Polyol compositions, urethane resin compositions, and polyurethane foams

Abstract

To provide a polyol composition that can give a polyurethane foam having a low calorific value in a middle period of combustion and excellent incombustibility.SOLUTION: A polyol composition contains a polyol compound, a flame retardant A having an acidity of less than pH 6.5 when heated to 500°C, and red phosphorus.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyol composition, a urethane resin composition containing the polyol composition, and a polyurethane foam made from the urethane resin composition. [Background technology]

[0002] Polyurethane foam, with its excellent thermal insulation properties, is used in practical applications for insulating and preventing condensation in various structures such as ceilings, roofs, and walls of buildings including apartment complexes, detached houses, and commercial buildings. Polyurethane foam is formed, for example, by spraying a urethane resin composition containing polyol compounds and polyisocyanate compounds onto the surface of each structure, followed by foaming and curing. Furthermore, while polyurethane foam offers excellent heat insulation and is lightweight, it is known to be highly flammable. Therefore, there is a demand for less flammable polyurethane foam, particularly from the perspective of preventing the spread of fire.

[0003] For example, Patent Document 1 describes an invention relating to a flame-retardant urethane resin composition comprising a polyisocyanate compound, a polyol compound, a catalyst, a blowing agent, a foam stabilizer, and an additive, wherein the additive comprises at least one of red phosphorus, clay minerals, layered polysilicic acid, and a molybdenum compound. It has been shown that a foam (polyurethane foam) formed from this flame-retardant urethane resin composition suppresses the generation of carbon monoxide and exhibits high flame retardancy. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2017-226831 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] While conventional polyurethane foams possess a certain degree of flame retardancy, there was room for improvement in terms of reducing the amount of heat generated during the middle stage of combustion throughout the entire combustion process (from the initial to the later stages of combustion) during a fire. Reducing the heat output during the mid-combustion phase of the entire combustion process during a fire makes it easier to stabilize the shape of the combustion residue after combustion. For example, it becomes easier to prevent flames from passing through from one side of the combustion residue to the other, and the overall heat output of the combustion process is reduced, improving its non-combustibility. Therefore, the present invention aims to provide a polyol composition that yields a polyurethane foam with low heat output during the middle of combustion and excellent non-flammability. [Means for solving the problem]

[0006] As a result of diligent research, the inventors have discovered that polyurethane foam obtained from a polyol composition containing a polyol compound, a flame retardant A having an acidity of less than pH 6.5 when heated to 500°C, and red phosphorus exhibits low heat generation during the middle stage of combustion and excellent non-flammability, thus completing the present invention. The present invention provides the following [1] to

[14] .

[0007] [1] A polyol composition containing a polyol compound, a flame retardant A having an acidity of less than pH 6.5 when heated to 500°C, and red phosphorus. [2] The polyol composition according to [1], wherein the amount of flame retardant A is 3 to 20 parts by mass per 100 parts by mass of the polyol compound. [3] The polyol composition according to [1] or [2] above, comprising a gas-generating flame retardant B having a decomposition initiation temperature of 330 to 450°C. [4] The polyol composition according to [3] above, wherein the content of the gas-generating flame retardant B is 15 to 40 parts by mass per 100 parts by mass of the polyol compound. [5] The polyol composition according to [3] or [4] above, wherein the ratio of the total mass of flame retardants A and B to the mass of red phosphorus is 0.2 or more and 3 or less. [6] The polyol composition according to any one of [1] to [5] above, wherein the flame retardant A is a tubular compound. [7] The polyol composition according to any one of [1] to [6] above, containing a foaming agent. [8] The polyol composition according to any one of [1] to [7] above, containing a catalyst containing a trimerization catalyst. [9] The polyol composition according to [8] above, wherein the trimerization catalyst contains a quaternary ammonium salt.

[10] The polyol composition according to [8] or [9] above, wherein the catalyst contains an imidazole derivative.

[11] The polyol composition according to any one of [8] to

[10] above, wherein the catalyst contains at least one metal catalyst selected from the group consisting of bismuth and tin.

[12] A urethane resin composition containing the polyol composition according to any one of [1] to

[11] above and a polyisocyanate composition.

[13] A polyurethane foam made of the urethane resin composition according to

[12] above.

[14] When a combustion test is performed using a cone calorimeter, the total heat release from 60 to 400 seconds is 1.6 MJ / m , , ,

[0008] , , , ,

[0010] , , , , , [Figure 2] , [Figure 1] ,

[0009] , , The polyurethane foam according to

[13] above, which is as follows.

Advantages of the Invention

[0008] According to the present invention, it is possible to provide a polyol composition that can obtain a polyurethane foam having a low heat release in the middle stage of combustion and excellent nonflammability.

Brief Description of the Drawings

[0009] [Figure 1] It is a schematic diagram showing an embodiment of a mixing system. [Figure 2] It is a schematic diagram showing another embodiment of a mixing system.

Modes for Carrying Out the Invention

[0010] [Polyol Composition] The polyol composition of the present invention contains a polyol compound, a flame retardant A with an acidity of less than pH 6.5 when heated to 500 °C, and red phosphorus. As described later, the polyol composition of the present invention can form a polyurethane foam by mixing with a polyisocyanate composition and foaming and curing.

[0011] <Flame retardant A> The polyol composition of the present invention contains a flame retardant A with an acidity of less than pH 6.5 when heated to 500 °C. When the flame retardant A is not contained, it becomes difficult to reduce the calorific value during the mid-stage of combustion of the polyurethane foam. When using a flame retardant A with an acidity of less than pH 6.5 when heated to 500 °C, the reason for being able to reduce the calorific value during the mid-stage of combustion of the polyurethane foam is not clear, but it is presumed that the flame retardant A with an acidity of less than pH 6.5 promotes the cross-linking of polyurethane at a high temperature of 500 °C or higher and promotes char formation.

[0012] The acidity of the flame retardant A when heated to 500 °C is preferably pH 6.3 or less, more preferably pH 6.0 or less, still more preferably pH 5.7 or less, and preferably pH 4.0 or more. The acidity when heated to 500 °C is measured as follows. First, 0.5 g of the flame retardant is heated at 500 °C for 60 minutes in an air atmosphere. Then, the flame retardant air-cooled to room temperature (23 °C) is dispersed in 1 g of water and the pH is measured. Ion-exchanged water is used as the water.

[0013] Examples of the flame retardant A include silicate minerals such as halloysite, montmorillonite, kaolinite, vermiculite, zinc molybdate, ammonium polyphosphate, etc. The flame retardant A may be used alone or in combination of two or more. In particular, the flame retardant A is preferably one or more selected from the group consisting of halloysite, montmorillonite, zinc molybdate, and ammonium polyphosphate, more preferably one or more selected from the group consisting of halloysite, montmorillonite, and ammonium polyphosphate, and even more preferably halloysite. Furthermore, even if these individual compounds are of the same type, differences in shape and surface condition may result in different acidity levels when heated to 500°C. Therefore, it is necessary to use compounds with an acidity level of less than pH 6.5 when heated to 500°C.

[0014] The flame retardant A is preferably a tubular (hollow tubular) compound, and is particularly preferably a tubular halloysite. When the flame retardant is tubular, the inner diameter and length are not particularly limited, but the inner diameter is, for example, 5 to 50 nm and the length is, for example, 50 to 100 nm.

[0015] The tubular halloysite has an outer surface composed of silicate (SiO2) and an inner surface composed of alumina (Al2O3). When the tubular halloysite is heated to high temperatures (e.g., 500°C or higher), some of the alumina (Al2O3) on the inner surface is exposed to the outer surface, and it is presumed that the acidity increases (pH decreases) due to the aluminol (Al-OH) present in the alumina (Al2O3), improving the non-flammability during the middle stage of combustion.

[0016] Montmorillonite is an inorganic layered compound that can contain metal ions such as sodium ions between its layers, and its acidity can be adjusted depending on the type of metal ion. Montmorillonite also tends to become more acidic at high temperatures, which improves its non-flammability during the middle stages of combustion.

[0017] From the viewpoint of improving non-flammability during the middle stage of combustion, it is preferable that the ammonium polyphosphate is coated with a resin. The resin coating the surface of the ammonium polyphosphate is preferably a thermosetting resin, and among these, melamine resin is more preferable. Ammonium polyphosphate with such a coated surface also tends to have higher acidity at high temperatures, which improves its non-flammability during the middle stage of combustion.

[0018] Zinc molybdate is a compound with excellent heat resistance; its acidity tends to increase at high temperatures, which improves its non-flammability during the middle stages of combustion.

[0019] As mentioned above, halloysite, montmorillonite, zinc molybdate, and ammonium polyphosphate become more acidic (lower pH) at high temperatures, but remain relatively acidic at low temperatures. Therefore, the storage stability of the polyol composition is also good.

[0020] The content of flame retardant A is preferably 3 to 20 parts by mass, more preferably 5 to 18 parts by mass, and even more preferably 8 to 12 parts by mass, per 100 parts by mass of the polyol compound. When the content of flame retardant A is within this range, it becomes easier to reduce the amount of heat generated during the mid-combustion phase of the formed polyurethane foam.

[0021] Flame retardant A is a solid flame retardant that is solid at 23°C. Red phosphorus, gas-generating flame retardant B, and boron-based flame retardants, which will be described later, are also solid flame retardants.

[0022] <Red phosphorus> The polyol composition of the present invention contains red phosphorus. By using the above-mentioned flame retardant A and red phosphorus in combination, it becomes easier to reduce the amount of heat generated during the middle stage of combustion of the resulting polyurethane foam, thereby improving the non-flammability of the entire combustion process. The red phosphorus may consist of pure red phosphorus, or it may be red phosphorus mixed with or coated with resin, metal hydroxide, metal oxide, etc. The red phosphorus content in the polyol composition is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 50 parts by mass, per 100 parts by mass of the polyol compound.

[0023] <Flame retardant B> The polyol composition of the present invention preferably contains a gas-generating flame retardant B, which has a decomposition initiation temperature of 330 to 450°C. By including the gas-generating flame retardant B, the total heat generated during the combustion process of the formed polyurethane foam can be reduced, thereby improving its non-flammability. The gas-generating flame retardant B is not particularly limited as long as it is a compound that has a decomposition initiation temperature greater than 330°C and 450°C or less, and generates gas during decomposition. Examples of the gas include at least one gas selected from the group consisting of nitrogen, water, ammonia, carbon dioxide, and hydrogen halides. The gas-generating flame retardant B is a solid flame retardant that is solid at 23°C. In this invention, the decomposition initiation temperature of the flame retardant is the 10% weight loss temperature, measured using a thermogravimetric analyzer under dry air conditions and a heating rate of 10°C / min. The 10% weight loss temperature is the temperature at which 10% of the weight of the sample before measurement is lost.

[0024] Examples of gas-generating flame retardants B include flame retardants that generate water (water vapor), such as calcium hydroxide and magnesium hydroxide, and flame retardants that generate hydrogen bromine. Among these, gas-generating flame retardants B that generate hydrogen bromide are preferred from the viewpoint of improving non-flammability. Preferred gas-generating agents B that generate hydrogen bromide are brominated polystyrene, ethylenebis(tetrabromophthalimide), or ethylenebis(pentabromophenyl), with ethylenebis(pentabromophenyl) being more preferred.

[0025] From the viewpoint of improving the non-flammability of polyurethane foam, the content of gas-generating flame retardant B in the polyol composition is preferably 15 to 40 parts by mass, and more preferably 20 to 40 parts by mass, per 100 parts by mass of the polyol compound.

[0026] The ratio of the total mass of flame retardant A and gas-generating flame retardant B to the mass of red phosphorus [(total mass of flame retardant A and gas-generating flame retardant B) / mass of red phosphorus] is preferably 0.2 or more and 3 or less, and more preferably 0.5 or more and 2 or less, from the viewpoint of improving the non-flammability of the resulting polyurethane foam.

[0027] <Boron-based flame retardant> The polyol composition of the present invention preferably contains a boron-based flame retardant as a flame retardant other than the flame retardant described above. This can improve the non-flammability of the polyurethane foam. The polyol composition of the present invention preferably contains the above-mentioned flame retardant A, red phosphorus, and boron-based flame retardant, and more preferably contains flame retardant A, red phosphorus, gas-generating flame retardant B, and boron-based flame retardant. Examples of boron-based flame retardants include zinc borate and calcium borate, with zinc borate being preferred.

[0028] The content of the boron-based flame retardant is not particularly limited, but is preferably 5 to 30 parts by mass, and more preferably 10 to 20 parts by mass, per 100 parts by mass of the polyol compound.

[0029] <Liquid Flame Retardant> The polyol composition of the present invention preferably contains a liquid flame retardant from the viewpoint of improving the non-flammability of the resulting polyurethane foam. Among liquid flame retardants, phosphate ester-based flame retardants are particularly preferred. Using a phosphate ester-based flame retardant can improve the non-flammability of the polyurethane foam, and also allows for appropriate control of the viscosity of the composition even when using the above-mentioned flame retardant A and gas-generating flame retardant B. Here, a liquid flame retardant is a flame retardant that is liquid at 23°C.

[0030] Examples of phosphate ester-based flame retardants include monophosphate esters and condensed phosphate esters. Examples of monophosphate esters, though not particularly limited, include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, and tris(β-chloropropyl) phosphate. Examples of condensed phosphate esters are not particularly limited, but include resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycrezyl phosphate (trade name CR-741), and aromatic condensed phosphate esters (trade name CR747).

[0031] The liquid flame retardant content is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more, and preferably 100 parts by mass or less, and more preferably 80 parts by mass or less, per 100 parts by mass of the polyol compound. If the liquid flame retardant content is above these lower limits, the non-flammability of the polyurethane foam can be improved, and if it is below these upper limits, the mechanical strength of the polyurethane foam can be improved.

[0032] <Polyol compounds> The polyol compound included in the polyol composition of the present invention is not particularly limited, but examples include polyether polyols, polyester polyols, and bromine-containing polyols. Among these, aromatic polyester polyols are preferred, and phthalic acid-based polyester polyols are more preferred, from the viewpoint of lowering the total calorific value and improving nonflammability, as will be described later. Furthermore, aromatic polyester polyols such as phthalic acid-based polyester polyols are preferably used alone as the polyol compound, but as will be described later, they may also be used in combination with other polyol compounds such as polyether polyols.

[0033] (Polyether polyol) Polyether polyols are polyoxyalkylene polyols obtained by ring-opening addition polymerization of alkylene oxide to an initiator having two or more active hydrogen atoms. Examples of initiators include aliphatic polyhydric alcohols (e.g., glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, cyclohexanedimethanol, etc.; triols such as trimethylolpropane, glycerin, etc.; tetrafunctional alcohols such as pentaerythritol, sucroses, sorbitols, etc.); aliphatic amines (e.g., alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, etc.; alkanolamines such as monoethanolamine, diethanolamine, etc.); and aromatic amines (e.g., aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, Mannich condensates, etc.). These may be used individually or in combination of two or more.

[0034] Preferred polyether polyols include tolylenediamine-based polyether polyols, Mannich-based polyether polyols, sucrose-based polyether polyols, sorbitol-based polyether polyols, and ethylenediamine-based polyether polyols. These polyether polyols may be used individually or in combination of two or more types.

[0035] The above-mentioned tolylenediamine-based polyether polyols refer to polyether polyols obtained using tolylenediamine as an initiator. The same applies to sucrose-based polyether polyols, sorbitol-based polyether polyols, and ethylenediamine-based polyether polyols. The above-mentioned Mannich-type polyether polyols are obtained using the Mannich reaction and are Mannich condensates having two or more hydroxyl groups in the molecule, or polyether polyols obtained by adding alkylene oxide to such Mannich condensates. More specifically, they are Mannich condensates obtained by the Mannich reaction of at least one of phenol and its alkyl-substituted derivatives, formaldehyde and alkanolamines, or polyether polyols obtained by ring-opening addition polymerization of these compounds with at least one of ethylene oxide and propylene oxide.

[0036] The hydroxyl value of the polyether polyol is preferably 200 to 1,000 mg KOH / g, more preferably 250 to 800 mg KOH / g, and even more preferably 300 to 500 mg KOH / g. The hydroxyl value is measured in accordance with JIS K1557-1:2007.

[0037] (Polyester polyol) Polyester polyols include aromatic polyester polyols and aliphatic polyester polyols, but when considering the non-flammability of the resulting polyurethane foam, it is preferable to use aromatic polyester polyols. Aromatic polyester polyols are preferably condensates of aromatic dicarboxylic acids such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), and naphthalenedicarboxylic acid with glycols. In particular, the polyol compound preferably contains phthalic acid-based polyester polyols, which are condensates of phthalic acid and glycols, and more preferably contains p-phthalic acid-based polyester polyols, which are condensates of p-phthalic acid and glycols. While the glycol is not particularly limited, it is preferable to use a low molecular weight aliphatic glycol known as a component of polyester polyols, such as ethylene glycol, propylene glycol, or diethylene glycol.

[0038] The aromatic polyester polyol content is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, even more preferably 90 parts by mass or more, and even more preferably 100 parts by mass, per 100 parts by mass of the polyol compound. As stated above, the aromatic polyester polyol is preferably a phthalate-based polyester polyol, and therefore, an embodiment in which the content of the phthalate-based polyester polyol is within the above range is more preferable.

[0039] The hydroxyl value of the polyester polyol is preferably 100 to 400 mg KOH / g, more preferably 150 to 350 mg KOH / g, and even more preferably 170 to 280 mg KOH / g.

[0040] (Bromine-containing polyol) Examples of bromine-containing polyols include aromatic bromine-containing polyols and aliphatic bromine-containing polyols. From the viewpoint of improving nonflammability, it is preferable that the bromine-containing polyol contains an aromatic bromine-containing polyol. Examples of aromatic bromine-containing polyols include aromatic bromine-containing polyester polyols and aromatic bromine-containing polyether polyols.

[0041] Aromatic bromine-containing polyester polyols can be obtained, for example, from the esterification reaction of a bromine-containing polycarboxylic acid such as tetrabromophthalic acid with a polyhydric alcohol. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, and bisphenol A, which can be used individually or in appropriate combinations of two or more.

[0042] As aromatic bromine-containing polyether polyols, for example, those obtained by addition polymerization of a bromine-containing polyhydric alcohol such as tetrabromobisphenol A with one or more alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide can be used. When using bromine-containing polyether polyols, it is particularly preferable to use aromatic bromine-containing polyether polyols having a tetrabromobisphenol A skeleton.

[0043] Examples of aliphatic bromine-containing polyols include aliphatic bromine-containing polyether polyols and aliphatic bromine-containing polyester polyols, and among these, aliphatic bromine-containing polyether polyols are preferred.

[0044] The hydroxyl value of the bromine-containing polyol is preferably 100 to 600 mg KOH / g, more preferably 110 to 450 mg KOH / g, and even more preferably 110 to 350 mg KOH / g.

[0045] <Foaming agent> The polyol composition of the present invention preferably contains a blowing agent. Specific examples of blowing agents include, for example, water, low-boiling hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, and hydrofluoroolefins. Furthermore, examples of blowing agents include organic physical blowing agents such as mixtures of these compounds, and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Examples of the low-boiling hydrocarbons mentioned above include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane. Examples of the above-mentioned chlorinated aliphatic hydrocarbon compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. Examples of the fluorine compounds mentioned above include CHF3, CH2F2, and CH3F. Examples of the above-mentioned hydrochlorofluorocarbon compounds include trichloromonofluoromethane, trichlorotrifluoroethane, and dichloromonofluoroethane (e.g., HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)). Examples of the above-mentioned hydrofluorocarbons include HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane). Examples of the ether compounds mentioned above include diisopropyl ether. Examples of the above-mentioned hydrofluoroolefins include HFO-1233zd(E) (trans-1-chloro-3,3,3-trifluoropropene), HFO-1234yf (2,3,3,3-tetrafluoro-1-propene), HFO-1336mzz(Z) (cis-1,1,1,4,4,4-hexafluorobuta-2-ene), and HFO-1224yd(Z).

[0046] In the present invention, the foaming agent preferably contains water, and more specifically, a foaming agent comprising water in combination with at least one compound selected from the low-boiling hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, and hydrofluoroolefins mentioned above is preferred. As water, for example, ion-exchanged water, distilled water, etc., can be used as appropriate. The amount of water per 100 parts by mass of polyol compound is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less, and even more preferably 1.0 part by mass or less. If the water content is above these lower limits, the urethane resin composition containing the polyol composition will be easier to foam. Also, if the water content is below these upper limits, the non-flammability will be easier to improve.

[0047] In the present invention, the foaming agent preferably contains a hydrofluoroolefin, and more preferably contains both the hydrofluoroolefin and the water described above. The amount of hydrofluoroolefin per 100 parts by mass of the polyol compound is preferably 10 to 60 parts by mass, more preferably 15 to 55 parts by mass, and even more preferably 20 to 50 parts by mass.

[0048] <Catalyst> (Resin-based catalyst) The polyol composition of the present invention preferably contains a catalyst. The catalyst may contain a trimerizing catalyst, a resinification catalyst, or both a trimerizing catalyst and a resinification catalyst. In particular, it is preferable that the catalyst contains both a trimerizing catalyst and a resinification catalyst. The resin catalyst preferably contains a metal catalyst (resin-based metal catalyst). In the present invention, the inclusion of the metal catalyst promotes the reaction between the polyol and the polyisocyanate, and in particular, the initial reaction rate can be increased. Furthermore, while including a certain amount or more of the above-mentioned flame retardants A and B tends to inhibit the reactivity of the polyurethane foam and reduce its foaming properties, including a metal catalyst makes it easier to maintain good foaming properties of the polyurethane foam. From the viewpoint of foaming properties and other factors, the catalyst in the present invention preferably contains at least one metal catalyst selected from the group consisting of bismuth and tin, and more preferably contains bismuth.

[0049] The above metal catalyst is preferably a metal salt selected from bismuth salts and tin salts, and more preferably a bismuth salt. The metal salt is preferably an organic acid metal salt, and more preferably a metal salt of a carboxylic acid having 5 or more carbon atoms. Having 5 or more carbon atoms in the carboxylic acid provides good stability against blowing agents, especially hydrofluoroolefins. Furthermore, from the viewpoint of catalytic activity, the number of carbon atoms in the carboxylic acid is preferably 18 or less, and more preferably 12 or less. The carboxylic acid is preferably an aliphatic carboxylic acid, and more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may be linear or have a branched structure, but it is preferable to have a branched structure. Specific examples of carboxylic acids include octyl acid, lauryl acid, versatic acid, pentanoic acid, and acetic acid, with octyl acid being preferred among these. In other words, the transition metal salt is preferably a metal salt of octyl acid. These carboxylic acids may be linear as described above, but they may also have a branched structure. An example of octyl acid having a branched structure is 2-ethylhexanoic acid. Preferred metal salts of carboxylic acids include bismuth salts and tin salts of carboxylic acids, with bismuth salts of octic acid being particularly preferred. Alternatively, the metal salt of the carboxylic acid may be an alkyl metal carboxylic acid salt. For example, the tin salt of the carboxylic acid may be a dialkyltin carboxylic acid salt, and preferably a dioctyltin carboxylic acid salt. Specific examples of metal salts of carboxylic acids include bismastrioctate, dioctyl tin versatate, dibutyl tin dilaurate, dioctyl tin dilaurate, and tin dioctylate, with bismastrioctate and dioctyl tin versatate being preferred, and bismastrioctate being more preferred.

[0050] The content of the above metal catalyst is not particularly limited, but is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, even more preferably 1.5 to 8 parts by mass, and still more preferably 2 to 7 parts by mass, per 100 parts by mass of the polyol compound.

[0051] (Imidazole derivatives) The catalyst used in the polyol composition of the present invention preferably contains a resinification amine catalyst as the resinification catalyst, and more preferably contains an imidazole derivative as the resinification amine catalyst. Imidazole derivatives are less affected by hydrofluoroolefins and facilitate the reaction between polyols and polyisocyanates. Therefore, by including imidazole derivatives in addition to the metal catalysts mentioned above, the reactivity between the polyol and polyisocyanate is enhanced, resulting in even better foaming properties. The imidazole derivative is preferably an imidazole in which the 1st and 2nd positions are independently substituted with alkyl groups having 8 or fewer carbon atoms, and the alkyl groups preferably have 6 or fewer carbon atoms, more preferably 4 or fewer carbon atoms. A suitable specific example of an imidazole derivative is represented by the following general formula (1).

[0052] [ka] (In general formula (1), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.

[0053] R in general formula (1) 1 and R 2Each independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. The alkyl group and the alkenyl group may each be linear or may have a branched structure. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. Specific examples of the alkenyl group include a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, and the like. R 1 and R 2 When the number of carbon atoms of the alkyl group or alkenyl group of R and R is equal to or greater than the lower limit value, the steric hindrance becomes large and it is less likely to be affected by a foaming agent such as hydrofluoroolefin, which is preferable. On the other hand, when the number of carbon atoms of the alkyl group of R and R is equal to or less than the upper limit value, the steric hindrance does not become extremely large, so that the reaction between the polyol and the polyisocyanate can proceed rapidly and the foaming property is also good. 1 and R 2 From these viewpoints, R and R are each independently preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group. From these viewpoints, R 1 and R 2 are each independently preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group.

[0054] Examples of the imidazole derivative represented by the general formula (1) include 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. Among them, from the viewpoints of improving the activity of the catalyst in the presence of hydrofluoroolefin and allowing the reaction to proceed rapidly, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferable. Further, from the viewpoint of further enhancing the stability, 1,2-dimethylimidazole is more preferable.

[0055] The content of the imidazole derivative in the polyol composition is preferably 0.1 to 20 parts by mass, more preferably 1 to 18 parts by mass, even more preferably 2 to 15 parts by mass, and particularly preferably 3 to 10 parts by mass, per 100 parts by mass of the polyol compound. If the content of the imidazole derivative is above the lower limit, urethane bonds are more likely to form, the reaction proceeds rapidly, and foaming properties are good. On the other hand, if the content of the imidazole derivative is below the upper limit, the reaction rate is easier to control, which is preferable.

[0056] The content of the resinification catalyst in the polyol composition is preferably 0.2 to 35 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 3 to 20 parts by mass, per 100 parts by mass of the polyol compound.

[0057] (trimerization catalyst) The catalyst included in the polyol composition of the present invention preferably contains a trimerizing catalyst. The trimerizing catalyst is a catalyst that reacts with the isocyanate groups contained in the polyisocyanate to trimerize them and promote the formation of an isocyanurate ring. The advantage of including a trimerizing catalyst is that a good polyurethane foam can be obtained by completing the reaction of unreacted isocyanate groups. Examples of trimerizing catalysts include metal catalysts and ammonium salts. Among these, the trimerizing catalyst preferably contains an ammonium salt, and more preferably contains a quaternary ammonium salt. Examples of metal catalysts used as trimerization catalysts (trimerization metal catalysts) include potassium organic acids, preferably potassium octoates such as potassium 2-ethylhexanoate, potassium acetate, potassium propionate, potassium butanoate, potassium benzoate, and other potassium carboxylates having 2 to 8 carbon atoms. As the ammonium salt, tertiary ammonium salts such as triethylammonium salt and triphenylammonium salt, and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, and tetraphenylammonium salt can be used, but among these, quaternary ammonium salts are preferred. The ammonium salt is, for example, an ammonium salt of a carboxylic acid. Examples of carboxylic acids in the ammonium salt include saturated fatty acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms. The hydrocarbon group of the saturated fatty acid may be linear or branched, but branching is preferred. Specific examples of carboxylic acids include 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid, but among these, 2,2-dimethylpropanoic acid is preferred. The trimerization catalyst may be used alone or two or more may be used in combination.

[0058] The content of the trimerizing catalyst in the polyol composition is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, even more preferably 2 to 20 parts by mass, and still more preferably 5 to 15 parts by mass, per 100 parts by mass of the polyol compound. If the content of the trimerizing catalyst is above the lower limit, there will be no significant difference in the activity between resinification and trimerization, preventing foaming from occurring in two stages and resulting in good foamability. On the other hand, if the content of the trimerizing catalyst is below the upper limit, the resinification reaction will proceed actively, and the heat of the resinification reaction will assist the activity of trimerization, resulting in good foamability and the formation of a good polyurethane foam.

[0059] From the above viewpoint, for example, when an ammonium salt is included as a trimerizing catalyst, the content of the ammonium salt is preferably 0.3 to 23 parts by mass, more preferably 0.7 to 19 parts by mass, even more preferably 1.5 to 15 parts by mass, and still more preferably 3 to 11 parts by mass, per 100 parts by mass of the polyol compound. Furthermore, when a metal catalyst is included as a trimerizing catalyst, the content of the metal catalyst is preferably 0.2 to 7 parts by mass, more preferably 0.3 to 6 parts by mass, even more preferably 0.5 to 5 parts by mass, and still more preferably 2 to 4 parts by mass, per 100 parts by mass of the polyol compound.

[0060] <Foam stabilizer> The polyol composition of the present invention may optionally contain a foam stabilizer. Examples of foam stabilizers include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, and surfactants such as silicone foam stabilizers such as organopolysiloxanes. However, the foam stabilizer is not limited to the above types, as any structure having polar and nonpolar parts within the molecule will provide a surfactant effect. Furthermore, the silicone foam stabilizer may include a graft copolymer of polydimethylsiloxane and polyethylene glycol. The foam stabilizer content is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the polyol compound. The foam stabilizer may be used alone or two or more types may be used.

[0061] <Other additives> The polyol composition of the present invention may contain, to the extent that it does not impede the effects of the present invention, additives such as antioxidants (phenol-based, amine-based, sulfur-based, etc.), heat and light stabilizers, metal damage inhibitors, antistatic agents, crosslinking agents, lubricants, softeners, pigments, dyes, tackifying resins, etc.

[0062] <Urethane resin composition> The urethane resin composition of the present invention comprises the polyol composition described above and a polyisocyanate composition. By foaming and curing the urethane resin composition, a polyurethane foam can be obtained. The polyisocyanate composition is a composition containing a polyisocyanate compound. The polyisocyanate composition may consist only of a polyol compound.

[0063] (Polyisocyanate compounds) As the polyisocyanate compound, various polyisocyanate compounds can be used, such as aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates, all of which have two or more isocyanate groups.

[0064] Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI).

[0065] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate. Examples of aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0066] Among these, aromatic polyisocyanates are preferred from the viewpoint of ease of handling, reaction speed, physical properties of the resulting polyurethane foam, and low cost, and liquid diphenylmethane diisocyanate (MDI) is more preferred. As liquid MDI, crude MDI (also called polymeric MDI) may also be used. Specific commercially available liquid MDIs include "44V-10" and "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.) and "Millionate MR-200" (Nippon Polyurethane Industry Co., Ltd.). Alternatively, uretonimine-containing MDIs (for example, "Millionate MTL" as a commercially available product: manufactured by Nippon Polyurethane Industry Co., Ltd.) may also be used. In addition to liquid MDI, other polyisocyanate compounds may be used in combination, and any polyisocyanate compound known in the field of polyurethanes can be used without limitation. Alternatively, a polyisocyanate may be used that has been treated in advance to increase its affinity with polyols by reacting some of the isocyanate active groups within the polyisocyanate with a hydroxyl group-containing compound.

[0067] (Isocyanate Index) The isocyanate index range of the urethane resin composition of the present invention is preferably 130 to 600, more preferably 150 to 550, and even more preferably 230 to 500. When the isocyanate index is within this range, the non-flammability tends to improve.

[0068] The isocyanate index (INDEX) is calculated using the following method. INDEX = Equivalents of isocyanate ÷ (Equivalents of polyol + Equivalents of water) × 100 Here, Equivalent weight of isocyanate = Number of polyisocyanates used × NCO content (%) × 100 / Molecular weight of NCO The equivalent weight of the polyol = OHV × the amount of polyol used ÷ the molecular weight of KOH, where OHV is the hydroxyl value of the polyol (mgKOH / g). Equivalent amount of water = Number of parts of water used × Number of OH groups in water / Molecular weight of water In the above formula, the unit of the number of parts used is weight (g), the molecular weight of the NCO group is 42, the NCO content is the proportion of NCO groups in the polyisocyanate compound expressed as mass%, and for the sake of unit conversion in the above formula, the molecular weight of KOH is assumed to be 56,100, the molecular weight of water is assumed to be 18, and the number of OH groups in water is assumed to be 2.

[0069] When dividing a urethane resin composition into two or more parts, the curing reaction should be initiated only after the components of the divided urethane resin composition are mixed, rather than each component curing on its own. Typically, a urethane resin composition is divided into a polyol composition containing a polyol compound and a polyisocyanate composition containing a polyisocyanate compound.

[0070] When using foaming agents, catalysts, foam stabilizers, and other additives, they may be contained in the polyol composition, in the polyisocyanate composition, or provided separately from the polyol composition and the polyisocyanate composition, but it is preferable that they be contained in the polyol composition.

[0071] Furthermore, as will be described later, when polyol compositions and polyisocyanate compositions are filled into aerosol containers or the like, each composition may contain a low-boiling-point compound as a foaming agent. Here, a low-boiling-point compound is a component that becomes a gas at 23°C and 1 atm. Examples of low-boiling-point compounds include hydrofluorocarbons (HFCs) such as trifluoromethane (HFC-23), difluoromethane (HFC-32), and 1,1,1,2-tetrafluoroethane (HFC-134a), dimethyl ether (DME), LPG (liquefied petroleum gas) mainly composed of propane and butanes, hydrocarbons with 2 to 5 carbon atoms such as propane, isobutane, and n-butane, carbon dioxide, nitrogen, helium, and air (compressed air). These low-boiling-point compounds can be used individually or in combination of two or more. The low-boiling point compound may be used in an amount of 0.01 to 10 parts by mass per 100 parts by mass of the polyol compound in a polyol composition, or in an amount of 0.01 to 10 parts by mass per 100 parts by mass of the polyisocyanate compound in a polyisocyanate composition.

[0072] The method for producing a urethane resin composition is not particularly limited, but examples include preparing a polyol composition and a polyisocyanate composition by kneading them in advance and then mixing the two, or kneading each component that makes up the urethane resin composition. However, it is usually produced by mixing a polyol composition and a polyisocyanate composition.

[0073] <Polyurethane foam> The polyurethane foam of the present invention is formed from the above-described urethane resin composition, and more specifically, is obtained by foaming and curing the urethane resin composition. From the viewpoint of improving the non-flammability during the middle stage of combustion, the polyurethane foam of the present invention preferably has a total heat output of 1.6 MJ / m² from 60 to 400 seconds when a combustion test is conducted using a cone calorimeter. 2 The following, and more preferably 1.5 MJ / m 2 The following, and more preferably 1.3 MJ / m 2 The following applies: From the viewpoint of improving the non-flammability throughout the entire combustion process, the polyurethane foam of the present invention preferably has a total heat output of 7 MJ / m² from 0 to 1200 seconds when a combustion test is conducted using a cone calorimeter. 2 The following, and more preferably 6.5 MJ / m 2 The following is more preferably 6 MJ / m 2 The following applies: Combustion tests using a cone calorimeter shall be conducted in accordance with the ISO-5660 test method, with a radiant heat intensity of 50 kW / m². 2 This will be done.

[0074] <Method for manufacturing polyurethane foam> The method for manufacturing polyurethane foam is not particularly limited, but for example, the following mixing systems can be used. As shown in Figure 1, the mixing system 10 comprises a first container 11 containing a polyol composition and a second container 12 containing a polyisocyanate composition. The first container 11 and the second container 12 are, for example, aerosol containers (spray cans). The polyol composition sealed in the first container 11 is discharged by the vapor pressure of the low-boiling compound contained in the polyol composition. The polyisocyanate composition sealed in the second container 12 is discharged by the vapor pressure of the low-boiling compound contained in the polyisocyanate composition. Inside the first container 11, some of the low-boiling compound vaporizes to form a gas phase. The same occurs inside the second container 12. The polyol composition and polyisocyanate composition discharged from the first and second containers 11 and 12 are mixed while being foamed with a low-boiling compound, and the polyisocyanate compound and polyol compound react to form a polyurethane foam.

[0075] The mixing system 10 may include a mixer 13. The discharge ports 11A and 12A of the first and second containers 11 and 12, respectively, are connected to the mixer 13 via supply lines 11B and 12B. The polyol composition and polyisocyanate composition discharged from the first and second containers 11 and 12 are supplied to the mixer 13 via supply lines 11B and 12B, respectively, and are mixed in the mixer 13. The polyol composition and polyisocyanate composition mixed in the mixer 13 may be sprayed onto the surface to be treated using a sprayer or the like.

[0076] The mixer 13 is preferably a static mixer, also known as a static mixer. A static mixer is a mixer without a drive unit, in which the fluid is mixed as it passes through the inside of a pipe. An example of a static mixer is one in which a mixer element 13B is arranged inside a pipe 13A, as shown in Figure 1. Mixer elements 13B can be spirally shaped or have multiple baffles formed on them. The stationary mixer may also function as an injector. In this case, as shown in Figure 1, the mixture of the polyol composition and the polyisocyanate composition mixed inside the tube 13A is injected from the tip 13C of the tube. Although Figure 1 shows how the polyol composition and polyisocyanate composition discharged from the first and second containers 11 and 12 are introduced into the mixer, a discharge gun or jig may be provided before the mixture is introduced into the mixer.

[0077] Figure 2 shows a mixing system 20 as an example of a configuration equipped with a dispensing gun before being introduced into the mixer. The mixing system 20 comprises a first container 11, a second container 12, supply lines 11B and 12B, a dispensing gun 14, and a mixer 13. The first container 11 and the second container 12 are as described above, and contain a polyol composition and a polyisocyanate composition, respectively. The polyol composition and the polyisocyanate composition are supplied from the first and second containers to the dispensing gun 14 via supply lines 11B and 12B, respectively. The dispensing gun 14 is equipped with a lever 14A and has an ON-OFF mechanism for liquid supply. Specifically, when the lever 14A is pulled, the polyol composition and the polyisocyanate composition are supplied to the mixer 13, and when the lever 14A is released, the supply to the mixer 13 is stopped. By using a mixing system 20 equipped with a discharge gun 14, liquid can be supplied as needed, thereby improving work efficiency when forming polyurethane foam. Such mixing systems are suitable for use as small-scale devices and are ideally suited for repair applications.

[0078] In addition to the mixing system described above, polyurethane foam may also be formed by spraying it onto a structure using a spraying device. Spraying can be carried out using a spraying device (e.g., GRACO A-25) and a spray gun (e.g., Gasmar D-gun). Spraying can be carried out by adjusting the temperature of the polyol composition and polyisocyanate composition in separate containers within the spraying device, mixing them by collision at the tip of the spray gun, and atomizing the mixture with air pressure. The volume ratio of the polyisocyanate composition to the polyol composition in the mixture (polyisocyanate composition / polyol composition) is not particularly limited, but is usually 0.8 to 1.2, and more generally 0.9 to 1.1. The spraying equipment and spray gun are well-known and commercially available products can be used. Furthermore, the stock solution temperature and pressure settings can be the same as those for general polyurethane foam spraying.

[0079] The uses of the polyol composition, the urethane resin composition containing the polyol composition, and the polyurethane foam of the present invention are not particularly limited, but they can be used for repairing structures such as buildings, furniture, automobiles, trains, and ships, for filling cavities in such structures, or for spraying onto such structures. [Examples]

[0080] The present invention will be described in more detail by reference to examples, but the present invention is not limited in any way by these examples.

[0081] The details of each component used in each example and comparative example are as follows.

[0082] <Polyol> (A-1) Phthalate-based polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g)

[0083] <Foam stabilizer> (B-1) Silicone foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193)

[0084] <Liquid Flame Retardant> (C-1) Phosphate ester: Tris(β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)

[0085] <Flame retardant A, gas-generating flame retardant B, boron-based flame retardant, red phosphorus, others> (D-1) Halloysite (manufactured by Fimatec, product name: DRAGONITE-HP), flame retardant A, acidity pH 4.67 when heated to 500°C. (D-2) Montmorillonite (manufactured by Hojun Co., Ltd., product name: Esben NTO), flame retardant A, acidity pH 6.23 when heated to 500°C. (D-3) Zinc molybdate (Huber, product name: Kemgard 911C), flame retardant A, acidity pH 6.48 when heated to 500°C. (D-4) Ammonium polyphosphate (Clariant, product name: AP462), ammonium polyphosphate with a melamine resin coating on the surface, flame retardant A, acidity of pH 5.95 when heated to 500°C. (D-5) Hydrotalcite (manufactured by Sakai Chemical Industry Co., Ltd., product name: STABIACE HT-1), acidity pH 9.93 when heated to 500°C. (D-6) Melamine cyanurate (manufactured by Sakai Chemical Industry Co., Ltd., product name: MC-1N), (D-7) Ethylenebis(pentabromophenyl) (manufactured by Albemarle, product name: SAYTEX8010), gas-generating flame retardant B, decomposition temperature 370°C, generated gas: hydrogen bromide (D-8) Zinc borate (manufactured by Hayakawa Shoji Co., Ltd., product name: FirebrakeZB), boron-based flame retardant (D-9) Red phosphorus (manufactured by Phosphorus Chemical Industry Co., Ltd., product name: Nova Excel 140)

[0086] Of the above (D-1) to (D-9), (D-1) to (D-4) correspond to flame retardant A in the present invention. The other (D-5) to (D-9) are flame retardants whose acidity when heated to 500°C becomes pH 6.5 or higher, or which decompose when heated to 500°C, making it impossible to measure their pH.

[0087] <Foaming agent> (E-1) Trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)) (Honeywell, product name: Solstice LBA) (E-2) Deionized water

[0088] <Trimerization catalyst> (F-1) Quaternary ammonium salt (manufactured by Evonik Japan, product name: TMR-7), mixture with ethylene glycol (concentration 45-55% by mass) (F-2) Potassium 2-ethylhexanoate (manufactured by Tokyo Chemical Industry Co., Ltd., product code: P0048)

[0089] <Resin-based catalyst> (G-1) Imidazole derivative 1,2-dimethylimidazole (manufactured by Kao Corporation, product name: Kaolizer No. 390) concentration 65-75% by mass (G-2) Bismuth-based catalyst: Bismuth 2-ethylhexanoate (manufactured by Nitto Chemical Co., Ltd., product name: Bi28), concentration 81-90% by mass

[0090] [evaluation] (Acidity when heated to 500°C) 0.5 g of flame retardant was heated at 500°C for 60 minutes in an air atmosphere. The heated flame retardant was then air-cooled to room temperature (23°C), dispersed in 1 g of water, and its pH was measured. Deionized water was used as the water. The pH was measured using a compact pH meter (Horiba pH-22B compact pH meter).

[0091] (Decomposition start temperature) The decomposition initiation temperature was evaluated as follows: A 10 mg sample of flame retardant was taken and used as a sample. Using a differential thermal-thermogravimetric analyzer (STA7200, manufactured by Hitachi High-Tech Science Corporation), under conditions of a heating rate of 10°C / min and a measurement temperature of 100-800°C, the temperature at which the mass of the flame retardant decreased by 10% was defined as the decomposition start temperature.

[0092] (Corn calorimeter test) Polyurethane foam with gypsum board as a base, prepared in each example and comparative example, was cut into pieces measuring 10 cm vertically, 10 cm horizontally, and 3.25 cm thick (with 12.5 mm of gypsum board remaining) to prepare samples for cone calorimeter testing. The cone calorimeter test samples were measured for radiant thermal intensity of 50 kW / m² in accordance with the ISO-5660 test method. 2 The total heat generated from 0 to 1200 seconds and the total heat generated from 60 to 400 seconds were determined when the food was heated. <Evaluation Criteria> ◎ Total heat generation from 60 to 400 seconds is 1.3 MJ / m³ 2 below The total heat generated from 60 to 400 seconds is 1.3 MJ / m³. 2 Super 1.6MJ / m 2 below × Total heat generation from 60 to 400 seconds is 1.6 MJ / m² 2 super

[0093] [Examples 1-10, Comparative Examples 1-2] Polyol compositions and polyisocyanate compositions consisting of liquid diphenylmethane diisocyanate (MDI) were prepared according to the formulations shown in Tables 1 and 2. Each composition was introduced into a spraying apparatus (GRACO: A-25). Using a spray gun (GRACO: AP gun), a polyurethane resin composition consisting of a mixture of the polyol composition and polyisocyanate composition shown in Tables 1 and 2 was sprayed onto a 12.5 mm thick gypsum board to form a polyurethane foam. The total heat generated from each polyurethane foam was measured as described above, and the results are shown in Tables 1 and 2.

[0094] [Table 1]

[0095] [Table 2]

[0096] Note that the mass parts for each catalyst in the table represent the mass parts of the finished product.

[0097] Polyurethane foams formed using the polyol compositions of each example containing flame retardant A showed low heat output during the mid-combustion phase. Furthermore, overall non-flammability was also good. A low heat output during the mid-combustion phase tended to lead to greater stabilization of the combustion residue after combustion. On the other hand, the polyurethane foam formed using the comparative example polyol composition without flame retardant A showed a high heat output during the middle of combustion. As a result, the overall non-flammability was inferior, or the shape of the combustion residue after combustion tended to be unstable. [Explanation of Symbols]

[0098] 10, 20 mixed system 11 The first container 12 Second container 11A, 12A outlet 11B, 12B supply lines 13 Mixer 13A Body 13B Mixer Element 13C tip

Claims

1. A polyol composition containing a polyol compound, a flame retardant A having an acidity of less than pH 6.5 when heated to 500°C, red phosphorus, and a blowing agent, wherein the flame retardant A is one or more selected from the group consisting of halloysite, montmorillonite, and zinc molybdate, A two-component foamed urethane resin composition, comprising a polyisocyanate composition, used for forming thermal insulation materials for buildings.

2. A two-component foamed urethane resin composition used to form a thermal insulation material for a building, wherein the amount of the flame retardant A is 3 to 20 parts by mass per 100 parts by mass of the polyol compound.

3. A two-component foamed urethane resin composition used to form a thermal insulation material for a building according to claim 1 or 2, wherein the polyol composition contains a gas-generating flame retardant B having a decomposition onset temperature of 330 to 450°C.

4. A two-component foamed urethane resin composition used to form a thermal insulation material for a building, wherein the content of the gas-generating flame retardant B is 15 to 40 parts by mass per 100 parts by mass of the polyol compound, according to claim 3.

5. A two-component foamed urethane resin composition used to form a thermal insulation material for a building according to claim 3 or 4, wherein the ratio of the total mass of the flame retardants A and B to the mass of the red phosphorus is 0.2 or more and 3 or less.

6. A two-component foamed urethane resin composition used to form a building insulation material according to any one of claims 1 to 5, wherein the polyol composition contains a catalyst including a trimerizing catalyst.

7. A two-component foamed urethane resin composition used to form a building insulation material according to claim 6, wherein the trimerizing catalyst contains a quaternary ammonium salt.

8. A two-component foamed urethane resin composition used to form a building insulation material according to claim 6 or 7, wherein the catalyst comprises an imidazole derivative.

9. A two-component foamed urethane resin composition used to form a building insulation material according to any one of claims 6 to 8, wherein the catalyst comprises at least one metal catalyst selected from the group consisting of bismuth and tin.

10. A polyurethane foam comprising a two-component foaming urethane resin composition, used to form an insulating material for a building according to any one of claims 1 to 9.

11. When a combustion test was conducted using a cone calorimeter, the total heat output from 60 to 400 seconds was 1.6 MJ / m³. ２ The polyurethane foam according to claim 10, which is as follows:

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