyol Compound

[0218] Ammonium polyphosphate/parts by weight: 20 or more and 75 or less [0219] Phosphoric ester/parts by weight: 40 or more and 80 or less

Range (G) of Amount Per 100 Parts by Weight of the Polyol Compound

[0220] Ammonium polyphosphate/parts by weight: 40 or more and 75 or less [0221] Phosphoric ester/parts by weight: 40 or more and 120 or less

Range (H) of Amount Per 100 Parts by Weight of the Polyol Compound

[0222] Ammonium polyphosphate/parts by weight: 40 or more and 100 or less [0223] Phosphoric ester/parts by weight: 60 or more and 120 or less

Range (I) of Amount Per 100 Parts by Weight of the Polyol Compound

[0224] Ammonium polyphosphate/parts by weight: 75 or more and 100 or less [0225] Phosphoric ester/parts by weight: 60 or more and 140 or less

[0226] It is to be noted that there was at least the fact that the specimen having the ammonium polyphosphate of 75 parts by weight and the phosphoric ester of 40 parts by weight per 100 parts by weight of the polyol compound did not arrive at uninflammable material as a result of the heat release test in Table 11, but the specimen having the same amount of contents arrived at uninflammable material as averaged results of larger sample number (N=3) of the heat release tests in Table 19.

(9) Experimental Examples 73 to 99 (Table 20 to 22)

[0227] Still further subsequently, Tables 20 to 22 show results of Experimental EXAMPLES 73 to 99 which are the same in heat release test as Experimental EXAMPLES 64 to 72 in Table 17 dependent upon various products containing the ammonium polyphosphate and the phosphoric ester.

TABLE-US-00020 TABLE 20 OH value/ EX- EX- EX- EX- EX- EX- EX- EX- EX- Product NCO AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE name Composition content 73 74 75 76 77 78 79 80 81 MAXIMOL A Terephthalic 200 100 100 100 100 100 100 100 100 100 RFK-509 acid polyester polyol BiCAT B1 Catalyst 2 2 2 2 2 2 2 2 2 8210 TMR-7 B2 Trimerization 5 5 5 5 5 5 5 5 5 catalyst POLYCAT B3 Trimerization 5 5 5 5 5 5 5 5 5 46 catalyst Taien CII C1 Flame 40 50 75 40 50 75 40 50 75 AP422 C1- retardant 4 ammonium polyphosphate TCPP C2 Flame TCP C2- retardant 40 40 40 60 60 60 80 80 80 1 phosphoric ester Solstice D1 Foaming 40 40 40 40 40 40 40 40 40 LBA agent HFO- 1233zd Opteon D2 Foaming 20 20 20 20 20 20 20 20 20 1100 agent HFO- 1336mzz Water D3 Foaming 6234 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (H.sub.2O) agent water (H.sub.2O) Polyol premix total 252.50 262.50 287.50 272.50 282.50 307.50 292.50 302.50 327.50 PM-200 I Polyisocyanate 31 252.50 262.50 287.50 272.50 282.50 307.50 292.50 302.50 327.50 polymeric MDI Polyol premix hydroxyl value 91.55 88.06 80.41 84.83 81.83 75.18 79.03 76.42 70.59 NCO Index 452 470 515 488 506 551 524 542 587 EX- EX- EX- EX- EX- EX- EX- EX- EX- AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE CCM Result 73 74 75 76 77 78 79 80 81 Foam density kg/m.sup.3 26.8 29.4 33.3 29.6 31.1 34.9 31.8 33.4 38.7 Gross calorific 10 min 5.2 4.6 3.7 3.4 3.3 3.6 4.1 4.9 4.0 value MJ/m.sup.2 20 min 6.4 6.0 5.1 4.7 4.4 4.8 5.3 6.8 5.8 MJ/m.sup.2 Maximum heat kW/m.sup.2 61.2 59.4 51.5 41.4 42.2 53.4 45.6 45.4 50.0 release rate

TABLE-US-00021 TABLE 21 OH value/ EX- EX- EX- EX- EX- EX- EX- EX- EX- Product NCO AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE name Composition content 82 83 84 85 86 87 88 89 90 MAXIMOL A Terephthalic 200 100 100 100 100 100 100 100 100 100 RFK-509 acid polyester polyol BiCAT B1 Catalyst 2 2 2 2 2 2 2 2 2 8210 TMR-7 B2 Trimerization 5 5 5 5 5 5 5 5 5 catalyst POLYCAT B3 Trimerization 5 5 5 5 5 5 5 5 5 46 catalyst Taien CII C1 Flame AP422 C1- retardant 40 50 75 40 50 75 40 50 75 4 ammonium polyphosphate TCPP C2 Flame 40 40 40 60 60 60 80 80 80 TCP C2- retardant 1 phosphoric ester Solstice D1 Foaming 40 40 40 40 40 40 40 40 40 LBA agent HFO- 1233zd Opteon D2 Foaming 20 20 20 20 20 20 20 20 20 1100 agent HFO- 1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 252.50 262.50 287.50 272.50 282.50 307.50 292.50 302.50 327.50 PM-200 I Polyisocyanate 31 252.50 262.50 287.50 272.50 282.50 307.50 292.50 302.50 327.50 polymeric MDI Polyol premix hydroxyl value 91.55 88.06 80.41 84.83 81.83 75.18 79.03 76.42 70.59 NCO Index 452 470 515 488 506 551 524 542 587 EX- EX- EX- EX- EX- EX- EX- EX- EX- AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE AMPLE CCM Result 82 83 84 85 86 87 88 89 90 Foam density kg/m.sup.3 27.9 29.9 34.4 29.8 32.2 35.6 32.5 35.1 36.9 Gross calorific 10 min 4.9 4.6 4.7 4.1 4.0 3.9 5.9 4.9 4.9 value MJ/m.sup.2 20 min 7.0 6.1 6.7 5.3 6.9 5.3 7.1 6.4 6.8 MJ/m.sup.2 Maximum heat kW/m.sup.2 51.3 49.7 62.4 56.4 46.3 50.3 62.6 65.0 64.9 release rate

TABLE-US-00022 TABLE 22 Product OH value/ EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE name Composition NCO content 91 92 93 94 95 MAXIMOL A Terephthalic acid 200 100 100 100 100 100 RFK-509 polyester polyol BiCAT B1 Catalyst 2 2 2 2 2 8210 TMR-7 B2 Trimerization 5 5 5 5 5 catalyst POLYCAT B3 Trimerization 5 5 5 5 5 46 catalyst Taien CII C1 Flame retardant AP422 C1-4 ammonium 40 50 75 40 50 polyphosphate TCPP C2 Flame retardant TCP C2-1 phosphoric ester 40 40 40 60 60 Solstice D1 Foaming agent 40 40 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 252.50 262.50 287.50 272.50 282.50 PM-200 I Polyisocyanate 31 252.50 262.50 287.50 272.50 282.50 polymeric MDI Polyol premix hydroxyl value 91.55 88.06 80.41 84.83 81.83 NCO Index 452 470 515 488 506 Product OH value/ EXAMPLE EXAMPLE EXAMPLE EXAMPLE name Composition NCO content 96 97 98 99 MAXIMOL A Terephthalic acid 200 100 100 100 100 RFK-509 polyester polyol BiCAT B1 Catalyst 2 2 2 2 8210 TMR-7 B2 Trimerization 5 5 5 5 catalyst POLYCAT B3 Trimerization 5 5 5 5 46 catalyst Taien CII C1 Flame retardant AP422 C1-4 ammonium 75 40 50 75 polyphosphate TCPP C2 Flame retardant TCP C2-1 phosphoric ester 60 80 80 80 Solstice D1 Foaming agent 40 40 40 40 LBA HFO-1233zd Opteon D2 Foaming agent 20 20 20 20 1100 HFO-1336mzz Water D3 Foaming agent 6234 0.5 0.5 0.5 0.5 (H.sub.2O) water (H.sub.2O) Polyol premix total 307.50 292.50 302.50 327.50 PM-200 I Polyisocyanate 31 307.50 292.50 302.50 327.50 polymeric MDI Polyol premix hydroxyl value 75.18 79.03 76.42 70.59 NCO Index 551 524 542 587 EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE CCM Result 91 92 93 94 95 Foam density kg/m.sup.3 27.5 28.8 33.5 28.7 30.8 Gross calorific 10 min 5.7 5.9 5.7 6.1 5.4 value MJ/m.sup.2 20 min 7.4 7.8 7.7 7.7 6.7 MJ/m.sup.2 Maximum heat kW/m.sup.2 72.3 67.9 79.5 62.9 57.0 release rate EXAMPLE EXAMPLE EXAMPLE EXAMPLE CCM Result 96 97 98 99 Foam density kg/m.sup.3 34.3 30.9 32.2 36.3 Gross calorific 10 min 4.5 6.0 5.3 5.6 value MJ/m.sup.2 20 min 6.4 7.3 6.6 7.5 MJ/m.sup.2 Maximum heat kW/m.sup.2 63.9 63.1 66.0 60.5 release rate

[0228] As shown in Tables 17, 20 to 22, there was at least the fact that equivalent uninflammability and quasi-uninflammability can be achieved by specimens irrespective of various products containing the ammonium polyphosphate having an amount within a range of 40 parts by weight to 75 parts by weight and the phosphoric ester having an amount within a range of 40 parts by weight to 80 parts by weight per 100 parts by weight of the polyol compound.

[0229] It is considered, therefore, that a urethane resin composition in an embodiment of the present invention having the ammonium polyphosphate and phosphoric ester whose respective amounts fall within any one of ranges from Range (A) to Range (E) is highly likely to become equivalent to a quasi-uninflammable material, irrespective of any changing of products having such ammonium polyphosphate and phosphoric ester. Further, it is also considered that a urethane resin composition in an embodiment of the present invention having the ammonium polyphosphate and phosphoric ester whose respective amounts fall within any one of ranges from Range (F) to Range (I) is highly likely to become equivalent to an uninflammable material, irrespective of any changing of products having such ammonium polyphosphate and phosphoric ester.