Urethane resin composition and polyurethane foam

Abstract

To provide a urethane resin composition that can give a polyurethane foam having excellent incombustibility.SOLUTION: A urethane resin composition contains a polyol compound, a polyisocyanate compound, a flame retardant, a foamer, and a catalyst. When a polyurethane foam comprising the urethane resin composition is subjected to a cone calorimeter test in accordance with the ISO-5660 test method, the gross calorific value X up to 0-1200 seconds is 8 MJ / m2 or less, while the gross calorific value Y up to 0-60 seconds is less than 30% of the gross calorific value X up to 0-1200 seconds.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Taking advantage of their excellent heat insulating properties, polyurethane foams are used in practice for heat insulation and condensation prevention in various structures such as ceilings, roofs, and walls of buildings such as apartment complexes, detached houses, commercial buildings, etc. Polyurethane foams are formed, for example, by spraying a urethane resin composition containing a polyol compound and a polyisocyanate compound onto the surface of the structure, followed by foaming and curing. Although polyurethane foam has excellent heat insulating properties and is lightweight, it is known to be highly flammable. Therefore, from the viewpoint of preventing the spread of fire, there is a demand for polyurethane foam that is less likely to burn.

[0003] Patent Document 1 describes a rigid urethane resin composition containing a polyol compound, a polyisocyanate, a blowing agent, a catalyst, and an additive, the additive containing a plurality of flame retardants with different decomposition temperatures. The rigid urethane foam formed from the composition is said to have good flame retardancy. Patent Document 2 describes a urethane resin composition having quasi-nonflammable properties, which contains red phosphorus as an essential component and also contains at least one of a phosphate-containing flame retardant and a chlorine-containing flame retardant. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6776279 [Patent Document 2] Patent No. 6725606 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in recent years, there has been a demand for polyurethane foams with higher flame retardancy, and from this perspective, the polyurethane foams of the inventions described in the above-mentioned Patent Documents 1 and 2 are insufficient. Furthermore, the inventions described in Patent Documents 1 and 2 do not describe or suggest the relationship between the total heat generation during the entire combustion process and the heat generation in the early stages of combustion. Therefore, an object of the present invention is to provide a urethane resin composition that can give a polyurethane foam having excellent non-flammability. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have found that a large amount of heat generated in the initial stage when a polyurethane foam ignites increases the amount of heat generated throughout the entire combustion process, thereby worsening non-flammability. In other words, they have found that non-flammability can be improved by reducing the amount of heat generated in the initial stage when a fire occurs, and have completed the present invention. The present invention provides the following [1] to

[16] .

[0007] [1] A urethane resin composition containing a polyol compound, a polyisocyanate compound, a flame retardant, a blowing agent, and a catalyst, wherein a polyurethane foam made of the urethane resin composition has a total calorific value X of 8 MJ / m from 0 to 1200 seconds when subjected to a cone calorimeter test in accordance with the ISO-5660 test method. 2 or less, and the total calorific value Y from 0 to 60 seconds is less than 30% of the total calorific value X. [2] The total calorific value Y from 0 to 60 seconds in the cone calorimeter test is 1.7 MJ / m 2 The urethane resin composition according to the above [1], which is: [3] The urethane resin composition according to [1] or [2] above, wherein the flame retardant contains at least one gas-generating flame retardant A that generates a gas upon thermal decomposition, and the gas is at least one selected from the group consisting of nitrogen, water, ammonia, carbon dioxide, and hydrogen halide. [4] The urethane resin composition according to [3] above, wherein the gas-generating flame retardant A is a powder and has a decomposition starting temperature of 160°C or higher and 330°C or lower. [5] The urethane resin composition according to [3] or [4] above, wherein the gas-generating flame retardant A is a brominated bisphenol A derivative and has bromine bonded to a tertiary carbon. [6] The urethane resin composition according to the above [3] or [4], wherein the gas-generating flame retardant A is at least one selected from the group consisting of guanidine phosphate and melamine cyanurate. [7] The urethane resin composition according to any one of the above [3] to [6], wherein the content of the gas-generating flame retardant A is 5 to 25 parts by mass per 100 parts by mass of the polyol compound. [8] The urethane resin composition according to any one of the above [1] to [7], wherein the flame retardant contains a gas-generating flame retardant B having a decomposition starting temperature of more than 330°C and not more than 450°C. [9] The urethane resin composition according to the above [8], wherein the content of the gas-generating flame retardant B is 25 to 40 parts by mass per 100 parts by mass of the polyol compound.

[10] The urethane resin composition according to any one of the above [1] to [9], wherein the flame retardant contains a solid-phase flame retardant.

[11] The urethane resin composition according to

[10] above, wherein the solid-phase flame retardant contains at least red phosphorus.

[12] The urethane resin composition according to any one of the above [1] to

[11] , wherein the catalyst comprises a trimerization catalyst.

[13] The urethane resin composition according to

[12] above, wherein the trimerization catalyst contains a quaternary ammonium salt.

[14] The urethane resin composition according to any one of the above [1] to

[13] , wherein the catalyst contains an imidazole derivative.

[15] The urethane resin composition according to any one of the above [1] to

[14] , wherein the catalyst comprises at least one metal catalyst selected from the group consisting of bismuth and tin.

[16] A polyurethane foam comprising the urethane resin composition according to any one of [1] to

[15] above. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a urethane resin composition that can give a polyurethane foam having excellent non-flammability. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic diagram illustrating one embodiment of a mixing system. [Figure 2] FIG. 1 is a schematic diagram illustrating another embodiment of a mixing system. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Urethane resin composition] The present invention relates to a urethane resin composition containing a polyol compound, a polyisocyanate compound, a flame retardant, a blowing agent, and a catalyst. The urethane resin composition is characterized in that a polyurethane foam formed from the composition has a total calorific value X of 8 MJ / m from 0 to 1200 seconds when subjected to a cone calorimeter test in accordance with the ISO-5660 test method. 2 or less, and the total calorific value Y from 0 to 60 seconds is less than 30% of the total calorific value X from 0 to 1200 seconds. Note that "from 0 to 1200 seconds" means from the start of measurement until 1200 seconds have elapsed, and "from 0 to 60 seconds" means from the start of measurement until 60 seconds have elapsed.

[0011] <Total heat generation> The urethane resin composition of the present invention is characterized in that a polyurethane foam made of the urethane resin composition has a total calorific value X of 8 MJ / m from 0 to 1200 seconds when subjected to a cone calorimeter test in accordance with the ISO-5660 test method. 2 The total calorific value X is 8MJ / m or less. 2 If it exceeds 1000 MJ / m, the non-combustibility of the polyurethane foam will be reduced. From the viewpoint of improving the non-combustibility, the total calorific value X of the polyurethane foam from 0 to 1200 seconds is preferably 7 MJ / m 2 or less, more preferably 6MJ / m 2The lower the total calorific value X, the better, and ideally it should be 0MJ / m 2 However, it is usually 1MJ / m 2 That's all. The total calorific value X can be easily adjusted to the desired value by adjusting the composition of the urethane resin composition, lowering the total calorific value Y, which will be described later, and the like. The gross calorific value in the present invention is measured for polyurethane foam by a cone calorimeter test in accordance with the test method of ISO-5660. The cone calorimeter test is carried out at a radiant heat intensity of 50 kW / m 2 The polyurethane foam to be subjected to the cone calorimeter test is formed from a urethane resin composition by the method described in the Examples.

[0012] In a cone calorimetry test based on ISO-5660 for a polyurethane foam made from the urethane resin composition of the present invention, the total calorific value Y from 0 to 60 seconds is less than 30% of the total calorific value X from 0 to 1200 seconds. If the total calorific value Y is 30% or more of the total calorific value X, the heat generated throughout the combustion process will be too great, resulting in reduced non-flammability of the polyurethane foam. In other words, reducing the calorific value in the early stages of combustion is important for improving non-flammability. From the viewpoint of improving the flame retardancy of the polyurethane foam, the total calorific value Y is preferably 28% or less, and more preferably 26% or less, of the total calorific value X. The total calorific value Y is preferably 1.7 MJ / m from the viewpoint of improving the non-flammability of the polyurethane foam. 2 or less, more preferably 1.6 MJ / m 2 or less, and more preferably 1.5 MJ / m 2 or less, and more preferably 1.4 MJ / m 2 The total calorific value Y is 0MJ / m 2 is preferable, but is usually 0.5MJ / m 2 That's all.

[0013] <Flame retardant> The urethane resin composition of the present invention contains a flame retardant. The flame retardant is a solid flame retardant that is solid at 23°C. Examples of the flame retardant include gas-generating flame retardant A, gas-generating flame retardant B, and solid-phase flame retardants, which will be described later. These will be described in detail.

[0014] (Flame retardant A) The flame retardant contained in the urethane resin composition of the present invention preferably contains at least one gas-generating flame retardant A that generates gas upon thermal decomposition. By including the gas-generating flame retardant A, the total calorific value Y described above can be easily reduced, and the non-flammability of the polyurethane foam can be improved. The decomposition starting temperature of the gas-generating flame retardant A is 330° C. or lower, preferably 160° C. or higher and 330° C. or lower. When the gas-generating flame retardant A has such a decomposition starting temperature, it becomes easier to reduce the total calorific value Y. Furthermore, the gas-generating flame retardant A is preferably in the form of a powder. In the present invention, the decomposition starting temperature of the flame retardant is the 10% weight loss temperature measured using a thermogravimetric analyzer under conditions of a dry air atmosphere and a temperature increase rate of 10°C / min. The 10% weight loss temperature is the temperature at which the weight of the sample before measurement decreases by 10%.

[0015] The gas-generating flame retardant A generates a gas upon thermal decomposition, and the gas is at least one gas selected from the group consisting of nitrogen, water, ammonia, carbon dioxide, and hydrogen halide.

[0016] Examples of the gas-generating flame retardant A that generates nitrogen upon thermal decomposition include melamine-based compounds and guanidine-based compounds. Examples of melamine-based compounds include melamine or melamine derivatives such as melamine, melem, and melon, and salts thereof. Examples of salts of melamine or melamine derivatives include melamine cyanurate, melamine sulfate, melamine pyrophosphate, melamine orthophosphate, melamine polyphosphate, melamine polymetaphosphate, melam pyrosulfate, melam organic sulfonate, melamine organic phosphonate, melamine organic phosphinate, and melamine borate. Examples of guanidine compounds include guanidine sulfamate, guanidine phosphate, and guanylurea phosphate. From the viewpoint of effectively reducing the total calorific value Y and improving the non-flammability of the polyurethane foam, the gas-generating flame retardant A is preferably at least one selected from the group consisting of guanidine phosphate and melamine cyanurate, among the above.

[0017] Examples of the gas-generating flame retardant A that generates water (water vapor) upon thermal decomposition include metal hydroxides, such as zinc hydroxide and aluminum hydroxide, with aluminum hydroxide being preferred.

[0018] Examples of the gas-generating flame retardant A that generates ammonia upon thermal decomposition include ammonium phosphate-based flame retardants such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and ammonium polyphosphate.

[0019] Examples of the gas-generating flame retardant A that generates carbon dioxide upon thermal decomposition include lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.

[0020] Examples of the gas-generating flame retardant A that generates hydrogen halide upon thermal decomposition include compounds that have a halogen atom and have a decomposition temperature of 330° C. or less. Of these, gas-generating flame retardants A that generate hydrogen bromide upon thermal decomposition are preferred, and specifically, aromatic brominated compounds are more preferred, with brominated bisphenol A derivatives being particularly preferred. Brominated bisphenol A derivatives are compounds having a bisphenol A skeleton and one or more bromine atoms. Preferred examples of the brominated bisphenol A derivatives include tetrabromobisphenol A-bis(2,3-dibromo-2-methylpropyl ether) and tetrabromobisphenol A-bis(2,3-dibromopropyl ether).

[0021] From the viewpoint of effectively reducing the total calorific value Y and improving the non-flammability of the polyurethane foam, the gas-generating flame retardant A is preferably a brominated bisphenol A derivative having bromine bonded to a tertiary carbon, and among these, tetrabromobisphenol A-bis(2,3-dibromo-2-methylpropyl ether) is particularly preferred.

[0022] From the viewpoint of reducing the total calorific value Y, the content of the gas-generating flame retardant A is preferably 5 to 25 parts by mass, more preferably 10 to 20 parts by mass, per 100 parts by mass of the polyol compound.

[0023] (Flame retardant B) From the viewpoint of improving the flame retardancy of the polyurethane foam, the flame retardant contained in the urethane resin composition of the present invention preferably contains a gas-generating flame retardant B having a decomposition onset temperature of more than 330°C and not more than 450°C. It is more preferable to use the gas-generating flame retardant A and the gas-generating flame retardant B in combination. This effectively reduces the total calorific values ​​X and Y, which tends to improve the flame retardancy of the polyurethane foam. The gas-generating flame retardant B is preferably in powder form.

[0024] The gas-generating flame retardant B is not particularly limited as long as it is a compound that has a decomposition initiation temperature of more than 330° C. and not more than 450° C. and generates a gas upon decomposition. Examples of the gas include at least one gas selected from the group consisting of nitrogen, water, ammonia, carbon dioxide, and hydrogen halide. Examples of the gas-generating flame retardant 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, from the viewpoint of improving non-flammability, gas-generating flame retardants B that generate hydrogen bromide are preferred. As the gas-generating agent B that generates hydrogen bromide, brominated polystyrene, ethylene bis(tetrabromophthalimide), or ethylene bis(pentabromophenyl) is preferred, and among these, ethylene bis(pentabromophenyl) is more preferred.

[0025] The content of the gas-generating flame retardant B in the urethane resin composition is preferably 25 to 40 parts by mass, more preferably 30 to 35 parts by mass, per 100 parts by mass of the polyol compound, from the viewpoint of improving the non-flammability of the polyurethane foam.

[0026] (Solid-phase flame retardant) From the viewpoint of improving the flame retardancy of the polyurethane foam, the flame retardant of the present invention preferably contains a solid-phase flame retardant. The solid-phase flame retardant is preferably used in combination with at least one of the above-mentioned gas-generating flame retardant A and gas-generating flame retardant B, and it is particularly preferable to use all of the gas-generating flame retardant A, gas-generating flame retardant B, and solid-phase flame retardant. That is, the flame retardant of the present invention preferably contains all of the gas-generating flame retardant A, gas-generating flame retardant B, and solid-phase flame retardant. By including all of these flame retardants, the total calorific value X and the total calorific value Y tend to decrease, improving the non-flammability of the polyurethane foam. The solid-phase flame retardant in the present invention is a flame retardant different from the gas-generating flame retardant A and the gas-generating flame retardant B, and is a flame retardant that does not generate gas upon thermal decomposition. Examples of solid-phase flame retardants include red phosphorus, zinc borate, and calcium borate. Among these, the solid-phase flame retardant preferably contains at least red phosphorus, and more preferably uses red phosphorus and zinc borate in combination. The red phosphorus may be made of simple red phosphorus, or may be red phosphorus mixed with or coated with a resin, a metal hydroxide, a metal oxide, or the like.

[0027] The content of the solid-phase flame retardant is not particularly limited, but is preferably 20 to 80 parts by mass, and more preferably 30 to 70 parts by mass, relative to 100 parts by mass of the polyol compound.

[0028] The total amount of flame retardants contained in the urethane resin composition of the present invention is not particularly limited, but is preferably 50 to 150 parts by mass, more preferably 60 to 140 parts by mass, and even more preferably 70 to 120 parts by mass.

[0029] (liquid flame retardant) The urethane resin composition of the present invention preferably contains a liquid flame retardant from the viewpoint of improving the flame retardancy of the resulting polyurethane foam. Among liquid flame retardants, phosphate ester flame retardants are particularly preferred. The use of a phosphate ester flame retardant can improve the flame retardancy of the polyurethane foam, and can also appropriately control the viscosity of the composition even when the above-mentioned gas-generating flame retardant A, gas-generating flame retardant B, and solid-phase flame retardant are used. Here, the liquid flame retardant is a flame retardant that is liquid at 23°C.

[0030] Examples of the phosphate flame retardant include monophosphate and condensed phosphate. The monophosphate ester is not particularly limited, but includes trimethyl phosphate, triethyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tris(β-chloropropyl) phosphate, and the like. The condensed phosphate ester is not particularly limited, but examples thereof include resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade name CR-741), and aromatic condensed phosphate ester (trade name CR747).

[0031] The content of the liquid flame retardant 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, more preferably 80 parts by mass or less, relative to 100 parts by mass of the polyol compound. When the content of the liquid flame retardant is equal to or more than these lower limits, the non-flammability of the polyurethane foam is improved, and when it is equal to or less than these upper limits, the mechanical strength of the polyurethane foam can be improved.

[0032] <Polyol compounds> The polyol compound contained in the urethane resin composition of the present invention is not particularly limited, but examples thereof include polyether polyols, polyester polyols, and bromine-containing polyols. Among them, from the viewpoint of reducing the total calorific value and improving non-flammability, as described below, aromatic polyester polyols are preferred, and phthalic acid-based polyester polyols are more preferred. Furthermore, aromatic polyester polyols such as phthalic acid-based polyester polyols are preferably used alone as polyol compounds, but may also be used in combination with other polyol compounds such as polyether polyols, as described below.

[0033] <Polyether polyol> Polyether polyol is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of alkylene oxide to an initiator having two or more active hydrogen atoms. Specific 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, and cyclohexanedimethanol; triols such as trimethylolpropane and glycerin; tetrafunctional alcohols such as pentaerythritol; and highly functional alcohols such as sucrose and sorbitol), aliphatic amines (e.g., alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine; alkanolamines such as monoethanolamine and diethanolamine), and aromatic amines (e.g., aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, and Mannich condensation products). These may be used alone or in combination of two or more.

[0034] The polyether polyol is preferably a tolylenediamine-based polyether polyol, a Mannich-based polyether polyol, a sucrose-based polyether polyol, a sorbitol-based polyether polyol, or an ethylenediamine-based polyether polyol. These polyether polyols may be used alone or in combination of two or more.

[0035] The tolylenediamine-based polyether polyol is a polyether polyol obtained using tolylenediamine as an initiator. The same applies to sucrose-based polyether polyols, sorbitol-based polyether polyols, and ethylenediamine-based polyether polyols. The Mannich polyether polyol is a polyether polyol obtained by utilizing the Mannich reaction, which is a Mannich condensation product having two or more hydroxyl groups in the molecule, or a polyether polyol obtained by adding an alkylene oxide to such a Mannich condensation product. More specifically, it is a Mannich condensation product obtained by the Mannich reaction of at least one of phenol and its alkyl-substituted derivatives, formaldehyde, and alkanolamine, or a polyether polyol obtained by ring-opening addition polymerization of this compound with at least one of ethylene oxide and propylene oxide.

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

[0037] <Polyester polyol> Examples of polyester polyols include aromatic polyester polyols and aliphatic polyester polyols. However, when considering the non-flammability of the resulting polyurethane foam, it is preferable to use aromatic polyester polyols. The aromatic polyester polyol is preferably a condensate of an aromatic dicarboxylic acid, such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), or naphthalenedicarboxylic acid, with a glycol. Among these, the polyol compound preferably contains a phthalic acid-based polyester polyol, which is a condensate of phthalic acid and a glycol, and more preferably contains a p-phthalic acid-based polyester polyol, which is a condensate of p-phthalic acid and a glycol. The glycol is not particularly limited, but it is preferable to use low molecular weight aliphatic glycols known as constituent components of polyester polyols, such as ethylene glycol, propylene glycol, and diethylene glycol.

[0038] The content of the aromatic polyester polyol 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 still more preferably 100 parts by mass, based on 100 parts by mass of the polyol compound. As described above, the aromatic polyester polyol is preferably a phthalic acid-based polyester polyol, and therefore, an embodiment in which the content of the phthalic acid-based polyester polyol is within the above range is more preferable.

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

[0040] <Bromine-containing polyol> Examples of the bromine-containing polyol include aromatic bromine-containing polyols and aliphatic bromine-containing polyols. From the viewpoint of improving non-flammability, the bromine-containing polyol preferably contains an aromatic bromine-containing polyol. Examples of the aromatic bromine-containing polyol include aromatic bromine-containing polyester polyols and aromatic bromine-containing polyether polyols.

[0041] As the aromatic bromine-containing polyester polyol, for example, a product obtained by an esterification reaction between a bromine-containing polycarboxylic acid such as tetrabromophthalic acid and a polyhydric alcohol can be used. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, and bisphenol A. These may be used alone or in appropriate combination of two or more.

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

[0043] Examples of the aliphatic bromine-containing polyol 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 from 100 to 600 mgKOH / g, more preferably from 110 to 450 mgKOH / g, and even more preferably from 110 to 350 mgKOH / g.

[0045] <Polyisocyanate compounds> As the polyisocyanate compound contained in the urethane resin composition of the present invention, various polyisocyanate compounds having two or more isocyanate groups, such as aromatic, alicyclic, and aliphatic polyisocyanate compounds, can be used.

[0046] Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI).

[0047] Examples of alicyclic polyisocyanates 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.

[0048] Among these, aromatic polyisocyanates are preferred, and liquid diphenylmethane diisocyanate (MDI) is more preferred, from the viewpoints of ease of handling, reaction speed, physical properties of the resulting polyurethane foam, and low cost. Liquid MDI may also be crude MDI (also known as polymeric MDI). Specific commercially available liquid MDI products include "44V-10" and "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.) and "Millionate MR-200" (manufactured by Nippon Polyurethane Industry Co., Ltd.). Uretonimine-containing MDI (e.g., commercially available product "Millionate MTL" manufactured by Nippon Polyurethane Industry Co., Ltd.) may also be used. Liquid MDI may also be used in combination with other polyisocyanate compounds, and any polyisocyanate compound known in the polyurethane technical field can be used without limitation. Alternatively, a polyisocyanate may be used which has been previously treated by reacting some of the isocyanate-active groups in the polyisocyanate with a hydroxyl group-containing compound to enhance its affinity with the polyol.

[0049] (Isocyanate Index) The isocyanate index of the urethane resin composition of the present invention is preferably in the range of 130 to 600, more preferably 150 to 550, and even more preferably 230 to 500. When the isocyanate index is in this range, non-flammability tends to be improved.

[0050] The isocyanate index (INDEX) is calculated by the following method. INDEX = number of equivalents of isocyanate ÷ (number of equivalents of polyol + number of equivalents of water) × 100 where: Isocyanate equivalents = number of parts of polyisocyanate used x NCO content (%) x 100 / NCO molecular weight Polyol equivalents = OHV x number of parts of polyol used ÷ molecular weight of KOH, where OHV is the hydroxyl value of the polyol (mgKOH / g). Equivalents of water = parts of water used x number of OH groups in water / molecular weight of water In the above formula, the unit 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 convenience of unit conversion in the above formula, the molecular weight of KOH is set to 56,100, the molecular weight of water is 18, and the number of OH groups in water is 2.

[0051] <Foaming agent> The urethane resin composition of the present invention contains a blowing agent. Specific examples of the blowing agent include water, low-boiling hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, and hydrofluoroolefins. Further examples of the blowing agent 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 point hydrocarbon include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane. Examples of the chlorinated aliphatic hydrocarbon compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. Examples of the fluorine compound include CHF3, CH2F2, and CH3F. Examples of the hydrochlorofluorocarbon compounds include trichloromonofluoromethane, trichlorotrifluoroethane, and dichloromonofluoroethane (e.g., HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), and HCFC142b (1-chloro-1,1-difluoroethane)). Examples of the hydrofluorocarbon include HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane). Examples of the ether compounds include diisopropyl ether. Examples of the hydrofluoroolefin 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-hexafluorobut-2-ene), and HFO-1224yd(Z).

[0052] In the present invention, the blowing agent preferably contains water. More specifically, a blowing agent containing water in combination with at least one compound selected from the group consisting of low-boiling hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, and hydrofluoroolefins is preferred. Examples of water that can be used include ion-exchanged water and distilled water. The amount of water per 100 parts by mass of the polyol compound is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, and is 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. When the water content is above these lower limits, the urethane resin composition is more easily foamed. When the water content is below these upper limits, non-flammability is more easily improved.

[0053] In the present invention, the blowing agent preferably contains a hydrofluoroolefin, and more preferably contains both the hydrofluoroolefin and the above-mentioned water. The amount of the 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.

[0054] <Catalyst> (Metal catalyst (resinized metal catalyst)) The urethane resin composition of the present invention contains a catalyst. The catalyst may contain, for example, one or both of a resinification catalyst and a trimerization catalyst, and preferably contains both. The resinification catalyst preferably contains a metal catalyst. This metal catalyst is generally called a resinification metal catalyst. In the present invention, the inclusion of the resinification metal catalyst promotes the reaction between the polyol and the polyisocyanate, thereby increasing the initial reaction rate in particular. Furthermore, if a certain amount or more of the flame retardant A, flame retardant B, or solid-phase flame retardant is contained, the reactivity of the polyurethane foam is inhibited and the foamability tends to decrease. However, the inclusion of the resinification metal catalyst makes it easier to maintain good foamability of the polyurethane foam. From the viewpoint of foamability, the metal catalyst is preferably at least one selected from the group consisting of bismuth and tin, and more preferably contains bismuth.

[0055] The resinified metal catalyst is preferably a metal salt selected from bismuth salts and tin salts, more preferably a bismuth salt. The metal salt is preferably an organic acid metal salt, more preferably a metal salt of a carboxylic acid having 5 or more carbon atoms. When the carboxylic acid has 5 or more carbon atoms, stability to a blowing agent, particularly a hydrofluoroolefin, is improved. Furthermore, from the viewpoint of catalytic activity, the number of carbon atoms of the carboxylic acid is preferably 18 or less, more preferably 12 or less. The carboxylic acid is preferably an aliphatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may be linear or may have a branched structure, but preferably has a branched structure. Specific examples of carboxylic acids include octylic acid, lauric acid, versatic acid, pentanoic acid, and acetic acid, among which octylic acid is preferred. That is, the transition metal salt is preferably a metal salt of octylic acid. These carboxylic acids may be linear as described above, but may also have a branched structure. An example of an octylic acid having a branched structure is 2-ethylhexanoic acid. As the metal salt of carboxylic acid, bismuth salt of carboxylic acid and tin salt of carboxylic acid are preferred, and among them, bismuth salt of octylic acid is preferred. Furthermore, the metal salt of carboxylic acid may be a carboxylate of an alkyl metal. For example, the tin carboxylate may be a dialkyltin carboxylate, and preferably a dioctyltin carboxylate. Specific examples of metal salts of carboxylic acids include bismuth trioctate, dioctyltin versatate, dibutyltin dilaurate, dioctyltin dilaurate, and tin dioctylate, with bismuth trioctate and dioctyltin versatate being preferred, and bismuth trioctate being more preferred.

[0056] The content of the resinified 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 even more preferably 2 to 5 parts by mass, relative to 100 parts by mass of the polyol compound.

[0057] (imidazole derivatives) The catalyst used in the urethane resin composition of the present invention preferably contains a resinified amine catalyst as the resinification catalyst, and more preferably contains an imidazole derivative as the resinification amine catalyst. The imidazole derivative is less susceptible to the influence of the hydrofluoroolefin and facilitates the reaction between the polyol and the polyisocyanate. Therefore, by containing the imidazole derivative in addition to the metal catalyst, the urethane resin composition has enhanced reactivity between the polyol and the polyisocyanate, resulting in further improved foamability. The imidazole derivative is preferably an imidazole substituted at the 1st and 2nd positions with an alkyl group having 8 or less carbon atoms, and the alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms. A preferred specific example of the imidazole derivative is represented by the following general formula (1).

[0058] [ka] (In general formula (1), R 1 and R 2 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.

[0059] 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 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, and an octyl group. 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, and an octenyl group. R 1 and R 2 When the number of carbon atoms in the alkyl group or alkenyl group in R is equal to or greater than the lower limit, steric hindrance increases, making the polymer less susceptible to the influence of blowing agents such as hydrofluoroolefins, which is preferable. 1 and R 2 When the number of carbon atoms in the alkyl group is equal to or less than the upper limit, the steric hindrance is not extremely large, so that the reaction between the polyol and the polyisocyanate can proceed quickly, and the foaming property is also good. From these perspectives, 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 further preferably a methyl group.

[0060] Examples of the imidazole derivative represented by 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, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferred from the viewpoint of improving the activity of the catalyst in the presence of hydrofluoroolefin and promoting the reaction rapidly. Furthermore, 1,2-dimethylimidazole is even more preferred from the viewpoint of further enhancing stability.

[0061] The content of the imidazole derivative in the urethane resin 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, relative to 100 parts by mass of the polyol compound. When the content of the imidazole derivative is equal to or greater than the lower limit, urethane bond formation is facilitated, the reaction proceeds rapidly, and foamability is improved. On the other hand, when the content of the imidazole derivative is equal to or less than the upper limit, the reaction rate is easily controlled, which is preferable.

[0062] The content of the resinification catalyst in the urethane resin 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, relative to 100 parts by mass of the polyol compound.

[0063] (trimerization catalyst) The catalyst contained in the urethane resin composition of the present invention preferably contains a trimerization catalyst. The trimerization catalyst is a catalyst that reacts isocyanate groups contained in polyisocyanate to trimerize them and promote the formation of isocyanurate rings. The inclusion of a trimerization catalyst has the advantage of completing the reaction of unreacted isocyanate groups, thereby producing a good polyurethane foam. Examples of trimerization catalysts include metal catalysts and ammonium salts. Among these, the trimerization 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, and preferred are potassium carboxylates having 2 to 8 carbon atoms, such as potassium octylate, such as potassium 2-ethylhexanoate, potassium acetate, potassium propionate, potassium butanoate, and potassium benzoate. Examples of ammonium salts that can be used include tertiary ammonium salts such as triethylammonium salt and triphenylammonium salt, and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt and tetraphenylammonium salt, with quaternary ammonium salts being preferred. The ammonium salt is, for example, an ammonium salt of a carboxylic acid. Examples of the carboxylic acid in the ammonium salt include saturated fatty acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms. The saturated fatty acid may have a hydrocarbon group that is either linear or branched, with branched being preferred. Specific examples of carboxylic acids include 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid, with 2,2-dimethylpropanoic acid being preferred. The trimerization catalyst may be used alone or in combination of two or more.

[0064] The content of the trimerization catalyst in the polyurethane resin 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 even more preferably 5 to 15 parts by mass, per 100 parts by mass of the polyol compound. When the content of the trimerization catalyst is at or above the lower limit, there is no significant difference in activity between resinification and trimerization, and two-stage foaming can be suppressed, resulting in good foamability. On the other hand, when the content of the trimerization catalyst is at or below the upper limit, the resinification reaction proceeds actively, and the heat from the resinification reaction can help activate the trimerization, resulting in good foamability and allowing the formation of a good polyurethane foam.

[0065] From the above viewpoints, for example, when an ammonium salt is contained as the trimerization 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 even more preferably 3 to 11 parts by mass, relative to 100 parts by mass of the polyol compound. Furthermore, when a metal catalyst is contained as the trimerization 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 even more preferably 2 to 4 parts by mass, relative to 100 parts by mass of the polyol compound.

[0066] <Foam stabilizer> The urethane resin composition of the present invention optionally contains a foam stabilizer. Examples of foam stabilizers include surfactants such as polyoxyalkylene foam stabilizers (e.g., polyoxyalkylene alkyl ethers) and silicone foam stabilizers (e.g., organopolysiloxanes). However, any surfactant with a structure containing polar and non-polar moieties in the molecule can provide a surfactant effect, so the type of foam stabilizer is not limited to the above. Furthermore, the silicone foam stabilizer may also contain a graft copolymer of polydimethylsiloxane and polyethylene glycol. The content of the foam stabilizer 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, relative to 100 parts by mass of the polyol compound. One type of foam stabilizer may be used alone, or two or more types may be used.

[0067] (Other additives) The urethane resin composition may contain additives such as phenolic, amine, and sulfur-based antioxidants, heat and light stabilizers, metal inhibitors, antistatic agents, crosslinking agents, lubricants, softeners, pigments, dyes, and tackifying resins, as long as the effects of the present invention are not impaired.

[0068] When the urethane resin composition is divided into two or more components, the components should be divided so that curing does not begin on their own, but the curing reaction begins after the components of the urethane resin composition are mixed together. Usually, the urethane resin composition is divided into a polyol composition containing a polyol compound and a polyisocyanate composition containing a polyisocyanate compound.

[0069] The flame retardant, blowing agent, catalyst, and foam stabilizer, which is blended as needed, may be contained in the polyol composition, may be contained in the polyisocyanate composition, or may be provided separately from the polyol composition and the polyisocyanate composition, but are preferably contained in the polyol composition.

[0070] Furthermore, as described below, when the polyol composition and polyisocyanate composition are filled into aerosol containers or the like for use, each composition may contain a low-boiling compound as a blowing agent. Here, a low-boiling compound is a component that becomes gaseous at 23°C and 1 atmosphere. Examples of low-boiling 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) primarily composed of propane and butanes; hydrocarbons having 2 to 5 carbon atoms such as propane, isobutane, and normal butane; carbon dioxide; nitrogen; helium; and air (compressed air). These low-boiling compounds may be used alone or in combination of two or more. The low-boiling compound may be used in an amount of, for example, 0.01 to 10 parts by mass per 100 parts by mass of the polyol compound in the polyol composition, and 0.01 to 10 parts by mass per 100 parts by mass of the polyisocyanate compound in the polyisocyanate composition.

[0071] The method for producing the urethane resin composition is not particularly limited, and examples thereof include a method in which a polyol composition and a polyisocyanate composition are prepared by kneading them in advance and then mixing them together, and a method in which the components constituting the urethane resin composition are kneaded together. Typically, the urethane resin composition is produced by mixing a polyol composition and a polyisocyanate composition.

[0072] <Polyurethane foam> The polyurethane foam of the present invention is formed from the above-described urethane resin composition, and specifically, is obtained by foaming and curing the urethane resin composition. The total calorific values ​​X and Y obtained when the polyurethane foam of the present invention was subjected to a cone calorimeter test in accordance with the test method of ISO 5660 are as described above. As a result, the polyurethane foam of the present invention can improve non-flammability by reducing the initial calorific value in the event of a fire, etc.

[0073] <Method of manufacturing polyurethane foam> The method for producing polyurethane foam is not particularly limited, but for example, the following mixing system can be used. 1, the mixing system 10 includes a first container 11 containing a polyol composition therein and a second container 12 containing a polyisocyanate composition therein. 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 point 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 point compound contained in the polyisocyanate composition. Note that, inside the first container 11, a portion of the low-boiling point compound vaporizes to form a gas phase. The same is true inside the second container 12. The polyol composition and the polyisocyanate composition discharged from the first and second containers 11, 12 are mixed while being foamed by a low-boiling point compound or the like, and the polyisocyanate compound and the polyol compound react to form a polyurethane foam.

[0074] 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 the 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 the polyisocyanate composition mixed in the mixer 13 may be sprayed onto the surface to be treated using a sprayer or the like.

[0075] The mixer 13 is preferably a static mixer known as a static mixer. A static mixer is a mixer without a driving part, in which fluids are mixed by passing through the inside of a tubular body. An example of a static mixer is one in which a mixer element 13B is arranged inside a tubular body 13A, as shown in FIG. 1. The mixer element 13B may be one formed in a spiral shape or one formed with a plurality of baffles. The static mixer may also function as an injector, in which case the mixture of the polyol composition and the polyisocyanate composition mixed inside the pipe 13A may be sprayed from the tip 13C of the pipe as shown in Fig. 1. Note that Fig. 1 shows an embodiment in which the polyol composition and the polyisocyanate composition discharged from the first and second containers 11 and 12 are introduced into the mixer, but a discharge gun, jig, or the like may be provided before the mixture is introduced into the mixer.

[0076] FIG. 2 shows a mixing system 20 as an example of an embodiment equipped with a discharge gun before introduction into the mixer. The mixing system 20 includes a first container 11, a second container 12, supply lines 11B and 12B, a discharge 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 delivered from the first and second containers to the discharge gun 14 via supply lines 11B and 12B, respectively. The discharge gun 14 is equipped with a lever 14A and has an ON / OFF mechanism for delivery. Specifically, when the lever 14A is pulled, the polyol composition and the polyisocyanate composition are delivered to the mixer 13, and when the lever 14A is released, delivery to the mixer 13 is stopped. By using the mixing system 20 equipped with the discharge gun 14, the liquid can be delivered as needed, improving workability when forming polyurethane foam. Such a mixing system is also suitable for use as a small device and is suitable for repair applications.

[0077] In addition to the above-mentioned mixing system, the 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., A-25 manufactured by GRACO) and a spray gun (e.g., D-gun manufactured by Gasmar). Spraying can be carried out by adjusting the temperature of the polyol composition and the polyisocyanate composition contained in separate containers in the spraying device, mixing them by collision at the tip of the spray gun, and turning the mixed liquid into mist using air pressure. The volume ratio of the polyisocyanate composition to the polyol composition in the mixed liquid (polyisocyanate composition / polyol composition) is not particularly limited, but is usually 0.8 to 1.2, more commonly 0.9 to 1.1. Spraying equipment and spray guns are well known and commercially available products can be used. In addition, the temperature settings and pressure of the raw liquid can be set to the same conditions as for spraying general urethane foam.

[0078] The uses of the urethane resin composition and polyurethane foam of the present invention are not particularly limited, and they can be used for repairing structures such as buildings, furniture, automobiles, trains, and ships, filling cavities in such structures, or spraying them onto such structures. [Example]

[0079] The present invention will be explained in more detail by way of examples, but the present invention is not limited to these examples in any way.

[0080] Details of each component used in each example and comparative example are as follows:

[0081] <Polyol> (A-1) Phthalic acid-based polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g)

[0082] <Foam stabilizer> (B-1) Silicone foam stabilizer (manufactured by Toray Dow Corning Co., Ltd., product name: SH-193)

[0083] <Liquid flame retardant> (C-1) Phosphate ester: Tris(β-chloropropyl)phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)

[0084] <Flame retardant> (D-1) Ammonium dihydrogen phosphate (manufactured by Taihei Chemical Industry Co., Ltd.), flame retardant A, decomposition temperature 200°C, generated gas: ammonia (D-2) Melamine cyanurate (manufactured by Sakai Chemical Industry Co., Ltd., product name: MC-1N), flame retardant A, decomposition temperature: 320°C, evolved gas: nitrogen (D-3) Ammonium polyphosphate (Clariant Chemicals, product name: Exolit AP422), flame retardant A, decomposition temperature: 280°C, evolved gas: ammonia (D-4) Tetrabromobisphenol A-bis(2,3-dibromo-2-methylpropyl ether) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Pyroguard SR-130), flame retardant A, decomposition temperature: 260°C, evolved gas: hydrogen bromide (D-5) Brominated polystyrene (Manac Corporation, product name: Prasafety 900), flame retardant B, decomposition temperature 360°C, evolved gas: hydrogen bromide (D-6) Aluminum hydroxide, flame retardant A, decomposition temperature 220°C, evolved gas: water (D-7) Calcium borate (Kinseimatec Co., Ltd., product name: Colemanite), solid-phase flame retardant (D-8) Guanidine phosphate (manufactured by Sanwa Chemical Co., Ltd.), flame retardant A, decomposition temperature: 260°C, evolved gas: nitrogen (D-9) Diammonium hydrogen phosphate (manufactured by Taihei Chemical Industry Co., Ltd.), flame retardant A, decomposition temperature 150°C, generated gas: ammonia (D-10) Ethylenebistetrabromophthalimide (manufactured by Albemarle, product name: BT93), flame retardant B, decomposition temperature: 450°C, evolved gas: hydrogen bromide (D-11) Red phosphorus (Rinkagaku Kogyo Co., Ltd., product name: Nova Excel 140), solid-phase flame retardant (D-12) Zinc borate (Hayakawa Shoji Co., Ltd., product name: FirebrakeZB), solid-phase flame retardant (D-13) Ethylenebis(pentabromophenyl) (manufactured by Albemarle, product name: SAYTEX8010), flame retardant B, decomposition temperature 370°C, evolved gas: hydrogen bromide

[0085] <Foaming agent> (E-1) trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)) (Honeywell, product name: Solstice LBA) (E-2) Ion-exchanged water

[0086] <Trimerization catalyst> (F-1) Quaternary ammonium salt (manufactured by Evonik Japan, product name: TMR-7) and a mixture with ethylene glycol (concentration: 45 to 55% by mass) (F-2) Potassium 2-ethylhexanoate (Tokyo Chemical Industry Co., Ltd., product code: P0048)

[0087] <Resinification catalyst> (G-1) Imidazole derivative 1,2-dimethylimidazole (Kao Corporation, product name: Kaolizer No. 390) concentration 65 to 75% by mass (G-2) Bismuth catalyst: bismuth 2-ethylhexanoate (manufactured by Nitto Kasei Co., Ltd., product name: Bi28), concentration 81 to 90 mass%

[0088] [evaluation] (Decomposition start temperature) The decomposition starting temperature of each flame retardant was evaluated as follows. A 10 mg sample of the flame retardant was taken as a sample, and the temperature at which the mass of the flame retardant decreased by 10% was measured using a differential thermal and thermogravimetric simultaneous analyzer (Hitachi High-Tech Science Corporation, "Differential Thermal and Thermogravimetric Simultaneous Analyzer STA7200") at a heating rate of 10°C / min and a measurement temperature of 100 to 800°C. This was taken as the decomposition initiation temperature.

[0089] (Cone calorimeter test) The polyurethane foams with gypsum board as a base prepared in each Example and Comparative Example were cut into a length of 10 cm, a width of 10 cm and a thickness of 3.25 cm (within which the gypsum board was 12.5 mm) to prepare samples for cone calorimeter testing. The cone calorimeter test samples were subjected to a radiant heat intensity of 50 kW / m in accordance with the test method of ISO-5660. 2 When heated at this temperature, the total calorific value X from 0 to 1200 seconds and the total calorific value Y from 0 to 60 seconds were determined. <Evaluation criteria> ◎ The ratio of total calorific value Y to total calorific value X is less than 30% and total calorific value Y is 1.4 MJ / m 2 below The ratio of total calorific value Y to total calorific value X is less than 30%, and total calorific value Y is 1.4 MJ / m 2 Super 1.7MJ / m 2 below △ The ratio of total calorific value Y to total calorific value X is less than 30% and total calorific value Y is 1.7 MJ / m 2 super × The ratio of total heat generation Y to total heat generation X is 30% or more

[0090] [Examples 1 to 14, Comparative Examples 1 to 4] Polyisocyanate compositions consisting of polyol compositions and liquid diphenylmethane diisocyanate (MDI) were prepared according to the formulations in Tables 1 to 3. Each composition was introduced into a spraying device (GRACO: A-25). A urethane resin composition consisting of a mixed liquid of the polyol composition and polyisocyanate composition shown in Tables 1 to 3 was sprayed onto a 12.5 mm thick gypsum board using a spray gun (GRACO: AP gun) to form a polyurethane foam. The gross calorific values ​​of the polyurethane foams were measured as described above, and the results are shown in Tables 1 to 3.

[0091] [Table 1]

[0092] [Table 2]

[0093] [Table 3]

[0094] The parts by mass of each catalyst in the table are parts by mass of the product.

[0095] It was found that the polyurethane foams formed from the urethane resin compositions of each Example had a low proportion of total calorific value Y, and therefore the total calorific value throughout the combustion process could be reduced, resulting in excellent non-combustibility. In contrast, the polyurethane foams formed from the urethane resin compositions of the comparative examples had a high proportion of the total calorific value Y, and therefore were inferior in non-flammability compared to the examples. [Explanation of symbols]

[0096] 10, 20 mixed system 11 First Container 12 Second Container 11A, 12A outlet 11B, 12B supply lines 13 Mixer 13A body 13B Mixer Element 13C tip

Claims

1. A spray urethane resin composition comprising a polyol compound, a polyisocyanate compound, a flame retardant, a blowing agent, and a catalyst, the flame retardant contains at least one gas-generating flame retardant A that generates a gas upon thermal decomposition, the gas being at least one selected from the group consisting of nitrogen, water, ammonia, carbon dioxide, and hydrogen halide; the gas-generating flame retardant A is a powder having a decomposition initiation temperature of 160°C or higher and 330°C or lower; the gas-generating flame retardant A is at least one selected from the group consisting of a brominated bisphenol A derivative having a bromine bonded to a tertiary carbon, guanidine phosphate, melamine cyanurate, and ammonium polyphosphate; the content of the gas-generating flame retardant A is 5 to 43 parts by mass relative to 100 parts by mass of the polyol compound, the catalyst comprises a trimerization catalyst, the trimerization catalyst comprises a quaternary ammonium salt; The composition further comprises a solid-phase flame retardant and a liquid flame retardant, the solid-phase flame retardant comprising red phosphorus, the content of the solid-phase flame retardant being 20 to 80 parts by mass relative to 100 parts by mass of the polyol compound, and the content of the liquid flame retardant being 20 parts by mass or more relative to 100 parts by mass of the polyol compound, The polyurethane foam made of the urethane resin composition for spray application was subjected to a cone calorimeter test in accordance with the ISO-5660 test method, and the total heat release amount X from 0 to 1200 seconds was 8 MJ / m. ２ or less, and the total heat release amount Y from 0 to 60 seconds is less than 30% of the total heat release amount X.

2. A spray urethane resin composition comprising a polyol compound, a polyisocyanate compound, a flame retardant, a blowing agent, and a catalyst, the flame retardant contains at least one gas-generating flame retardant A that generates a gas upon thermal decomposition, the gas being at least one selected from the group consisting of nitrogen, water, ammonia, carbon dioxide, and hydrogen halide; the gas-generating flame retardant A is a powder having a decomposition initiation temperature of 160°C or higher and 330°C or lower; the gas-generating flame retardant A is at least one selected from the group consisting of a brominated bisphenol A derivative having a bromine bonded to a tertiary carbon, guanidine phosphate, melamine cyanurate, and ammonium polyphosphate; the content of the gas-generating flame retardant A is 5 to 43 parts by mass relative to 100 parts by mass of the polyol compound, the catalyst includes a resinification catalyst, and the content of the resinification catalyst is 2 to 30 parts by mass relative to 100 parts by mass of the polyol compound; The composition further comprises a solid-phase flame retardant and a liquid flame retardant, the solid-phase flame retardant comprising red phosphorus, the content of the solid-phase flame retardant being 20 to 80 parts by mass relative to 100 parts by mass of the polyol compound, and the content of the liquid flame retardant being 20 parts by mass or more relative to 100 parts by mass of the polyol compound, The polyurethane foam made of the urethane resin composition for spray application was subjected to a cone calorimeter test in accordance with the ISO-5660 test method, and the total heat release amount X from 0 to 1200 seconds was 8 MJ / m. ２ or less, and the total heat release amount Y from 0 to 60 seconds is less than 30% of the total heat release amount X.

3. The total heat generation amount Y from 0 to 60 seconds in the cone calorimeter test is 1.7 MJ / m ２ 3. The spray urethane resin composition according to claim 1, wherein:

4. 4. The spray urethane resin composition according to claim 1, wherein the content of the gas-generating flame retardant A is 5 to 25 parts by mass per 100 parts by mass of the polyol compound.

5. The spray urethane resin composition according to any one of claims 1 to 4, wherein the flame retardant contains a gas-generating flame retardant B having a decomposition onset temperature of more than 330°C and not more than 450°C.

6. 6. The spray urethane resin composition according to claim 5, wherein the content of the gas-generating flame retardant B is 25 to 40 parts by mass per 100 parts by mass of the polyol compound.

7. The spray urethane resin composition according to any one of claims 2 to 6, wherein the catalyst comprises a trimerization catalyst, and the trimerization catalyst comprises a quaternary ammonium salt.

8. The spray urethane resin composition according to any one of claims 1 to 7, wherein the catalyst comprises an imidazole derivative as a resinification catalyst.

9. The spray urethane resin composition according to any one of claims 1 to 8, wherein the catalyst comprises at least one metal catalyst selected from the group consisting of bismuth and tin as a resinification catalyst.

10. 10. The spray urethane resin composition according to claim 9, wherein the content of the metal catalyst is 0.1 to 15 parts by mass per 100 parts by mass of the polyol compound.

11. A polyurethane foam comprising the spray urethane resin composition according to any one of claims 1 to 10.

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