JP7823151B2 - Urethane resin composition - Google Patents

Description

The present invention relates to a urethane resin composition used as a heat insulating material for buildings.

In reinforced concrete and steel-framed houses, sprayed rigid polyurethane foam insulation is often used to prevent condensation, provide insulation, and save energy.
In recent years, there have been rare cases of fires caused by insulation igniting due to improper construction management, etc. In addition, even in the case of general fires, the fire may spread to insulation, causing the fire to spread.
In order to prevent such urethane foam from burning, a fire-resistant coating (such as a cement-based inorganic spray material) may be applied, but this has problems such as the time required for application and the fact that the coating does not adhere well to the urethane foam after application, causing it to fall off.

As a result, the urethane resin compositions shown in the following Patent Documents 1 and 2 are known as urethane resin compositions that have been imparted with flame retardancy.

Patent No. 6200435 Patent No. 6725606

In the heat generation test according to ISO-5660 for evaluating the flame retardancy of a urethane resin composition, a testing device called a cone calorimeter is used.
The cone calorimeter comprises a cone heater placed above a test specimen cut to a predetermined size, and a spark rod provided between the test specimen and the cone heater.
In the heat generation test in accordance with ISO-5660, combustible gas is generated from the test specimen by heating it with a cone heater, and the combustible gas is ignited by a spark from a spark rod, causing combustion. The total amount of heat generated by the combustion is measured using a specified measurement method, and the flame retardancy is evaluated in light of the performance requirements shown in Table 1 below.
These performance requirements are set by the General Building Research Corporation of Japan and the Japan Testing Center for Construction Materials as standards for conforming to the technical standards set forth in Article 2, Paragraph 9 of the Building Standards Act, Article 1, Paragraphs 5 and 6 of the Enforcement Order of the Building Standards Act, and Article 108-2 of the Enforcement Order of the Building Standards Act.

[Table 1]

During the heat generation tests, some test specimens swelled when heated by the cone heater, and in some cases the swollen area of the test specimen came into contact with the spark plug, or discharge was confirmed even without contact between the expanded test specimen and the plug (these phenomena are hereinafter referred to as "spark contact").
Test specimens in which spark contact has occurred will not produce valid results when conforming to ISO-5660, so it is necessary to check for spark contact each time.

Furthermore, when the urethane resin composition is used as a heat insulating material, the expansion caused by heating can apply pressure to interior materials (such as gypsum boards) placed around the heat insulating material, causing damage.
If the interior materials are damaged, heat from a fire will be more easily transferred to the insulation, increasing the possibility that the heat will have a thermal impact on the exterior materials.

Therefore, one of the objects of the present invention is to provide a urethane resin composition that is less likely to swell when heated.

To solve the above problems, the present invention provides a urethane resin composition that forms a foam that constitutes a thermal insulation material for buildings, and that contains at least a polyisocyanate compound, a polyol compound, a trimerization catalyst, a blowing agent, and a flame retardant, but does not contain a foam stabilizer or a surface conditioner.

According to the present invention, a urethane resin composition that is less likely to swell when heated can be obtained.
In a preferred embodiment of the present invention, a urethane resin composition can be obtained that does not cause spark contact even in a heat buildup test in accordance with ISO-5660.
Furthermore, in a preferred embodiment of the present invention, a urethane resin composition can be obtained that, when used as a heat insulating material for buildings, prevents the heat insulating material from expanding beyond the clearance between the heat insulating material and the interior material, and does not push up and damage the interior material.
Furthermore, in a preferred embodiment of the present invention, the number of raw materials required to form the urethane resin composition can be reduced, thereby contributing to cost reduction.

<1> Overall Configuration The urethane resin composition according to the present invention is used to form a foam that constitutes a thermal insulating material for buildings, and contains at least a polyisocyanate compound, a polyol compound, a trimerization catalyst, a blowing agent, and a flame retardant, but does not contain a foam stabilizer or a surface conditioner.
The urethane resin composition according to the present invention may also be configured to further contain a material derived from a mineral such as a clay mineral.
The above composition can be separated into a polyisocyanate compound (first liquid) and other components (second liquid), and the two components are mixed while being sprayed, or the two components are mixed and sprayed, etc., to form a heat insulating layer on a building.

<2> Various Performance Properties The urethane resin composition according to the present invention can be provided with the following performance properties by adjusting the blending ratio of each material.

<2.1> Non-flammability The urethane resin composition according to the present invention can be provided with non-flammability as specified by a heat buildup test in accordance with ISO-5660.

<2.1.1> ISO-5660 Testing In heat generation tests conforming to ISO-5660, a testing device called a cone calorimeter is used.
The cone calorimeter is equipped with a cone heater placed above a test specimen cut to a specified size, and a spark rod installed between the test specimen and the cone heater. Combustible gas is generated from the test specimen by heating it with the cone heater, and the combustible gas is ignited by a spark from the spark rod, causing combustion. The total heat generated by the combustion is measured using a specified measurement method, and the flame retardancy is evaluated in light of the performance requirements shown in Table 2 below.

[Table 2]

<2.2> Swelling upon heating (maximum expansion length) The urethane resin composition according to the present invention can swell to an extent that does not cause spark contact when an ISO-5660 test is carried out.
A guideline for preventing spark contact is that the maximum expansion length in the height direction of the test specimen is less than 8 mm, more preferably 2 mm or less.
With the above configuration, spark contact can be avoided, and effective results can be obtained in the ISO-5660 test.

<2.2.1> Method for Measuring the Amount of Swelling The method for measuring the amount of swelling in the height direction of the test specimen described above is described below.
(1) Before the heat generation test, the height position of the upper surface of the test specimen is marked on the windshield frame provided in front of the cone calorimeter.
(2) After the heat generation test, the height from the marking on the windshield frame to the highest point on the upper surface of the expanded test specimen is measured visually.

<2.3> Density The urethane resin composition according to the present invention can provide a foam having a density of 30 kg/m3 or more.
By setting the density of the foam to 30 kg/m 3 or more, it is possible to obtain a sufficient effect of suppressing deformation against impact from outside when used as a heat insulating material for buildings.

<3> Polyisocyanate Compound The polyisocyanate compound is a material used as a main component in the urethane resin composition according to the present invention.
Examples of the polyisocyanate compound include aromatic polyisocyanates, alicyclic polyisocyanates, aliphatic polyisocyanates, and modified polyisocyanates.
Examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.
Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.
Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.
The modified polyisocyanate is an isocyanate group-terminated prepolymer obtained by reacting a polyol component with a polyisocyanate compound, and examples thereof include urethane-modified products, carbodiimide-modified products, urea-modified products, biuret-modified products, and allophanate-modified products.
The polyisocyanate compounds may be used singly or in combination of two or more.
In particular, polymethylene polyphenyl polyisocyanate (polymeric MDI, crude MDI) is preferred because it is liquid at room temperature and is readily available.
Examples of the polymethylene polyphenyl polyisocyanate include Millionate MR-200, MR-100, and MR-400 manufactured by Tosoh Corporation, Sumidur 44V20L and Dismodur 44V20L manufactured by Covestro Corporation, PM-200 and PM-400 manufactured by Wanka Chemical Industry Co., Ltd., and PAPI27 and PAPI135 manufactured by Dow Chemical Industry Co., Ltd.

The amount of polyisocyanate contained in the urethane resin composition is preferably set so that the isocyanate index is 150 to 1000. If the isocyanate index is 150 or more, the flame retardancy is further improved, and if it is 1000 or less, the adhesion to the frame or the like is good.
In particular, in the present invention, the isocyanate index is most preferably in the range of 400 to 600.
The isocyanate index is calculated as the equivalent ratio of the isocyanate group contained in the isocyanate component to the active hydrogen contained in the polyol component and water or the like of the blowing agent.
[Isocyanate group]/[OH group] (molar ratio)×100

<4> Polyol Compound The polyol compound is a material used as a curing agent in the urethane resin composition according to the present invention.
The polyol compound comprises an ester-based polyol compound, an ether-based polyol compound, or a combination thereof.

<4.1> Ester-Based Polyol Compounds Examples of ester-based polyol compounds include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone, and condensates of hydroxycarboxylic acids and the above-mentioned polyhydric alcohols.
Specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, succinic acid, etc. In terms of flame retardancy, terephthalic acid-modified polybasic acids are preferred.

<4.2> Other Polyol Compounds Examples of other polyol compounds include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polymer polyols, and polyether polyols.
Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.
Examples of the polycarbonate polyol include polyols obtained by dealcoholization reaction of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, or nonanediol with diethylene carbonate or dipropylene carbonate.
Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, and cresol novolac.
Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.
Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.
Examples of the polyhydric polyether polyols include 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, and cyclohexane-1,4-diol. Examples of suitable initiators include low molecular weight polyols such as bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol, and sucrose, and aromatic and aliphatic polyamines such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine, and triethanolamine, and polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, and alkyl glycidyl ethers such as methyl glycidyl ether, aryl glycidyl ether, and tetrahydrofuran.
In addition, polyether polyols containing bromine, phosphorus, etc. may also be used.

<5> Mineral-derived materials Mineral-derived materials are materials that are intended to improve flame retardancy and density.
As the mineral-derived material, silicate compounds are preferred, and examples of the mineral-derived material that can be used include montmorillonite, saponite, hectorite, vermiculite, kaolinite, mica, and talc.
An example of the material containing kaolinite as a main component is kaolin.
The kaolin also includes calcined kaolin obtained by treating kaolin at high temperatures. Calcined kaolin is preferred because it has a small moisture content and a small particle size distribution.

There are no particular restrictions on the amount of the mineral-derived material, but it is desirable for it to be 15 to 85 parts by weight per 100 parts by weight of the polyol compound.

<6> Trimerization Catalyst The trimerization catalyst is a material for promoting the formation of isocyanurate rings by reacting isocyanate groups contained in a polyisocyanate compound to cause trimerization.
Examples of the trimerization catalyst that can be used include nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; alkali metal carboxylates such as potassium acetate, potassium 2-ethylhexanoate, and potassium octylate; and quaternary ammonium salts such as tetramethylammonium salts, tetraethylammonium salts, and tetraphenylammonium salts.
In terms of low temperature adhesion and flame retardancy, a combination of an alkyl metal carboxylate and a quaternary ammonium salt is preferred.
Examples of trimerization catalysts include Toyocat-TRX, Toyocat-TRV, and Toyocat-TR20 manufactured by Tosoh Corporation, DABCO TMR, DABCO TMR-2, DABCO TMR-7, DABCO K-15, UCAT 18X, and Polycat 46 manufactured by Evonik, and KAOLIZER NO. 410 and KAOLIZER NO. 420 manufactured by Kao Corporation.

The amount of the trimerization catalyst is not particularly limited, but is preferably 1 to 20 parts by weight per 100 parts by weight of the polyol compound. At 1 part by weight or more, flame retardancy will be even better, while at 20 parts by weight or less, problems such as clogging of the mixing section of the spray gun due to an overly rapid reaction can be prevented.

<7> Foaming Agent The foaming agent is a material that promotes a decrease in density of the molded product by generating gas inside the resin when the polyisocyanate compound (first liquid) is mixed with other components (second liquid).
An example of a blowing agent is water. Carbon dioxide is generated by the reaction of isocyanate with water, and the carbon dioxide is trapped inside the foam, promoting a decrease in the density of the molded product.

Other examples of blowing agents include the so-called physical blowing agents listed below. Although they are liquid at room temperature, they gasify inside the resin due to the exothermic reaction between isocyanate and polyol, promoting a decrease in the density of the molded product.

[1] Hydrocarbon compounds: propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, methyl formate, and the like.

[2] Chlorinated aliphatic hydrocarbon compounds: dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, and the like.

[3] Fluorine compounds: CHF3, CH2F2, CH3F, etc.

[4] Hydrochlorofluorocarbon compounds Trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)), and the like.

[5] Hydrofluorocarbons HFC-245fa (1,1,1,3,3-pentafluoropropane) manufactured by Central Glass Co., Ltd., HFC-365mfc (1,1,1,3,3-pentafluorobutane) manufactured by Honeywell, and the like.

[6] Hydrofluoroolefins: Solstice LBA (HFO-1233zd, (E)-1-chloro-3,3,3-trifluoropropene) manufactured by Honeywell; Opteon 1100 (HFO-1336mzz(Z), (Z)-1,1,1,4,4,4-hexafluoro-2-butene) manufactured by Chemours; Opteon 1150 (HFO-1336mzz(E), (E)-1,1,1,4,4,4-hexafluoro-2-butene) manufactured by Chemours; Amorea 1224yd ((Z)-1-chloro-2,3,3,3-tetrafluoropropene) manufactured by AGC; and the like.

[7] Organic compounds: methyl formate, diisopropyl ether, etc.

Other foaming agents that can be used include nitrogen gas, oxygen gas, argon gas, carbon dioxide gas, etc., which can be dispersed or dissolved in the polyol component or isocyanate component.

There are no particular restrictions on the amount of blowing agent, but it is preferable that it be between 1 and 100 parts by weight per 100 parts by weight of polyol. The more parts by weight of blowing agent used, the lower the foam density, but at the same time, the lower the dimensional stability and compressive strength. Therefore, the number of parts by weight of blowing agent should be set to match the density design.

In addition, in the present invention, one or more of the above-mentioned foaming agents may be used.

<8> Flame Retardant The flame retardant is a material for imparting flame retardancy to the urethane resin composition according to the present invention.
In the present invention, the flame retardant is not particularly limited, but is preferably one containing at least one selected from the group consisting of red phosphorus, ammonium polyphosphate, and phosphate ester, in order to obtain high flame retardancy.
In particular, a combination of two or more components, such as ammonium polyphosphate and phosphate ester, in addition to red phosphorus, is preferred in that even higher flame retardancy can be obtained.

<8.1> Red phosphorus Red phosphorus is a material that suppresses the total heat generated during combustion.
There is no limitation on the red phosphorus used in the present invention, and commercially available products can be appropriately selected and used.

The amount of red phosphorus is not particularly limited, but it is desirable for the amount to be 15 to 35 parts by weight per 100 parts by weight of the polyol compound.

<8.2> Phosphate-containing flame retardants Phosphate-containing flame retardants, like red phosphorus, are materials that suppress the total heat generated during combustion.
The phosphate-containing flame retardant used in the present invention contains phosphoric acid.

Examples of the phosphate-containing flame retardant include phosphates formed from salts of the various phosphoric acids and at least one metal or compound selected from metals of Groups IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines.
Examples of the metals of Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.
Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and piperazine.
Examples of the aromatic amine include pyridine, triazine, melamine, and ammonium.
The phosphate-containing flame retardant may be subjected to a known treatment for improving water resistance, such as treatment with a silane coupling agent or coating with a melamine resin, and may also contain a known foaming aid such as melamine or pentaerythritol.

Specific examples of the phosphate-containing flame retardant include monophosphates, pyrophosphates, and polyphosphates.
Examples of the monophosphate salts include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, and sodium hypophosphite; potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, and potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, and lithium hypophosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, and barium hypophosphite; magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; and zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite.
Examples of the polyphosphate salt include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate.

Among these, it is preferable to use polyphosphates, as this improves the self-extinguishing properties of the phosphate-containing flame retardant, and it is even more preferable to use ammonium polyphosphate or aluminum phosphite, which forms a foam layer when heated.

The above-mentioned phosphate-containing flame retardants can be used singly or in combination.

The amount of the phosphate-containing flame retardant is not particularly limited, but it is preferably 20 to 50 parts by weight per 100 parts by weight of the polyol compound.

<8.3> Chlorine-containing flame retardant Chlorine-containing flame retardants are elements that suppress the maximum heat release rate in the early stage of combustion.
The following five types of flame retardants are widely used as chlorine-containing flame retardants.
(a) Tris(chloroethyl)phosphate (TCEP)
(b) Tris(β-chloropropyl)phosphate (TCPP)
(c) Tris(dichloropropyl)phosphate (TDCP)
(d) Tetrakis(2-chloroethyl)dichloroisopentyl diphosphate (V6)
(e) Polyoxyalkylene bis(dichloroalkyl)phosphate (CR-504L)

The content of the chlorine-containing flame retardant is not particularly limited, but it is preferably 60 to 120 parts by weight per 100 parts by weight of the polyol compound.

<9> Foam stabilizers and surface conditioners The foam stabilizers and surface conditioners not included in the formulation of the present invention will be explained below.

<9.1> Foam Stabilizer The foam stabilizer is an organosiloxane-polyoxyalkylene copolymer or the like used in the production of polyurethane foam.
Examples of the foam stabilizer include L-6900 manufactured by MOMENTIVE and SH-193 manufactured by Toray Dow Corning.

<9.2> Surface Conditioner A surface conditioner is an additive that controls surface tension and acts as a defoaming agent, leveling agent, and anti-foaming agent, thereby forming a good coating film.
Examples of the surface conditioner include acrylic polymers such as SEI-W01 and SEI-1501 manufactured by Kusumoto Chemicals.

<10> Others The urethane resin composition according to the present invention may also contain the following materials as appropriate.

<10.1> Catalyst The catalyst used in forming urethane foam is a material that promotes the reaction between isocyanate and active hydrogen in the polyol and the reaction between isocyanate and water.

Examples of catalysts having an amine group include N-alkylpolyalkylenepolyamines 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.
Examples of catalysts containing organic metals include bismuth octoate, lead octoate, tin(II) 2-ethylhexanoate, dibutylbis[(1-oxooctyl)oxy]stannane, dibutyltin diacetate, and dibutyltin dilaurate.

Examples of amine catalyst products include TEDA-L33, TOYOCAT-ET, TOYOCAT-MR, TOYOCAT-TE, TOYOCAT-DT, TOYOCAT-NP, RX-5, RX-10, and TOYOCAT-DM70 manufactured by Tosoh, 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 manufactured by Evonik, and KAOLIZER NO. 1 and 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, KAOLIZER No. 390, and the like.
These catalysts can be used singly or in combination of two or more.

<1> Test Conditions The following tests were carried out on the foamed product made of the urethane resin composition according to the present invention. Details of each material are as follows:

(1) Polyol Compound A: Terephthalic Acid Polyester Polyol (manufactured by Air Water Material, product name: Maximol RFK-505, hydroxyl value = 250 mg KOH/g)

(2) Foam stabilizer B: Silicone foam stabilizer (manufactured by Momentive, product name: L-6900)

(3) Surface conditioner C: acrylic polymer (manufactured by Kusumoto Chemicals, product name: SEI-W01)

(4) Catalyst D1: Amine catalyst (manufactured by Evonik, product name: DABCO 2040)
D2: Amine catalyst (manufactured by Evonik, product name: Polycat 201)
D3: organometallic catalyst (manufactured by Shepherd, product name: Bicat 8210)

(5) Trimerization catalyst E1: quaternary ammonium salt (manufactured by Evonik, product name: TMR-7)
E2: Potassium acetate catalyst (manufactured by Evonik, product name: Polycat 46)

(6) Mineral-derived materials F: Calcined kaolin (manufactured by Imerys Minerals, product name: Glomax LL)

(7) Flame retardant G1: Red phosphorus (manufactured by Rinkagaku Kogyo Co., Ltd., product name: Novaexcel 140)
G2: Ammonium polyphosphate (manufactured by Taihei Chemical Industry Co., Ltd., product name: Taien CII)
G3: Phosphate ester (manufactured by Wansheng, product name: TCPP)

(8) Foaming agent H1: HFO-1233zd (manufactured by Honeywell, product name: Solstice LBA)
H2: HFO-1336mzz (manufactured by Chemours, product name: Opteon 1100)
H3: Water (hydroxyl value = 6234 mg KOH/g)

(9) Polyisocyanate I: Polymeric MDI (manufactured by Tosoh Corporation, product name: Millionate MR-200, NCO content = 31%)

<2> Method for Preparing Test Specimens According to the formulations in the tables of each figure, polyol, catalyst, trimerization catalyst, flame retardant, blowing agent, surface conditioner, and foam stabilizer components were weighed into a 1000 mL polypropylene beaker and stirred.
Hereinafter, this mixture will be referred to as a polyol premix.
The polyol premix and isocyanate were kept at a temperature of 5°C.
The isocyanate component was added to the temperature-adjusted polyol premix component according to the formulation in the table of each figure. After stirring for about 3 seconds with a hand mixer, the mixture was quickly poured into a 200 x 200 x 200 mm wooden box that had been adjusted to 20°C, yielding a foam. (Because the polyol premix component contains powder, the isocyanate component was pre-mixed and dispersed immediately before mixing.)
After foaming, the foam was cured for 24 hours and then cut into a size of 99 mm x 99 mm x 50 mm. The mass was measured (the foam density was calculated from the mass and size), and then a cone calorie test specimen was prepared (the test specimen was cut to a height of 50 mm in the foaming direction).

<3> Test details Each test specimen was subjected to a heat generation test in accordance with the ISO-5660 test method, in which a radiant heat intensity of 50 kW/m2 was used for a heating time of 20 minutes, and the total heat generation amount (after 10 minutes of heating and after 20 minutes of heating), maximum heat generation rate, time exceeding 200 kW/m2 (time during which the maximum heat generation rate continuously exceeded 200 kW/m2), maximum expansion length of the test specimen (in the height direction), and whether or not there was contact with a spark were evaluated.
Details of the test equipment used in this test are as follows:
- Toyo Seiki Seisakusho, product name: Cone calorimeter, model: C4
Distance between test piece and spark plug: 12.5 mm

<4> Test Results Experimental examples for comparison are extracted from all test results and will be explained with reference to the figures.

(1) Experimental Examples 1 and 2 (Table 3)
[When either a foam stabilizer or a surface conditioner is included]
Experimental Examples 1 and 2 (Table 3) contain either a foam stabilizer or a surface conditioner.

[Table 3]

Spark contact occurred in all test specimens.

(2) Experimental Examples 3 to 21 (Tables 4 to 7)
[When the amount of kaolinite is changed]
In Experimental Examples 3 to 21 (Tables 4 to 7), no foam stabilizer or surface conditioner was contained, and the amount of kaolinite blended was varied from 0 to 100 parts by weight.

[Table 4]

[Table 5]

[Table 6]

[Table 7]

The maximum expansion length of all the test specimens was 2 mm or less, and no spark contact occurred.
Furthermore, in Experimental Examples 3, 4, 20, and 21, the test specimens were equivalent to quasi-noncombustible materials, and in Experimental Examples 5 to 19 (in which the amount of kaolinite blended was 15 to 85 parts by weight), the test specimens were equivalent to noncombustible materials.
In addition, the test specimens according to Experimental Examples 4 to 21 (in which the amount of kaolinite blended was 10 parts by weight to 100 parts by weight) had a foam density of 30 kg/m 3 or more.

(3) Experimental Examples 22 to 32 (Tables 8 to 10)
[When the amount of flame retardant added is changed]
In Experimental Examples 22 to 32 (Tables 8 to 10), no foam stabilizer or surface conditioner was added, the amount of kaolinite was fixed at 25 parts by weight, and the amount of flame retardant was changed.

[Table 8]

[Table 9]

[Table 10]

The maximum expansion length of all the test specimens was 2 mm or less, and no spark contact occurred.
Furthermore, the test specimens according to Experimental Examples 23 to 26 and Experimental Examples 29 to 32 were equivalent to non-combustible materials, and the foam density was 30 kg/m3 or more.

(4) Experimental Examples 33 to 40 (Tables 11 and 12)
[When the amount of foaming agent is changed]
In Experimental Examples 33 to 40 (Tables 11 and 12), no foam stabilizer or surface conditioner was contained, and the amount of kaolinite blended was 0 parts by weight, 25 parts by weight, 50 parts by weight, and 75 parts by weight, while the amount of each foaming agent blended was changed.

[Table 11]

[Table 12]

The maximum expansion length of all the test specimens was 2 mm or less, and no spark contact occurred.
Further, Experimental Examples 33 and 40 were equivalent to quasi-noncombustible materials, and Experimental Examples 34 to 39 were equivalent to noncombustible materials.
In addition, the foam density of all the test specimens was 30 kg/m3 or more.

Claims (1)

A urethane resin composition for forming a foam constituting a thermal insulation material for a building,
The composition contains at least a polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent, calcined kaolin, and a flame retardant, but does not contain a foam stabilizer or a surface conditioner;
The foaming agent is contained in an amount of 20.5 parts by weight or more and 40.5 parts by weight or less, and the calcined kaolin is contained in an amount of 25 parts by weight or more and 50 parts by weight or less, relative to 100 parts by weight of the polyol compound,
The flame retardant contains at least red phosphorus, ammonium polyphosphate, and a phosphate ester,
The density of the foam is 42.1 kg/ ^m3 or more,
In a heat generation test in accordance with ISO-5660, a test specimen made of the foam has a maximum expansion length in the height direction of 2 mm or less, and the test specimen is equivalent to a non-combustible material.
Urethane resin composition.