Polyol-containing composition, foamable urethane resin composition, and polyurethane foam

Abstract

To provide a polyol-containing composition which prevents clogging in a filter inside a foaming machine while exhibiting good foamability, and enables formation of a polyurethane foam having high flame retardancy, in a process of reacting and foaming polyisocyanate by the foaming machine.SOLUTION: A polyol-containing composition contains polyol, a foaming agent, a catalyst, and a flame retardant, wherein the catalyst contains at least one metal catalyst selected from a bismuth compound and a tin compound, and the flame retardant contains a bromine-based flame retardant having a structure including at least two benzene rings per one molecule.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Taking advantage of their excellent heat insulating properties, polyurethane foams are used in practice for heat insulation and condensation prevention in building components such as ceilings, roofs, and walls of buildings such as apartment complexes, detached houses, commercial buildings, etc. Polyurethane foams are formed by spraying a foamable urethane resin composition containing a polyol compound and a polyisocyanate compound onto the surface of each structure, followed by foaming and curing.

[0003] Although polyurethane foams are lightweight, they are organic and therefore flammable. To improve this, polyurethane foams with high flame retardancy are needed. As a means for improving the flame retardancy of polyurethane foams, for example, as described in Patent Document 1, it is known to include a brominated flame retardant in a polyol composition. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-172603 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when such conventional polyol compositions are reacted with polyisocyanate and foamed using a foaming machine, the brominated flame retardant aggregates and becomes large in particle size, which can cause clogging of the filter inside the foaming machine. In such cases, it is not possible to discharge an amount of the polyol composition sufficient for reaction with polyisocyanate and foaming, resulting in problems such as a decrease in the production efficiency of polyurethane foam. Therefore, an object of the present invention is to provide a polyol-containing composition that exhibits good foaming properties in the step of reacting with polyisocyanate and foaming in a foaming machine, does not clog the filter inside the foaming machine, and can form a polyurethane foam that is highly flame-retardant. [Means for solving the problem]

[0006] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by a polyol-containing composition having the following configuration, and have completed the present invention.

[0007] The present invention is summarized as follows [1] to

[21] . [1] A polyol-containing composition comprising a polyol, a blowing agent, a catalyst, and a flame retardant, wherein the catalyst comprises at least one metal catalyst selected from bismuth salts and tin salts, and the flame retardant comprises a brominated flame retardant having a structure containing at least two benzene rings per molecule. [2] The polyol-containing composition according to [1], wherein at least two of the benzene rings constituting the brominated flame retardant are chemically bonded via an ethylene group. [3] The polyol-containing composition according to [1] or [2], wherein the brominated flame retardant contains at least one brominated benzene ring. [4] The polyol-containing composition according to any one of [1] to [3], wherein the bromine content in the brominated flame retardant is 50 mass % or more based on the total amount of the brominated flame retardant. [5] The polyol-containing composition according to any one of [1] to [4], wherein the brominated flame retardant is ethylenebis(pentabromophenyl). [6] The polyol-containing composition according to any one of [1] to [5], wherein the flame retardant comprises a red phosphorus-based flame retardant. [7] The polyol-containing composition according to [6], wherein the content of the red phosphorus-based flame retardant is 6 to 36 mass % based on the total amount of the polyol-containing composition. [8] The polyol-containing composition according to any one of [1] to [7], wherein the blowing agent contains a hydrofluoroolefin. [9] The polyol-containing composition according to any one of [1] to [8], wherein the catalyst comprises an imidazole derivative.

[10] The polyol-containing composition according to any one of [1] to [9], wherein the catalyst comprises a trimerization catalyst.

[11] The polyol-containing composition according to

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

[12] The polyol-containing composition according to any one of [1] to

[11] , wherein the weighted average aromatic concentration of the polyol is 10% by mass or more.

[13] The polyol-containing composition according to any one of [1] to

[12] , wherein the content of the flame retardant is 20 to 60 mass % based on the total amount of the polyol-containing composition.

[14] The polyol-containing composition according to any one of [1] to

[13] , wherein the content of the brominated flame retardant is 20 mass % or less based on the total amount of the polyol-containing composition.

[15] The polyol-containing composition according to any one of [1] to

[14] , which is used for spraying.

[16] A foamable urethane resin composition comprising the polyol-containing composition according to any one of [1] to

[15] and a polyisocyanate.

[17] The foamable urethane resin composition according to

[16] , wherein the polyisocyanate is an aromatic polyisocyanate.

[18] The foamable urethane resin composition according to

[16] or

[17] , which has an isocyanate index of 300 or more.

[19] The foam obtained by foaming the foamable urethane resin composition has a core density of 25 to 60 kg / m 3 The foamable urethane resin composition according to any one of

[16] to

[18] , wherein

[20] The polyurethane foam obtained by foaming the foamable urethane resin composition has a radiant heat intensity of 50 kW / m in a cone calorimeter test in accordance with the ISO-5660 test method. 2 When heated for 20 minutes, the total calorific value is 8MJ / m 2The foamable urethane resin composition according to any one of

[16] to

[19] , wherein the foamable urethane resin composition is less than 100%.

[21] A polyurethane foam formed by reacting and foaming the foamable urethane resin composition according to any one of

[16] to

[20] . [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a polyol-containing composition that exhibits good foaming properties in the step of reacting with polyisocyanate and foaming in a foaming machine, does not clog the filter inside the foaming machine, and can form a polyurethane foam that is highly flame-retardant. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below. [Polyol-containing composition] The polyol-containing composition of the present invention contains a polyol, a blowing agent, a catalyst, and a flame retardant. The polyol-containing composition is used to produce a polyurethane foam by reacting it with a polyisocyanate. The flame retardant includes at least a brominated flame retardant.

[0010] (Flame retardant) <Brominated flame retardants> The brominated flame retardant contained in the polyol-containing composition of the present invention has a structure containing at least two benzene rings per molecule. This structure prevents the brominated flame retardant from agglomerating and becoming large in particle size, thereby preventing clogging of the filter inside the foaming machine when the polyol-containing composition and polyisocyanate are reacted and foamed in the foaming machine. While the underlying mechanism is unclear, it is believed that the brominated flame retardant used in the present invention has a structure containing at least two benzene rings in the same molecule, which prevents benzene rings from overlapping or bromine atoms from being attracted to each other through interactions. As a result, it is believed that aggregation and particle size increase of the brominated flame retardant can be prevented. Specific examples of bromine-based flame retardants having the above structure include polybromobiphenyl, 1-benzyloxy-4-bromobenzene, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

[0011] The brominated flame retardant used in the present invention preferably has at least two benzene rings among the benzene rings constituting the flame retardant chemically bonded via ethylene groups. Chemical bonding via ethylene groups increases the degree of freedom of rotation about the bond axis between the benzene rings, making it easier to have a three-dimensional structure, which makes it easier to more effectively prevent aggregation and particle size increase of the brominated flame retardant. In addition, it is preferable that at least one benzene ring constituting the brominated flame retardant is brominated. Here, brominated means that at least one of the hydrogen atoms in the benzene ring, excluding the hydrogen atom substituted with the ethylene group, is substituted with a bromine atom. The benzene ring constituting the brominated flame retardant may have any one benzene ring brominated or two or more benzene rings brominated. However, from the viewpoint of ensuring that the bromine content in the brominated flame retardant falls within the desired range, as described below, it is more preferable that two or more benzene rings are brominated. In addition, it is more preferable that two or more hydrogen atoms of the brominated benzene ring are substituted with bromine atoms, and even more preferable that all hydrogen atoms are substituted with bromine atoms.

[0012] The bromine content in the brominated flame retardant used in the present invention (hereinafter sometimes referred to as "bromine content") is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more, based on the total amount of the brominated flame retardant, from the viewpoint of enhancing the flame retardancy of the polyurethane foam. On the other hand, the upper limit of the bromine content is not particularly limited, but is, for example, less than 100% by mass, preferably 90% by mass or less. From the above viewpoints, it is particularly preferable that the brominated flame retardant used in the present invention is ethylenebis(pentabromophenyl).

[0013] The content of the brominated flame retardant is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 17% by mass or less, based on the total amount of the polyol-containing composition. When the content of the brominated flame retardant is equal to or less than the above upper limit, the viscosity value of the polyol-containing composition can be easily adjusted to an appropriate range, resulting in excellent handleability and foamability. The content of the brominated flame retardant is not particularly limited, but from the viewpoint of flame retardancy, it is preferably 3% by mass or more, more preferably 6% by mass or more, and even more preferably 9% by mass or more.

[0014] In order to more effectively enhance the flame retardancy of polyurethane foams, the polyol-containing composition of the present invention preferably contains, in addition to the above-described brominated flame retardant, a solid flame retardant other than the brominated flame retardant. The solid flame retardant is a flame retardant that becomes solid at 23°C and 1 atmosphere. Examples of the solid flame retardant include red phosphorus-based flame retardants, boron-based flame retardants, phosphate-containing flame retardants, chlorine-containing flame retardants, antimony-containing flame retardants, needle fillers, and metal hydroxides.

[0015] <Red phosphorus flame retardant> The red phosphorus-based flame retardant may consist of red phosphorus alone, may be red phosphorus coated with a resin, metal hydroxide, metal oxide, or the like, or may be a mixture of red phosphorus with a resin, metal hydroxide, metal oxide, or the like. The resin with which the red phosphorus is coated or mixed is not particularly limited, but examples include thermosetting resins such as phenolic resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, aniline resins, and silicone resins. From the viewpoint of flame retardancy, metal hydroxides are preferred as the coating or mixed compound. Examples of metal hydroxides that can be used include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, and the like.

[0016] <Boron-based flame retardants> Examples of boron-based flame retardants include borax, boron oxide, boric acid, borate salts, etc. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide. Examples of borates include borates of alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the periodic table, and ammonium. Specific examples include alkali metal borates such as lithium borate, sodium borate, potassium borate, and cesium borate, alkaline earth metal borates such as magnesium borate, calcium borate, and barium borate, zirconium borate, zinc borate, aluminum borate, and ammonium borate. The boron-based flame retardants may be used alone or in combination of two or more. The boron-based flame retardant used in the present invention is preferably a borate, more preferably zinc borate.

[0017] <Phosphate-containing flame retardants> Specific examples of phosphate-containing flame retardants include phosphates formed from salts of various phosphoric acids with at least one metal or compound selected from metals in Groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. The phosphoric acid is not particularly limited, but examples thereof include monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid. Examples of metals in Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum. Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, etc. Examples of aromatic amines include aniline, o-toliidine, 2,4,6-trimethylaniline, anisidine, 3-(trifluoromethyl)aniline, etc. Examples of heterocyclic compounds containing nitrogen in the ring include pyridine, triazine, melamine, etc.

[0018] Specific examples of phosphate-containing flame retardants include monophosphates, pyrophosphates, polyphosphates, etc. Here, the polyphosphates are not particularly limited, but examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate. The phosphate-containing flame retardants may be used alone or in combination of two or more of the above.

[0019] <Chlorine-containing flame retardants> Chlorine-containing flame retardants include those commonly used in polyurethane foams, such as polychlorinated naphthalenes, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene, sold under the trade name "Dechlorane Plus."

[0020] <Antimony-containing flame retardants> Examples of antimony-containing flame retardants include antimony oxide, antimony salts, and pyroantimony salts. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimony salts include sodium antimonate and potassium antimonate. Examples of pyroantimonate salts include sodium pyroantimonate and potassium pyroantimonate. The antimony-containing flame retardants may be used singly or in combination of two or more. The antimony-containing flame retardant used in the present invention is preferably antimony oxide.

[0021] <Needle filler> Examples of needle-like fillers include potassium titanate whiskers, aluminum borate whiskers, silicon-containing whiskers, wollastonite, sepiolite, zonolite, elestadite, boehmite, asbestos fibers, carbon fibers, graphite fibers, slag fibers, silica fibers, alumina fibers, zirconia fibers, boron nitride fibers, stainless steel fibers, etc. The aspect ratio (length / diameter) of the needle-like fillers is preferably in the range of 5 to 50, and more preferably in the range of 10 to 40.

[0022] <Metal hydroxide> Examples of metal hydroxides include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, etc. The metal hydroxides may be used alone or in combination of two or more.

[0023] The content of the solid flame retardant other than the brominated flame retardant is preferably 7 to 51 mass%, more preferably 9 to 40 mass%, and even more preferably 12 to 22 mass%, based on the total amount of the polyol-containing composition. When the content of the solid flame retardant other than the brominated flame retardant is equal to or greater than the above lower limit, the flame retardancy of the polyurethane foam can be enhanced. On the other hand, when the content of the solid flame retardant other than the brominated flame retardant is equal to or less than the above upper limit, the viscosity of the polyol-containing composition can be easily adjusted to an appropriate range and the content relative to the blowing agent can be easily prevented from becoming too high, resulting in excellent handleability and foamability.

[0024] As the solid flame retardant other than the bromine-based flame retardant, it is preferable to contain at least a red phosphorus-based flame retardant among the above-mentioned ones, from the viewpoint of more effectively enhancing flame retardancy. The content of the red phosphorus-based flame retardant is preferably 6 to 36% by mass, more preferably 8 to 30% by mass, and even more preferably 10 to 15% by mass, based on the total amount of the polyol-containing composition. When the content of the red phosphorus-based flame retardant is equal to or greater than the above-mentioned lower limit, the flame retardancy of the polyurethane foam can be enhanced. On the other hand, when the content of the red phosphorus-based flame retardant is equal to or less than the above-mentioned upper limit, it becomes easier to adjust the viscosity of the polyol-containing composition to an appropriate range and to prevent the content from becoming too high relative to the blowing agent, resulting in excellent handleability and foamability.

[0025] Also preferred is an embodiment in which a solid flame retardant other than a red phosphorus-based flame retardant, such as a boric acid-based flame retardant, is used in combination with the red phosphorus-based flame retardant. The content of the boron-based flame retardant is preferably 1 to 15 mass%, more preferably 1.5 to 10 mass%, and even more preferably 2 to 7 mass%, based on the total amount of the polyol-containing composition. When the content of the boron-based flame retardant is equal to or greater than the above lower limit, the flame retardancy of the polyurethane foam can be improved. On the other hand, when the content of the boron-based flame retardant is equal to or less than the above upper limit, it becomes easier to adjust the viscosity of the polyol-containing composition to an appropriate range and to prevent the content from becoming too high relative to the blowing agent, resulting in excellent handleability and foamability.

[0026] <Phosphate ester flame retardants> The polyol-containing composition of the present invention may further contain a liquid flame retardant. The liquid flame retardant is a flame retardant that becomes liquid at 23°C and 1 atmosphere. The liquid flame retardant preferably contains a phosphate ester-based flame retardant. The use of a phosphate ester makes it easier to increase the flame retardancy of the polyurethane foam without reducing the fluidity of the polyol-containing composition.

[0027] Examples of phosphate ester-based flame retardants that can be used include monophosphate esters and condensed phosphate esters. Monophosphate esters are phosphate esters having one phosphorus atom in the molecule. Examples of monophosphate esters include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tri(2-ethylhexyl)phosphate; halogen-containing phosphate esters such as tris(β-chloropropyl)phosphate; trialkoxy phosphates such as tributoxyethyl phosphate; aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl)phosphate, cresyl diphenyl phosphate, and diphenyl(2-ethylhexyl)phosphate; and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate.

[0028] Examples of the condensed phosphate ester include aromatic condensed phosphate esters such as trialkyl polyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate. Commercially available condensed phosphate esters include, for example, "CR-733S," "CR-741," and "CR747" manufactured by Daihachi Chemical Industry Co., Ltd., and "ADEKA STAB PFR" and "FP-600" manufactured by ADEKA Corporation.

[0029] The phosphate ester-based flame retardants may be used singly or in combination of two or more of the above-mentioned ones. Among them, from the viewpoint of easily adjusting the viscosity of the polyol-containing composition to an appropriate level and from the viewpoint of improving the flame retardancy of the polyurethane foam, monophosphate esters are preferred, and halogen-containing phosphate esters such as tris(β-chloropropyl)phosphate are more preferred. The content of the phosphate ester-based flame retardant in the polyol-containing composition is preferably 1 to 15 mass%, more preferably 1.5 to 10 mass%, and even more preferably 2 to 7 mass%, based on the total amount of the polyol-containing composition. When the content of the phosphate ester-based flame retardant is equal to or greater than the above lower limit, the flame retardancy of the polyurethane foam can be effectively improved. On the other hand, when the content of the phosphate ester-based flame retardant is equal to or less than the above upper limit, the viscosity of the polyol-containing composition can be maintained at a certain level or higher, resulting in excellent handleability.

[0030] The content (total content) of the flame retardant in the polyol-containing composition of the present invention is preferably 20 to 60 mass %, more preferably 30 to 55 mass %, and even more preferably 35 to 50 mass %, based on the total amount of the polyol-containing composition. When the content of the flame retardant is equal to or greater than the above lower limit, the flame retardancy of the polyol-containing composition can be effectively improved. Furthermore, when the content of the flame retardant is equal to or less than the above upper limit, it becomes easier to adjust the viscosity of the polyol-containing composition to an appropriate range and to prevent the content from becoming too high relative to the blowing agent, resulting in excellent handleability and foamability.

[0031] (catalyst) <Urethanization catalyst> The polyol-containing composition of the present invention contains at least one metal catalyst selected from bismuth salts and tin salts as a urethane-forming catalyst. The inclusion of these metal catalysts improves the initial activity of the urethane resin composition, thereby improving the foamability of the composition. This reduces dripping after foaming and improves the flame retardancy of the polyurethane foam. Furthermore, the polyol-containing composition is less likely to lose its activity even when stored for a long period of time. The catalyst is preferably a metal salt of an organic acid, 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, the 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.

[0032] The content of the metal catalyst is preferably 0.1 to 2.5 mass% based on the total amount of the polyol-containing composition, more preferably 0.2 to 2 mass%, and even more preferably 0.5 to 1.5 mass%. When the content of the metal catalyst is equal to or greater than the lower limit, the initial activity of the foamable urethane resin composition is improved, and accordingly, the foamability of the composition is also improved. On the other hand, when the content of the metal catalyst is equal to or less than the upper limit, the foamable urethane resin composition can react and foam at an appropriate rate.

[0033] The urethanization catalyst used in the polyol-containing composition of the present invention preferably contains an amine catalyst in addition to the metal catalyst, and more preferably contains an imidazole derivative as the urethanization amine catalyst. The imidazole derivative is less susceptible to the influence of the hydrofluoroolefin and facilitates the reaction between the polyol and the polyisocyanate while increasing the stability of the polyol-containing composition. Therefore, by including the imidazole derivative in the polyol-containing composition in addition to the metal catalyst, the reactivity between the polyol and the polyisocyanate is increased and the foaming property is further improved. 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).

[0034] [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.

[0035] R in general formula (1) 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. 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.

[0036] 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 more preferred from the viewpoint of further enhancing stability.

[0037] The content of the imidazole derivative in the polyol-containing composition is preferably 0.5 to 8 mass%, more preferably 1 to 5 mass%, and even more preferably 1.5 to 3 mass%, based on the total amount of the polyol-containing composition. 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 foaming properties are improved. On the other hand, when the content of the imidazole derivative is equal to or less than the upper limit, the reaction rate can be easily controlled, which is preferable.

[0038] <Trimerization catalyst> The polyol-containing composition of the present invention preferably contains a trimerization catalyst in addition to the urethanization catalyst. The trimerization catalyst promotes trimerization to form isocyanurate bonds, and the promotion of trimerization in the polyol-containing composition improves the flame retardancy and resistance to flame spread of the polyurethane foam. Examples of trimerization catalysts that can be used include aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; alkali metal salts such as potassium acetate, sodium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, potassium formate, potassium octoate, and sodium octoate; aziridines such as 2-ethylaziridine; lead compounds such as lead naphthenate and lead octoate; alcoholate compounds such as sodium methoxide; phenolate compounds such as potassium phenoxide; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt; and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, and tetraphenylammonium salt. Among these, quaternary ammonium salts are preferred. The use of quaternary ammonium salts maintains good catalytic activity, even when a hydrofluoroolefin compound such as a hydrochlorofluoroolefin is used as a blowing agent, resulting in appropriate trimerization and improved flame retardancy. The trimerization catalyst may be used alone or in combination of two or more, but from the viewpoint of sufficiently enhancing the flame retardancy of the polyurethane foam, it is preferable to use two or more in combination. When two or more are used in combination, it is preferable to use an alkali metal salt and a quaternary ammonium salt, and it is more preferable to use potassium 2-ethylhexanoate and a tetramethylammonium salt.

[0039] When a quaternary ammonium salt is contained as the trimerization catalyst, the content of the quaternary ammonium salt is not particularly limited, but is preferably 0.5 to 10 mass%, more preferably 1 to 5 mass%, and even more preferably 1.5 to 3 mass%, based on the total amount of the polyol-containing composition. By setting the content of the trimerization catalyst within the above range, isocyanurate bonds are formed appropriately, and flame retardancy is improved.

[0040] When an alkali metal salt is contained as the trimerization catalyst, the content of the alkali metal salt is not particularly limited, but is preferably 0.1 to 3 mass%, more preferably 0.5 to 2.5 mass%, and even more preferably 0.8 to 2 mass%, based on the total mass of the polyol-containing composition. By keeping the content of the trimerization catalyst within the above range, isocyanurate bonds are formed appropriately, and flame retardancy is improved.

[0041] The content of the trimerization catalyst is not particularly limited, but is preferably 0.6 to 13 mass %, more preferably 1.5 to 7.5 mass %, and even more preferably 2.3 to 5 mass %, based on the total amount of the polyol-containing composition. By setting the content of the trimerization catalyst within the above range, isocyanurate bonds are appropriately formed, and flame retardancy is improved.

[0042] (Polyol) Examples of the polyol used in the present invention include polylactone polyol, polycarbonate polyol, polyester polyol, polymer polyol, and polyether polyol.

[0043] Examples of polylactone polyols include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Examples of polycarbonate polyols include polyols obtained by dealcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, and the like.

[0044] Examples of polyester polyols include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, and condensates of hydroxycarboxylic acids and the above-mentioned polyhydric alcohols. Examples of polybasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), o-phthalic acid (phthalic acid), naphthalenedicarboxylic acid, and succinic acid. Examples of polyhydric alcohols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol. Examples of hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

[0045] Examples of polymer polyols include polymers obtained by graft polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, or methacrylate with an aromatic polyol, alicyclic polyol, aliphatic polyol, or polyester polyol, polybutadiene polyol, or hydrogenated products thereof.

[0046] Examples of polyether polyols include polymers obtained by ring-opening polymerization of an alkylene oxide having 2 to 6 carbon atoms, specifically at least one of ethylene oxide, propylene oxide, tetrahydrofuran, etc., in the presence of at least one low-molecular-weight active hydrogen compound having two or more active hydrogens, such as a polyhydric alcohol. Examples of the alkylene oxide include at least one of ethylene oxide and propylene oxide. Examples of low molecular weight active hydrogen compounds having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol; triols such as glycerin and trimethylolpropane; tetrahydric to octahydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methyl glucoside, and derivatives thereof; phloroglucinol; and cresol. polyols such as pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8-tetrahydroxyanthracene; polyfunctional (e.g., having 2 to 100 functional groups) polyols such as castor oil polyol, (co)polymers of hydroxyalkyl (meth)acrylate, and polyvinyl alcohol; condensates of phenol and formaldehyde (novolac), amines such as ethylenediamine, and butylenediamine.

[0047] The polyol used in the present invention is preferably a polyester polyol or a polyether polyol. Furthermore, a polyol compound having two hydroxyl groups is preferred. Among these, aromatic polyester polyols, which are polyester polyols having an aromatic ring, are preferred from the viewpoint of enhancing the flame retardancy of polyurethane foams. In this case, the weighted average aromatic concentration of the polyol is preferably 10% by mass or more, more preferably 12% by mass or more. Here, the aromatic concentration is obtained by the mass % of the total of carbon atoms and hydrogen atoms constituting the aromatic rings in the polyol, and the weighted average aromatic concentration is the aromatic concentration calculated by taking a weighted average of the respective contents of carbon atoms and hydrogen atoms in the aromatic rings. 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, from the viewpoint of improving the flame retardancy, particularly the flame spread resistance, of the polyurethane foam, the aromatic polyester polyol more preferably contains a phthalic acid-based polyester polyol which is a condensate of phthalic acid and a glycol, and even more preferably contains at least one selected from p-phthalic acid-based polyester polyol which is a condensate of p-phthalic acid and a glycol, and o-phthalic acid-based polyester polyol which is a condensate of o-phthalic acid and a glycol.

[0048] When the polyol contains an aromatic polyester polyol, its content is not particularly limited, but is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 100 parts by mass, per 100 parts by mass of the polyol compound in the polyol-containing composition.

[0049] The weighted average hydroxyl value of the polyol is preferably 20 to 350 mgKOH / g, more preferably 30 to 300 mgKOH / g, and even more preferably 50 to 250 mgKOH / g. When the hydroxyl value of the polyol is equal to or less than the upper limit, the viscosity of the polyol-containing composition tends to decrease, which is preferable from the viewpoint of handleability, etc. On the other hand, when the hydroxyl value of the polyol is equal to or more than the lower limit, the crosslink density of the polyurethane foam increases, thereby increasing the strength and improving the workability when sprayed. The hydroxyl value of the polyol can be measured in accordance with JIS K 1557-1:2007.

[0050] Here, the weighted average hydroxyl value of a polyol is calculated by multiplying the hydroxyl values ​​of the individual polyols constituting the polyol by the mass fraction of each polyol in the polyol. For example, when two types of polyol (d1) and polyol (d2) are used as the polyol compound, the weighted average hydroxyl value is expressed by the following formula, where X1 is the hydroxyl value of polyol (d1), m1 is the blending amount, and X2 is the hydroxyl value of polyol (d2), m2 is the blending amount. The blending amounts m1 and m2 are the mass parts per 100 parts by mass of the polyol compound. Weighted average hydroxyl value (mgKOH / g)=X1×(m1 / (m1+m2))+X2×(m2 / (m1+m2))

[0051] (foaming agent) Specific examples of blowing agents include water, low-boiling hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, hydrofluoroolefins, etc. Further 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 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 (for example, 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] Among the above, the foaming agent preferably contains a hydrofluoroolefin, and more preferably contains a hydrofluoroolefin and water in combination. From the viewpoint of adjusting the core density of the foam within a desired range, the content of the blowing agent is preferably 5 to 26 mass %, more preferably 8 to 20 mass %, and even more preferably 10 to 15 mass %, based on the total amount of the polyol-containing composition.

[0053] The content of the hydrofluoroolefin used as a blowing agent is preferably 5 to 25 mass%, more preferably 8 to 20 mass%, and even more preferably 10 to 15 mass%, based on the total amount of the polyol-containing composition, from the viewpoint of setting the core density of the polyurethane foam in a desired range.

[0054] As the water used as a blowing agent, for example, ion-exchanged water, distilled water, etc. can be used as appropriate. Among these, ion-exchanged water is preferably used. The water content is preferably 0.05 to 1 mass %, more preferably 0.1 to 0.5 mass %, and even more preferably 0.2 to 0.3 mass %, based on the total amount of the polyol-containing composition. By setting the water content within the above range, a good balance between flame retardancy and foamability can be achieved.

[0055] (Foam stabilizer) The polyol-containing composition of the present invention may contain a foam stabilizer. The foam stabilizer can improve the foamability of the polyurethane foam, and can promote foaming when reacting with polyisocyanate during spraying, for example. Specific examples of the foam stabilizer include surfactants, more specifically, nonionic surfactants, cationic surfactants, anionic surfactants, etc. Specific examples of nonionic surfactants include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, and silicone foam stabilizers such as organopolysiloxanes. The foam stabilizer used in the present invention is not particularly limited, but silicone foam stabilizers are preferred from the viewpoint of foaming properties. One type of foam stabilizer may be used alone, or two or more types may be used in combination.

[0056] The content of the foam stabilizer in the polyol-containing composition of the present invention is preferably 0.3 to 2 mass%, more preferably 0.5 to 1.5 mass%, and even more preferably 0.7 to 1.2 mass%, based on the total amount of the polyol-containing composition. When the content of the foam stabilizer is equal to or greater than the lower limit, the mixture of the polyol-containing composition and the polyisocyanate is easily foamed, making it possible to obtain a homogeneous polyurethane foam. Furthermore, when the content of the foam stabilizer is equal to or less than the upper limit, the balance between production costs and the obtained effects is optimal.

[0057] (Other ingredients) The polyol-containing composition may contain, as needed, one or more selected from phenol-based, amine-based, sulfur-based and other antioxidants, heat stabilizers, light stabilizers, metal inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, dyes, fillers other than solid flame retardants, and the like, within the scope of the object of the present invention.

[0058] (Manufacturing method) The method for producing the polyol-containing composition of the present invention is not particularly limited, and the composition can be produced, for example, by stirring the components at about room temperature for about 30 seconds to 20 minutes using a homodisper or the like.The polyol-containing composition of the present invention contains a brominated flame retardant having a predetermined structure in the composition, which can prevent the brominated flame retardant from aggregating even during production of the composition, and therefore has good handleability during production.

[0059] [Foamable urethane resin composition and polyurethane foam] The foamable urethane resin composition of the present invention contains the above-mentioned polyol-containing composition and a polyisocyanate. The foamable urethane resin composition is obtained by mixing the above-mentioned polyol-containing composition and a polyisocyanate.

[0060] (Polyisocyanate) In the present invention, examples of the polyisocyanate include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates. Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI).

[0061] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0062] Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0063] Among these, from the viewpoints of ease of use and availability, aromatic polyisocyanates are preferred, diphenylmethane diisocyanate, polymeric MDI, or a mixture thereof is more preferred, and diphenylmethane diisocyanate is even more preferred, with 4,4'-diphenylmethane diisocyanate being particularly preferred. One type of polyisocyanate may be used alone, or two or more types may be used in combination. Furthermore, known additives that are blended into polyisocyanates may be appropriately blended into the polyisocyanate before mixing with the polyol-containing composition.

[0064] It is preferable that the polyol-containing composition and the polyisocyanate mixed therein have substantially the same volume. Specifically, the volume ratio of the polyisocyanate to the polyol-containing composition is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05.

[0065] (Isocyanate Index) The isocyanate index of the foamable urethane resin composition of the present invention is not particularly limited, but is preferably 300 or greater. When the isocyanate index is equal to or greater than the lower limit, the amount of polyisocyanate relative to the polyol becomes excessive, facilitating the formation of isocyanurate bonds due to the polyisocyanate trimer, resulting in improved flame retardancy of the polyurethane foam. It also makes it possible to impart flame retardancy. Furthermore, when the isocyanate index is equal to or greater than the lower limit, combined with the use of the various catalysts described above, it is easy to produce a polyurethane foam having sufficient isocyanurate bonds, i.e., a polyurethane foam that combines high levels of flame retardancy and thermal insulation. From these perspectives, the isocyanate index is more preferably 350 or greater, and even more preferably 400 or greater. The isocyanate index is preferably not more than 1,000, more preferably not more than 800, and even more preferably not more than 600. When the isocyanate index is not more than the upper limit, flame retardancy that is sufficiently commensurate with the production cost can be obtained.

[0066] The isocyanate index can be calculated by the following method. Isocyanate Index = number of equivalents of polyisocyanate ÷ (number of equivalents of polyol + number of equivalents of water) × 100 Here, each equivalent number can be calculated as follows: Polyisocyanate equivalent number = Amount of polyisocyanate used (g) × NCO content (mass%) / Molecular weight of NCO (mol) × 100 Equivalent weight of polyol = OHV × amount of polyol used (g) ÷ molecular weight of KOH (mmol) OHV is the hydroxyl value of the polyol (mg KOH / g). Equivalents of water = Amount of water used (g) / Molecular weight of water (moles) × Number of OH groups in water In the above formulas, the molecular weight of NCO is 42 (mol), the molecular weight of KOH is 56,100 (mmol), the molecular weight of water is 18 (mol), and the number of OH groups in water is 2.

[0067] (Total heat generation) The polyurethane foam made from the foamable urethane resin composition of the present invention has a total calorific value of 8 MJ / m when tested with a cone calorimeter in accordance with the ISO-5660 test method. 2 The total calorific value is preferably less than 8MJ / m 2 When the above-mentioned temperature is lower than 1000°C, the polyurethane foam made from the foamable urethane resin composition of the present invention has a predetermined flame retardancy. From the viewpoint of further improving the flame retardancy of the foam, the total calorific value is set to 7.8 MJ / m 2 More preferably, it is less than 7.5 MJ / m 2 The lower the total calorific value, the better, and ideally 0 MJ / m 2 However, it is usually 1MJ / m2 That's all. The total calorific value can be easily adjusted to the desired value by adjusting the composition of the foamable urethane resin composition, generally by adjusting the content of the flame retardant. The above cone calorimeter test was conducted at a radiation heat intensity of 50 kW / m 2 The polyurethane foam to be subjected to the cone calorimeter test is formed from a foamable urethane resin composition by the method described in the Examples.

[0068] (core density) The core density of the polyurethane foam made from the foamable urethane resin composition of the present invention is not particularly limited, but is preferably 25 to 60 kg / m 3 The density is preferably in the range of 60 kg / m 3 By setting the weight below 25 kg / m, the polyurethane foam becomes lighter and easier to apply to structures. 3 From these viewpoints, the core density of the polyurethane foam is set to 25 to 55 kg / m or more, thereby making it easier to exhibit the desired flame retardancy. 3 More preferably, it is in the range of 30 to 50 kg / m 3 The core density can be determined by forming a foam from the foamable urethane resin composition by the method described in the examples and measuring the core density of the foam.

[0069] There are no particular limitations on the method for producing the polyurethane foam, but it is preferable to produce the polyurethane foam by mixing the polyol-containing composition with polyisocyanate in a foaming machine or the like, and reacting and foaming the resulting mixed liquid (foamable urethane resin composition).

[0070] The foaming machine may be provided with a filter for removing dust contained in the polyol-containing composition. The filter may be a mesh filter or the like, which allows the solid flame retardant contained in the polyol-containing composition to pass through while removing dust. The filter may be installed in a position prior to mixing with the polyisocyanate. The polyol-containing composition is preferably fed to a foaming machine and impingedly mixed with polyisocyanate fed from another container, etc. In this process, since the brominated flame retardant contained in the polyol-containing composition has a predetermined structure, aggregation of the brominated flame retardant does not occur, and clogging of the filter inside the foaming machine can be prevented.

[0071] The polyol-containing composition and the foamable urethane resin composition are preferably used for spray applications. Therefore, it is preferable to use a spray device having a spray gun or the like as the foaming machine. When a spray device is used, the mixed liquid (foamable urethane resin composition) obtained by collision mixing the polyol-containing composition and the polyisocyanate is discharged from a discharge port of the spray gun or the like, and the discharged foamable urethane resin composition is used to form a polyurethane foam. The mixed solution discharged from the spray device is preferably sprayed onto a target surface at a constant discharge pressure and foamed to form a polyurethane foam on the target surface. The polyurethane foam may be formed on a target surface such as a wall, ceiling, roof, or floor. The isocyanate and polyol-containing composition in the foaming solution are reacted at an equal volume ratio, so that the foaming solution can be reacted at a volume ratio of 1.0 to 0.8 to 1.2. More specifically, spraying can be performed using a spraying device (e.g., A-25 manufactured by GRACO) and a spray gun (e.g., D-gun manufactured by Gasmar Co., Ltd.) Spraying can be performed by adjusting the temperature of a polyol-containing composition for spraying and a polyisocyanate contained in separate containers in the spraying device, causing them to collide and mix at the tip of the spray gun, and turning the mixed liquid into a mist using air pressure. As described above, the spraying device and spray gun are publicly known and commercially available products can be used. In addition, the temperature setting of the concentrate, pressure, etc. can be the same as those used for spraying general polyurethane foams. [Example]

[0072] 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.

[0073] Details of each component used in each example and comparative example are as follows. (Polyisocyanate) Polyisocyanate (MDI, manufactured by Sumika Covestro Urethane Co., Ltd., product name: Sumidur 44V20)

[0074] (Polyol) Aromatic polyester polyol p-phthalic acid-based polyester polyol (Kawasaki Chemical Industries, Ltd., product name "Maximol RLK-087", aromatic concentration 8% by mass, hydroxyl value = 200 mg KOH / g) Aromatic polyester polyol p-phthalic acid-based polyester polyol (Kawasaki Chemical Industries, Ltd., product name "Maximol RFK-509", aromatic concentration 24%, hydroxyl value = 200 mg KOH / g)

[0075] (Foam stabilizer) Silicone foam stabilizer (manufactured by Dow Toray, product name "SH-193")

[0076] (catalyst) (1) Trimerization catalyst Alkali metal salt: Potassium 2-ethylhexanoate (manufactured by Evonik, product name "DABCO K-15"), concentration 70-80% by mass Quaternary ammonium salt: 2,2-dimethylpropanoic acid tetramethylammonium salt (manufactured by Evonik, product name "DABCO TMR7") concentration 45 to 55% by mass (2) Urethane catalyst Amine catalyst 1: 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-DM70) concentration 65 to 75% by mass Metal catalyst: bismuth trioctate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600) concentration 55 to 58% by mass (3) Foaming catalyst Amine catalyst 2: Bis(2-dimethylaminoethyl) ether (manufactured by Momentive Performance Materials Japan, product name "NIAX CATALYST A-1"), concentration approximately 70% by mass

[0077] (Flame retardant) Red phosphorus flame retardant (Rinkagaku Kogyo Co., Ltd., product name: NovaExcel 140) Phosphate ester flame retardant: Tris(β-chloropropyl)phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP) Boron-based flame retardant: Zinc borate (manufactured by Hayakawa Shoji Co., Ltd., product name: FirebrakeZB) Brominated flame retardant 1: ethylene bis(pentabromophenyl) (manufactured by Albemarle Corporation, product name: SAYTEX 8010, bromine content 82% by mass) Brominated flame retardant 2: Hexabromobenzene (HBB) (manufactured by Nippoh Chemical Co., Ltd., product name: FR-B, bromine content 87% by mass) Brominated flame retardant 3: Tetrabromobisphenol A bis(2,3-dibromo-2-methylpropyl) ether (manufactured by Daiichi Pharmaceutical Co., Ltd., product name: Pyroguard SR-130, bromine content 65% by mass) Brominated flame retardant 4: Tetrabromobisphenol A (manufactured by Tosoh Corporation, product name: Flamecut 120G, bromine content 59% by mass)

[0078] [Examples 1 to 7, Comparative Examples 1 to 3] A spraying device was filled with a polyol-containing composition and a polyisocyanate. The temperature of the filled polyol-containing composition and polyisocyanate was adjusted in the spraying device, and a spray gun was used to impinge and mix the polyol-containing composition and polyisocyanate in the formulation shown in Table 1 to obtain a foamable urethane resin composition. The foamed urethane resin composition was sprayed in the form of a mist onto a gypsum board to foam, thereby obtaining a polyurethane foam. Both the spraying device and the spray gun were commercially available products.

[0079] The methods for measuring the physical properties of the polyurethane foam and evaluating the properties of the polyol-containing composition are as follows. [Total heat generation] The total calorific value of the polyurethane foams produced in each of the Examples and Comparative Examples was evaluated by the following method. (1) To obtain a test specimen for measuring the total heat generation, the foamable urethane resin composition obtained in each Example and Comparative Example was sprayed onto a 12.5 mm thick gypsum board using the above-mentioned spraying machine to a thickness of 10 mm, thereby obtaining a first layer of polyurethane foam. (2) A foamable urethane resin composition was sprayed onto the first-layer polyurethane foam to a thickness of 20 mm to obtain a second-layer polyurethane foam. At this point, the total thickness of the polyurethane foam from the first to second layers was 30 mm. The polyurethane foam specimens obtained by the above methods (1) and (2) were prepared as samples for cone calorimeter testing. The samples were subjected to a cone calorimeter test in accordance with the ISO-5660 test method at a radiant heat intensity of 50 kW / m 2 The total heat generated was measured when heated at 400°C for 20 minutes.

[0080] [Core Density] A polyurethane foam specimen similar to that used for measuring the gross calorific value was prepared. A rectangular parallelepiped specimen measuring approximately 100 mm long, 50 mm wide, and 10 mm high was cut out from the second layer of the specimen, excluding the skin layer. The mass and volume of the specimen were measured, and the core density was calculated from the measured mass and volume.

[0081] [Filter clogging] Two types of foaming machine filters (40 micron mesh and 80 micron mesh) with different mesh sizes were prepared. Each filter was installed in the path through which the polyol-containing composition passed through the foaming machine, and the presence or absence of clogging of the filter was visually confirmed after approximately 10 L of a foamable urethane resin composition obtained by mixing the polyol-containing composition and polyisocyanate was discharged from the foaming machine. The evaluation criteria for filter clogging were as follows: A: A 40 micron mesh filter was installed, and no clogging occurred. △: Clogging occurred when a 40 micron mesh filter was loaded, but no clogging occurred when an 80 micron mesh filter was loaded. ×: An 80 micron mesh filter was loaded and clogging occurred.

[0082] [Dripping] The polyol-containing composition and polyisocyanate were mixed according to the formulation shown in Table 1, and the mixture was sprayed onto a substrate (gypsum board) using a sprayer under the above-mentioned polyurethane foam production conditions, so that the polyurethane foam had a thickness of 30 mm or less, and the presence or absence of dripping was visually confirmed. The evaluation criteria for dripping were as follows: ○: No dripping occurred. △: Partial dripping occurred. ×: Dripping occurred all over the surface.

[0083] [Flame retardant] The flame retardancy of the polyurethane foam was evaluated based on the total calorific value measured by the above method. The flame retardancy evaluation criteria are as follows: 〇:8MJ / m 2 less than △:8MJ / m 2 More than 10MJ / m 2 less than ×:10MJ / m 2 End

[0084] [Inactivation] A foamable urethane resin composition was obtained by mixing a polyol-containing composition and a polyisocyanate according to the formulation shown in Table 1. Then, under the polyurethane foam production conditions described above, the composition was sprayed onto a substrate (gypsum board) using a sprayer in a scattering manner so that the thickness of the polyurethane foam became 5 mm or less, and the tack-free time (TFT), which is the time it took for the surface to harden after spraying, was measured. In this case, the polyol-containing composition was subjected to an accelerated aging test at 60°C for one week. The spraying operation and TFT measurement were carried out before and after the accelerated aging test. The deactivation of the foamable urethane resin composition was evaluated based on the difference between the TFT before and after the accelerated aging test. The evaluation criteria for deactivation are as follows: ○: The increase rate of TFT during accelerated deterioration testing is less than 30% ×: The increase rate of TFT due to accelerated deterioration test is 30% or more

[0085] The polyurethane foam thus obtained was subjected to the above-mentioned evaluations. The evaluation results for each item are shown in Table 1.

[0086] [Table 1]

[0087] The parts by mass of each catalyst are parts by mass of the product.

[0088] As described above, the polyol-containing compositions prepared in each Example all exhibited good foaming properties and prevented clogging of the filter inside the foaming machine. Furthermore, the polyurethane foams formed by reacting the compositions with polyisocyanates and foaming them all exhibited excellent flame retardancy. In contrast, the polyol-containing composition prepared in Comparative Example 1 did not contain a brominated flame retardant having a predetermined structure, and therefore clogged the filter inside the foaming machine, making it impossible to discharge a sufficient amount of the polyol-containing composition. Furthermore, the polyol-containing compositions prepared in Comparative Examples 2 and 3 were able to prevent the filter inside the foaming machine from clogging, but at least one of the foaming properties of the composition and the flame retardancy of the polyurethane foam formed from the composition was impaired.

Claims

1. A polyol-containing composition comprising a polyol, a blowing agent, a catalyst, and a flame retardant, the catalyst comprises at least one metal catalyst selected from bismuth salts and tin salts; A polyol-containing composition, wherein the flame retardant comprises a brominated flame retardant having a structure containing at least two benzene rings per molecule.

2. The polyol-containing composition according to claim 1 , wherein at least two of the benzene rings constituting the brominated flame retardant are chemically bonded via an ethylene group.

3. The polyol-containing composition according to claim 1 or 2, wherein the brominated flame retardant contains at least one brominated benzene ring.

4. The polyol-containing composition according to any one of claims 1 to 3, wherein the bromine content in the brominated flame retardant is 50 mass% or more based on the total amount of the brominated flame retardant.

5. The polyol-containing composition according to any one of claims 1 to 4, wherein the brominated flame retardant is ethylenebis(pentabromophenyl).

6. The polyol-containing composition according to any one of claims 1 to 5, wherein the flame retardant comprises a red phosphorus-based flame retardant.

7. The polyol-containing composition according to claim 6, wherein the content of the red phosphorus-based flame retardant is 6 to 36 mass% based on the total amount of the polyol-containing composition.

8. The polyol-containing composition of any one of claims 1 to 7, wherein the blowing agent comprises a hydrofluoroolefin.

9. The polyol-containing composition according to any one of claims 1 to 8, wherein the catalyst comprises an imidazole derivative.

10. The polyol-containing composition of any one of claims 1 to 9, wherein the catalyst comprises a trimerization catalyst.

11. The polyol-containing composition of claim 10 , wherein the trimerization catalyst comprises a quaternary ammonium salt.

12. The polyol-containing composition according to any one of claims 1 to 11, wherein the weighted average aromatic concentration of the polyol is 10% by mass or more.

13. The polyol-containing composition according to any one of claims 1 to 12, wherein the content of the flame retardant is 20 to 60 mass% based on the total amount of the polyol-containing composition.

14. The polyol-containing composition according to any one of claims 1 to 13, wherein the content of the brominated flame retardant is 20 mass% or less based on the total amount of the polyol-containing composition.

15. The polyol-containing composition of any one of claims 1 to 14, for use in spray applications.

16. A foamable urethane resin composition comprising the polyol-containing composition according to any one of claims 1 to 15 and a polyisocyanate.

17. 17. The foamable urethane resin composition according to claim 16, wherein the polyisocyanate is an aromatic polyisocyanate.

18. 18. The foamable urethane resin composition according to claim 16 or 17, having an isocyanate index of 300 or more.

19. The foam obtained by foaming the foamable urethane resin composition has a core density of 25 to 60 kg / m ３ The foamable urethane resin composition according to any one of claims 16 to 18,

20. The polyurethane foam obtained by foaming the foamable urethane resin composition has a radiant heat intensity of 50 kW / m2 when tested with a cone calorimeter in accordance with the ISO-5660 test method. ２ The total heat generated when heated for 20 minutes is 8 MJ / m ２ The foamable urethane resin composition according to any one of claims 16 to 19, wherein the viscosity is less than 1000 MPa.

21. A polyurethane foam formed by reacting and foaming the foamable urethane resin composition according to any one of claims 16 to 20.

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