Polyol composition, urethane resin composition, and polyurethane foam

Abstract

To provide a polyol composition that can form a polyurethane foam resistant to shrinkage after application, and can suppress the occurrence of caking.SOLUTION: The present invention provides a polyol composition that is reacted with polyisocyanate to yield a polyurethane foam. The polyol composition contains a polyol compound, a catalyst, a foamer, and a filler.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to polyol compositions, urethane resin compositions, and polyurethane foams. [Background technology]

[0002] Polyurethane foam is used in practical applications for insulation and condensation prevention in various structures such as ceilings, roofs, and walls of buildings, including apartment buildings, detached houses, and commercial buildings, due to its excellent thermal insulation properties. Polyurethane foam is formed, for example, by spraying a urethane resin composition containing a polyol composition and polyisocyanate onto the surface of each structure, followed by foaming and curing. As a urethane resin composition for forming polyurethane foam, for example, Patent Document 1 discloses a flame-retardant urethane resin composition comprising a polyisocyanate compound, a polyol compound, a trimerizing catalyst, a blowing agent, a foam stabilizer, and additives. Furthermore, Patent Document 2 discloses a sprayable polyol-containing composition containing a solid flame retardant for obtaining polyurethane foam by reacting with polyisocyanate. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Patent No. 6200435 [Patent Document 2] Japanese Patent Publication No. 2022-123400 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, conventional polyurethane foams made from urethane resin compositions or polyol compositions have a problem of shrinking after application and peeling off from the application site. In addition, when polyol compositions containing powders such as solid flame retardants are stored, the powder may settle and aggregate over time, leading to a problem called caking, where it becomes impossible to redisperse. When caking occurs in a polyol composition, the solid flame retardant does not properly disperse within the foam when it is mixed with polyisocyanate and foamed to form a polyurethane foam, making it impossible to improve flame retardancy. Therefore, the object of the present invention is to provide a polyol composition that can form a polyurethane foam in which shrinkage after construction is suppressed and in which the occurrence of caking is suppressed. [Means for solving the problem]

[0005] As a result of diligent research, the inventors of the present invention have found that the above problems can be solved by including a polyol compound, a catalyst, a foaming agent, and a filler in the polyol composition, and have completed the present invention. The present invention provides the following [1] to [8].

[0006] [1] A polyol composition for obtaining a polyurethane foam by reacting with a polyisocyanate, wherein the polyol composition contains a polyol compound, a catalyst, a blowing agent, and a filler, and the content of the filler is 20 to 140 parts by mass per 100 parts by mass of the polyol compound. [2] The polyol composition according to [1], wherein the filler is selected from the group consisting of flame retardants and inorganic fillers. [3] The polyol composition according to [1] or [2], comprising the catalyst a trimerizing catalyst. [4] The polyol composition according to [1] or [2], wherein the catalyst comprises a bismuth compound or a tin compound. A polyol composition according to [5][1] or [2], and a urethane resin composition containing a polyisocyanate compound. [6] The urethane resin composition according to [5], wherein the urethane resin composition is for spray application. [7] The urethane resin composition according to [5] or [6], wherein the isocyanate index is 150 or higher. A polyurethane foam obtained by reacting and foaming the urethane resin composition described in [8], [5], or [6]. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a polyol composition that can form a polyurethane foam in which shrinkage after construction is suppressed and in which the occurrence of caking is suppressed. [Modes for carrying out the invention]

[0008] [Polyol composition] The polyol composition of the present invention is a polyol composition for obtaining a polyurethane foam by reacting it with a polyisocyanate compound. The polyol composition of the present invention contains a polyol compound, a catalyst, a blowing agent, and a filler.

[0009] <Filler> The polyol composition of the present invention contains a filler. The inclusion of a filler can suppress the shrinkage of the polyurethane foam. The filler is preferably at least one of a flame retardant and an inorganic filler. The flame retardant used as the filler is a solid flame retardant. A solid flame retardant is a flame retardant that becomes solid at room temperature (23°C) and normal pressure (1 atm).

[0010] (Solid flame retardant) The polyol composition preferably contains a solid flame retardant. The inclusion of a solid flame retardant makes it easier to impart flame retardancy to the polyurethane foam. Examples of solid flame retardants include phosphate-containing flame retardants, red phosphorus-based flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, metal hydroxides, and needle-shaped fillers. Examples of phosphate-containing flame retardants include phosphates comprising salts of various phosphoric acids with at least one metal or compound selected from metals of 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 may be monophosphates such as phosphorous acid and hypophosphorous acid, or it may be pyrophosphate, polyphosphate, etc. Examples of metals in groups IA through 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, and piperazine. Examples of aromatic amines include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, and 3-(trifluoromethyl)aniline. Examples of heterocyclic compounds containing nitrogen in the ring include pyridine, triazine, and melamine.

[0011] Specific examples of phosphate-containing flame retardants include monophosphates such as aluminum phosphite and trialuminum phosphate, pyrophosphates, and polyphosphates. Here, the polyphosphates are not particularly limited, but examples include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, and aluminum polyphosphate. One or more of the above-mentioned phosphate-containing flame retardants can be used. In the present invention, trialuminum phosphate is preferred.

[0012] The red phosphorus-based flame retardant may consist of elemental red phosphorus, or may be red phosphorus coated with a resin, metal hydroxide, metal oxide, etc., or may be a mixture of red phosphorus and a resin, metal hydroxide, metal oxide, etc. The resin for coating red phosphorus or mixing with red phosphorus is not particularly limited, but examples include thermosetting resins such as phenolic resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. From the viewpoint of flame retardancy, metal hydroxides are preferred as the compound for coating or mixing. The metal hydroxides described later may be appropriately selected and used.

[0013] The bromine-containing flame retardant is not particularly limited as long as it is a compound containing bromine in its molecular structure and being solid at normal temperature and pressure. Examples include brominated aromatic ring-containing aromatic compounds. Examples of the brominated aromatic ring-containing aromatic compounds include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylene bis(pentabromophenyl), ethylene bis(tetrabromophthalimide), and tetrabromobisphenol A.

[0014] In addition, the brominated aromatic ring-containing aromatic compound may be a bromine compound polymer. Specifically, examples include polycarbonate oligomers produced from brominated bisphenol A as a raw material, brominated polycarbonates such as copolymers of this polycarbonate oligomer and bisphenol A, diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin, and the like. Furthermore, brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, poly(brominated benzyl acrylate), condensates of brominated phenols of brominated polyphenylene ether, brominated bisphenol A and cyanuric chloride, brominated (polystyrene), poly(brominated styrene), brominated polystyrenes such as crosslinked brominated polystyrene, crosslinked or non-crosslinked brominated poly(-methylstyrene), and the like can be mentioned. Moreover, it may be a compound other than the brominated aromatic ring-containing aromatic compound such as hexabromocyclododecane. These bromine-containing flame retardants may be used alone or in combination of two or more. Among those described above, brominated aromatic ring-containing aromatic compounds are preferred, and among them, monomeric organic bromine compounds such as hexabromobenzene are preferred.

[0015] Examples of the boron-containing flame retardant used in the present invention include borax, boron oxide, boric acid, borate, and the like. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, tetraboron pentoxide, and the like. Examples of borates include borates of alkali metals, alkaline earth metals, elements of Group 4, Group 12, and Group 13 of the periodic table, and ammonium. Specifically, alkali metal borates such as lithium borate, sodium borate, potassium borate, cesium borate, alkaline earth metal borates such as magnesium borate, calcium borate, barium borate, zirconium borate, zinc borate, aluminum borate, ammonium borate, and the like can be mentioned. The boron-containing flame retardant may be used alone or in combination of two or more. The boron-containing flame retardant used in the present invention is preferably a borate, and more preferably zinc borate.

[0016] Examples of antimony-containing flame retardants include antimony oxide, antimonate salts, and pyroantimonate salts. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimonate salts include sodium antimonate and potassium antimonate. Examples of pyroantimonate salts include sodium pyroantimonate and potassium pyroantimonate. Antimony-containing flame retardants may be used alone or in combination of two or more types. The preferred antimony-containing flame retardant used in this invention is antimony trioxide.

[0017] Examples of metal hydroxides used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, and tin hydroxide. A single metal hydroxide may be used, or two or more may be used in combination. A preferred metal hydroxide used in the present invention is aluminum hydroxide.

[0018] Examples of needle-shaped fillers include potassium titanate whiskers, aluminum borate whiskers, magnesium-containing whiskers, silicon-containing whiskers, silicon-based fillers, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fibers, carbon fibers, graphite fibers, metal fibers, slag fibers, gypsum fibers, silica fibers, alumina fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, stainless steel fibers, and the like. These needle-shaped fillers may be used individually or in combination of two or more types.

[0019] The aspect ratio (length / diameter) of the needle-shaped filler used in the present invention is preferably in the range of 5 to 50, and more preferably in the range of 10 to 40. This aspect ratio can be determined by observing the needle-shaped filler with a scanning electron microscope and measuring its length and width.

[0020] The solid flame retardants used in the present invention may be used individually or in combination of two or more types. When using two or more types in combination, for example, two or more solid flame retardants of the same classification may be used, such as containing potassium titanate whiskers and aluminum borate whiskers as needle-shaped fillers, or one or more solid flame retardants of different classifications may be used, such as containing a red phosphorus-based flame retardant and needle-shaped fillers. Furthermore, it is preferable to use at least one of the following solid flame retardants: a red phosphorus-based flame retardant, a bromine-containing flame retardant, and a boron-containing flame retardant. It is more preferable to use at least two of these, and even more preferable to use all three.

[0021] (Inorganic fillers) The polyol composition of the present invention preferably contains an inorganic filler, and in particular, it is preferable to contain an inorganic filler in addition to the solid flame retardant described above as a filler. By containing a solid flame retardant and an inorganic filler, the polyol composition can be made flame retardant, less prone to caking, and have post-construction shrinkage suppressed. Examples of inorganic fillers include diatomaceous earth, alumina, titanium dioxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass beads, silica balloons, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon balloons, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash, silica alumina fibers, and zirconia fibers. These inorganic fillers may be used individually or in combination of two or more types. In the present invention, it is preferable to use at least one of calcium carbonate or barium sulfate as the inorganic filler. By using calcium carbonate or barium sulfate as the inorganic filler, it is possible to appropriately suppress shrinkage and caking after construction while keeping production costs down.

[0022] The filler content in the polyol composition of the present invention is 20 to 140 parts by mass per 100 parts by mass of the polyol compound. If the filler content is less than 20 parts by mass, it becomes difficult to suppress the shrinkage of the polyurethane foam. If the filler content exceeds 140 parts by mass, it becomes difficult to suppress the occurrence of caking of the polyol composition due to the aggregation of the filler. Considering these points, the filler content is preferably 25 to 125 parts by mass, and more preferably 50 to 110 parts by mass, per 100 parts by mass of the polyol compound. Furthermore, if the filler content is above the lower limit mentioned above, it becomes easier not only to suppress the shrinkage of the polyurethane foam but also to add various functions such as flame retardancy.

[0023] The amount of solid flame retardant is not particularly limited, but is preferably 15 to 120 parts by mass, more preferably 22 to 110 parts by mass, and even more preferably 45 to 100 parts by mass, per 100 parts by mass of the polyol compound. Increasing the amount of solid flame retardant makes it easier to impart high flame retardancy. On the other hand, decreasing the amount of solid flame retardant makes it easier to suppress the occurrence of caking. The amount of inorganic filler is not particularly limited, but is preferably 1 to 35 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 4 to 25 parts by mass, per 100 parts by mass of the polyol compound. By setting the amount of inorganic filler within the above predetermined range, it becomes easier to further suppress shrinkage and caking of the polyurethane foam. Furthermore, from the viewpoint of suppressing aggregation and preventing caking, the amount of inorganic filler is more preferably 5 to 15 parts by mass. Furthermore, from the viewpoint of more effectively suppressing shrinkage, the amount of inorganic filler is more preferably 15 to 25 parts by mass.

[0024] As described above, it is preferable to use a solid flame retardant and an inorganic filler in combination as the filler contained in the polyol composition of the present invention. In the polyol composition of the present invention, when a solid flame retardant and an inorganic filler are used in combination as fillers, the ratio of the solid flame retardant to the inorganic filler (solid flame retardant / inorganic filler) is not particularly limited, but is preferably 2 to 50, more preferably 3 to 30, and even more preferably 4.5 to 25. When the solid flame retardant / inorganic filler ratio is within the above range, it is possible to achieve a good balance between improving the flame retardancy of the polyurethane foam, reducing the production cost of the polyol composition, and suppressing the occurrence of caking.

[0025] <Catalyst> (trimerization catalyst) The catalyst used in this invention preferably contains a trimerizing catalyst. The trimerizing catalyst is a catalyst that reacts with the isocyanate groups contained in the polyisocyanate to trimerize them and promote the formation of an isocyanurate ring. By including a trimerizing catalyst, an isocyanurate ring can be formed, thereby increasing flame retardancy. In addition, the reaction of the isocyanate groups is completed, making it easier to obtain a polyurethane foam with good foaming properties. Examples of trimerizing catalysts include metal catalysts and ammonium salts. Examples of metal catalysts used as trimerization catalysts (trimerization metal catalysts) include potassium organic acids, preferably potassium octoates such as potassium 2-ethylhexanoate, potassium acetate, potassium propionate, potassium butanoate, potassium benzoate, and other potassium carboxylates having 2 to 8 carbon atoms. As the ammonium salt, tertiary ammonium salts such as triethylammonium salt and triphenylammonium salt, and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, and tetraphenylammonium salt can be used, but among these, quaternary ammonium salts are preferred. The ammonium salt is, for example, an ammonium salt of a carboxylic acid. Examples of carboxylic acids in the ammonium salt include saturated fatty acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms. The hydrocarbon group of the saturated fatty acid may be linear or branched, but branching is preferred. Specific examples of carboxylic acids include 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid, but among these, 2,2-dimethylpropanoic acid is preferred. The trimerization catalyst may be used alone or two or more may be used in combination. The trimerizing catalyst preferably contains a quaternary ammonium salt. Including a quaternary ammonium salt as the trimerizing catalyst improves stability with respect to hydrofluoroolefins, thereby preventing decomposition of the hydrofluoroolefins and resulting in good foaming properties. Furthermore, it allows for a reaction rate above a certain level, improving the workability when spraying the urethane resin composition. The trimerization catalyst more preferably contains a quaternary ammonium salt and a trimerized metal catalyst.

[0026] The content of quaternary ammonium salt in the polyol composition is preferably 0.1 to 15 parts by mass, more preferably 0.4 to 10 parts by mass, and even more preferably 1 to 8 parts by mass, per 100 parts by mass of the polyol compound. By setting the above content of quaternary ammonium salt above the lower limit, stability against HFO and workability during spraying can be improved. Furthermore, by setting the above content of quaternary ammonium salt below the upper limit, the reaction rate can be appropriately controlled. The content of the trimerized metal catalyst is not particularly limited, but is preferably 0.2 to 13 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 0.6 to 5 parts by mass, per 100 parts by mass of the polyol compound. Furthermore, the content of the trimerizing catalyst in the polyol composition is preferably 0.3 to 28 parts by mass, more preferably 0.7 to 20 parts by mass, and even more preferably 2 to 13 parts by mass, per 100 parts by mass of the polyol compound.

[0027] (Resin-based catalyst) The catalyst used in this invention preferably contains a metal catalyst as a resinification catalyst. This metal catalyst is generally called a resinification metal catalyst. In this invention, the inclusion of the above resinification metal catalyst promotes the reaction between the polyol compound and the polyisocyanate compound, and in particular, the initial reaction rate can be increased. Furthermore, the inclusion of the resinification metal catalyst makes it easier to appropriately control the reaction rate between the polyol compound and the polyisocyanate compound. The above resinification metal catalyst is preferably a bismuth compound containing bismuth or a tin compound containing tin, with bismuth compounds being more preferable, from the viewpoint of forming a polyurethane foam that has foaming properties and suppresses shrinkage after application. Bismuth compounds have low reactivity to HFO and high storage stability. Furthermore, they make it easier to achieve good initial activity without reducing the flame retardancy of the polyurethane foam.

[0028] The resinified metal catalyst described above is preferably a metal salt selected from bismuth and tin, and more preferably a bismuth salt. The metal salt is preferably an organic acid metal salt, and more preferably a metal salt of a carboxylic acid having 5 or more carbon atoms. Having 5 or more carbon atoms in the carboxylic acid provides good stability against blowing agents, especially hydrofluoroolefins. Furthermore, from the viewpoint of catalytic activity, the number of carbon atoms in the carboxylic acid is preferably 18 or less, and more preferably 12 or less. The carboxylic acid is preferably an aliphatic carboxylic acid, and more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may be linear or have a branched structure, but it is preferable to have a branched structure. Specific examples of carboxylic acids include octyl acid, lauryl acid, versatic acid, pentanoic acid, and acetic acid, with octyl acid being preferred among these. In other words, the transition metal salt is preferably a metal salt of octyl acid. These carboxylic acids may be linear as described above, but they may also have a branched structure. An example of octyl acid having a branched structure is 2-ethylhexanoic acid. Preferred metal salts of carboxylic acids include bismuth salts and tin salts of carboxylic acids, with bismuth salts of octic acid being particularly preferred. Alternatively, the metal salt of the carboxylic acid may be an alkyl metal carboxylic acid salt. For example, the tin salt of the carboxylic acid may be a dialkyltin carboxylic acid salt, and preferably a dioctyltin carboxylic acid salt. Specific examples of metal salts of carboxylic acids include bismastrioctate, dioctyltin versatate, dibutyltin dilaurate, dioctyltin dilaurate, and tin dioctylate, with bismastrioctate and dioctyltin versatate being preferred, and bismastrioctate being more preferred.

[0029] The polyol composition of the present invention may contain a nitrogen-containing heterocyclic compound as a resinification catalyst. The inclusion of a nitrogen-containing heterocyclic compound as a resinification catalyst improves stability with respect to hydrofluoroolefins, thereby preventing decomposition of hydrofluoroolefins and resulting in good foaming properties. Furthermore, it allows for a reaction rate above a certain level, improving the workability when spraying the urethane resin composition. Among nitrogen-containing heterocyclic compounds, the inclusion of an imidazole derivative is more preferable. As described above, imidazole derivatives are less affected by hydrofluoroolefins and facilitate the reaction between polyols and polyisocyanates while increasing the stability of the polyol composition. Therefore, by containing imidazole derivatives, the reactivity between the polyol compound and the polyisocyanate compound is enhanced, resulting in even better foaming properties. The imidazole derivative is preferably an imidazole in which the 1st and 2nd positions are independently substituted with alkyl groups having 8 or fewer carbon atoms, and the alkyl groups preferably have 6 or fewer carbon atoms, more preferably 4 or fewer carbon atoms. A suitable specific example of an imidazole derivative is represented by the following general formula (1).

[0030] [ka] (In general formula (1), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.

[0031] R in general formula (1) 1 and R 2 Each of these independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. The alkyl group and 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, an octyl group, and the like. Specific examples of the alkenyl group include a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, and the like. R 1 and R 2 When the number of carbon atoms of the alkyl group or alkenyl group of R and R is equal to or greater than the lower limit value, steric hindrance increases and it becomes difficult to be affected by a foaming agent such as hydrofluoroolefin, which is preferable. On the other hand, when the number of carbon atoms of the alkyl group of R and R is equal to or less than the upper limit value, steric hindrance does not extremely increase, so that the reaction between the polyol and the polyisocyanate can proceed rapidly and the foaming property also becomes good. 1 and R 2 When the number of carbon atoms of the alkyl group of R and R is equal to or less than the upper limit value, steric hindrance does not extremely increase, so that the reaction between the polyol and the polyisocyanate can proceed rapidly and the foaming property also becomes good. From these viewpoints, R 1 and R 2 are each independently preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group.

[0032] Examples of the imidazole derivative represented by the general formula (1) include 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. Among them, from the viewpoints of improving the activity of the catalyst in the presence of hydrofluoroolefin and allowing the reaction to proceed rapidly, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferable. Further, from the viewpoint of further enhancing stability, 1,2-dimethylimidazole is more preferable.

[0033] The content of the resinified metal catalyst in the polyol composition is not particularly limited, but is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass, and even more preferably 3 to 7 parts by mass, per 100 parts by mass of the polyol compound. If the resinified metal catalyst is above the lower limit, the reaction rate between the polyol compound and the polyisocyanate compound is increased, and shrinkage of the polyurethane foam is suppressed, making it easier to form a high-quality polyurethane foam. If the resinified metal catalyst is below the upper limit, the reaction rate between the polyol compound and the polyisocyanate compound can be appropriately controlled. The content of nitrogen-containing heterocyclic compounds in the polyol composition is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 2 to 6 parts by mass, per 100 parts by mass of the polyol compound. If the content of nitrogen-containing heterocyclic compounds is above the lower limit, urethane bond formation is more likely to occur, the reaction proceeds rapidly, and foaming properties are good. On the other hand, if the content of nitrogen-containing heterocyclic compounds is below the upper limit, the reaction rate is easier to control, which is preferable. The total content of the resinification catalyst in the polyol composition is not particularly limited, but is preferably 2 to 20 parts by mass, more preferably 3 to 16 parts by mass, and even more preferably 5 to 13 parts by mass, per 100 parts by mass of the polyol compound.

[0034] <Polyol compounds> The polyol compound is not particularly limited, but examples include polyether polyols and polyester polyols. From the viewpoint of improving the flame retardancy of polyurethane foam, it is preferable that the polyol compound contains polyester polyol. Furthermore, from the viewpoint of improving flame retardancy, the use of halogen-containing polyols and phosphorus-containing polyols is also preferable. From this viewpoint, it is preferable that of 100 parts by mass of the polyol compound, polyester polyol be 20 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 80 parts by mass or more, and particularly preferably 100 parts by mass.

[0035] The average hydroxyl value of the polyol compound used in the present invention is preferably 100 to 500 mg KOH / g, more preferably 150 to 450 mg KOH / g, and even more preferably 200 to 400 mg KOH / g, from the viewpoint of improving the flame retardancy of the polyurethane foam. The average hydroxyl value is the hydroxyl value of a single polyol compound if only one polyol compound is used, and the average value of hydroxyl groups according to the blending ratio of the two or more polyol compounds if two or more polyol compounds are used. For example, when using two types of polyol compounds, polyol (d1) and polyol (d2), if the hydroxyl value of polyol (d1) is X1 and the blending ratio is m1, and the hydroxyl value of polyol (d2) is X2 and the blending ratio is m2, the average hydroxyl value is expressed by the following formula. Note that the blending ratio is on a mass basis. Average hydroxyl value (mgKOH / g)=X1×(m1 / (m1+m2))+X2×(m2 / (m1+m2)) The hydroxyl value is measured in accordance with JIS K1557-1:2007.

[0036] (Polyester polyol) The polyester polyol may be a polyester polyol having an aromatic ring or an aliphatic polyester polyol, but when considering the flame retardancy of the resulting polyurethane foam, it is preferable to use a polyester polyol having an aromatic ring. The polyester polyol having an aromatic ring 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. In particular, from the viewpoint of improving the flame retardancy of the polyurethane foam, the polyol compound preferably contains a phthalic acid-based polyester polyol, which is a condensate of phthalic acid and glycol, and more preferably contains a p-phthalic acid-based polyester polyol, which is a condensate of p-phthalic acid and glycol. While the glycol is not particularly limited, it is preferable to use a low molecular weight aliphatic glycol known as a component of polyester polyols, such as ethylene glycol, propylene glycol, or diethylene glycol.

[0037] The hydroxyl value of the polyester polyol is preferably 100-500 mgKOH / g, more preferably 150-450 mgKOH / g, and even more preferably 200-400 mgKOH / g.

[0038] (Polyether polyol) Examples of polyether polyols include polyoxyalkylene polyols obtained by ring-opening addition polymerization of alkylene oxide to an initiator having two or more active hydrogen atoms. Examples of initiators include aliphatic polyhydric alcohols (e.g., glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, and cyclohexanedimethanol; triols such as trimethylolpropane and glycerin; tetrafunctional alcohols such as pentaerythritol; 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, Mannich condensates, etc.). Of these, polyether polyols produced using an initiator having an aromatic ring are polyether polyols having an aromatic ring. For example, polyether polyols produced using an aromatic amine as an initiator are polyether polyols having an aromatic ring. Among polyether polyols having an aromatic ring, tolylenediamine-based polyether polyols and Mannich-based polyether polyols can be suitably used.

[0039] Tolylenediamine-based polyether polyols are tolylenediamine-based polyether polyols manufactured using tolylenediamine as an initiator. The above-mentioned Mannich-type polyether polyols are obtained using the Mannich reaction and are Mannich condensates having two or more hydroxyl groups in the molecule, or polyether polyols obtained by adding alkylene oxide to such Mannich condensates. More specifically, they are Mannich condensates obtained by the Mannich reaction of at least one of phenol and its alkyl-substituted derivatives, formaldehyde and alkanolamines, or polyether polyols obtained by ring-opening addition polymerization of these compounds with at least one of ethylene oxide and propylene oxide.

[0040] The hydroxyl value of the polyether polyol is preferably 200 to 2000 mg KOH / g, and more preferably 300 to 1000 mg KOH / g.

[0041] <Foaming agent> The blowing agent promotes the foaming of the urethane resin composition. Examples of blowing agents include organic physical blowing agents such as water, low-boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane; chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride; ether compounds such as hydrofluoroolefins (hereinafter sometimes referred to as "HFO") and diisopropyl ether; or mixtures of these compounds; and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Of these, it is preferable to include hydrofluoroolefin (HFO), which has high stability as a blowing agent, is less prone to a decrease in catalytic activity, and also has a low environmental impact.

[0042] Suitable HFOs as blowing agents include fluoroalkenes with approximately 3 to 6 carbon atoms. Alternatively, the HFO may be a hydrochlorofluoroolefin containing a chlorine atom, and therefore may also be a chlorofluoroalkene with approximately 3 to 6 carbon atoms. Examples of HFOs include trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorodifluoropropene, chlorotrifluoropropene such as HFO-1233, and chlorotetrafluoropropene. More specifically, 3,3,3-trifluoropropene (HFO-1243zf), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,1,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), and trans-1,2,3,3,3-pene. Examples include tafluoropropene (HFO-1225ye(E)), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1,1,2,3,3-pentafluoropropene (HFO-1225yc), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)), and 1,1,1,4,4,4-hexafluorobuto-2-ene (HFO-1336mzz). Among these, HFO-1233zd(E) is preferred.

[0043] The content of the blowing agent is not particularly limited, but is preferably 20 to 50 parts by mass, more preferably 25 to 46 parts by mass, and even more preferably 29 to 41 parts by mass, per 100 parts by mass of the polyol compound. If the content of the blowing agent is above the lower limit, foaming is promoted, resulting in good foamability and a reduction in the density of the polyurethane foam. On the other hand, if the content of the blowing agent is below the upper limit, excessive foaming can be suppressed. Furthermore, by keeping the content of the blowing agent within the above range, it becomes easier to adjust the gel time of the urethane resin composition to a predetermined range.

[0044] The above-mentioned foaming agents can be used one or more types. In the urethane resin composition of the present invention, it is preferable to use the above-mentioned HFO in combination with other foaming agents. For example, HFO may be used in combination with water, oxygen gas, or carbon dioxide gas, which have excellent handling properties. Water is particularly preferred from the viewpoint of adjusting the isocyanate index and ease of handling. The HFO content is preferably 19 to 48 parts by mass, more preferably 24 to 44 parts by mass, and even more preferably 30 to 40 parts by mass, per 100 parts by mass of the polyol compound. The water content is preferably 0.1 to 2 parts by mass, more preferably 0.2 to 1.5 parts by mass, and even more preferably 0.5 to 1 part by mass, per 100 parts by mass of the polyol compound.

[0045] <Liquid Flame Retardant> In addition to the solid flame retardant described above, the polyol composition of the present invention may also contain a liquid flame retardant. A liquid flame retardant is one that becomes liquid at room temperature (25°C) and normal pressure (1 atm). The liquid flame retardant is not particularly limited, but a phosphate ester-based flame retardant is preferred.

[0046] As phosphate ester-based flame retardants, monophosphate esters, condensed phosphate esters, etc., can be used. A monophosphate ester is a phosphate ester that has one phosphorus atom in its 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, cresyldiphenyl phosphate, and diphenyl(2-ethylhexyl) phosphate; and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate.

[0047] Examples of condensed phosphate esters include aromatic condensed phosphate esters such as trialkyl polyphosphates, resorcinol polyphenyl phosphates, bisphenol A polycresyl phosphates, and bisphenol A polyphenyl phosphates. Examples of commercially available condensed phosphate esters include "CR-733S," "CR-741," and "CR747" from Daihachi Chemical Industry Co., Ltd., and "ADEKA Stab PFR" and "FP-600" from ADEKA Corporation.

[0048] The phosphate ester flame retardants may be used individually from the above-mentioned types, or two or more may be used in combination. Among these, monophosphate esters are preferred from the viewpoint of making it easier to adjust the viscosity of the polyol composition and improving the flame retardancy of the polyurethane foam, and halogen-containing phosphate esters such as tris(β-chloropropyl) phosphate are more preferred.

[0049] The content of the phosphate ester-based flame retardant in the polyol composition is not particularly limited, but is preferably 15 to 90 parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 25 to 70 parts by mass, per 100 parts by mass of the polyol compound. When the content of the phosphate ester-based flame retardant is above these lower limits, it becomes easier to impart flame retardancy to the polyurethane foam without making the viscosity of the polyol composition too high or the content of the solid flame retardant too high. Furthermore, when the content of the phosphate ester-based flame retardant is below these upper limits, foaming is not inhibited, making it easier to manufacture the polyurethane foam.

[0050] <Foam stabilizer> The polyol composition of the present invention may contain a foam stabilizer. Suitable foam stabilizers include compounds having polar and non-polar portions within their molecule and exhibiting surfactant properties. The foam stabilizer is not particularly limited, but examples include surfactants such as polyoxyalkylene foam stabilizers like polyoxyalkylene alkyl ethers and silicone foam stabilizers like organopolysiloxanes. As a silicone foam stabilizer, a graft copolymer of polyoxyalkylene glycol (a polymer of ethylene oxide or propylene oxide) and polydimethylsiloxane may also be used. Commercially available products can also be used, specifically foam stabilizers such as SH-193 (Toray Dow Corning), S-824-02 (Nippon Unicar), SZ-1704 (Nippon Unicar), F501 (Shin-Etsu Chemical Co., Ltd.), and SF-2937F (Dow Toray). The amount of foam stabilizer is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of the polyol compound.

[0051] <Thickening agent> The polyol composition of the present invention may contain a thickening agent. Examples of thickening agents include powdered silica such as fumed silica, colloidal silica, and silica gel, organic affinity phyllosilicates, hydrogenated castor oil wax, and fatty acid amide wax. Among these, fumed silica is preferred, and hydrophobic fumed silica is particularly preferred. As fumed silica, Aerosil® from Nippon Aerosil Co., Ltd. can be used. By containing a thickening agent, the polyol composition increases viscosity, allowing for uniform dispersion of fillers and making it easier to suppress filler aggregation. The thickening agent is, for example, 0.1 to 10 parts by mass, preferably 0.4 to 8 parts by mass, and more preferably 0.8 to 5 parts by mass, per 100 parts by mass of the polyol compound.

[0052] <Other ingredients> In addition to the above, the polyol composition of the present invention may contain, as necessary and within the limits that do not impair its purpose, one or more additives selected from phenolic, amine, and sulfur-based antioxidants, heat stabilizers, metal damage inhibitors (metal deactivators), antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, plasticizers, pigments, tackifying resins, polybutene, petroleum resins, and other tackifying agents.

[0053] [Urethane resin composition] The present invention also provides a urethane resin composition. The urethane resin composition of the present invention contains a polyol compound, a catalyst, a blowing agent, and a filler, in addition to a polyisocyanate compound. Furthermore, the urethane resin composition may contain liquid flame retardants such as phosphate esters, as well as foam stabilizers, thickeners, and other components. The details of each component contained in the urethane resin composition are as described above, and their explanation will be omitted here.

[0054] The urethane resin composition of the present invention preferably comprises the above-mentioned polyol composition and a polyisocyanate compound, and is obtained by mixing these. Furthermore, the polyurethane foam of the present invention is a reaction product obtained by reacting and foaming the urethane resin composition.

[0055] <Polyisocyanate compounds> In the present invention, examples of polyisocyanate compounds 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).

[0056] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0057] Examples of aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0058] Among these, aromatic polyisocyanates are preferred from the viewpoint of ease of use and availability, diphenylmethane diisocyanate, polymeric MDI, or mixtures thereof are more preferred, with diphenylmethane diisocyanate being even more preferred, and 4,4'-diphenylmethane diisocyanate being particularly preferred. Polyisocyanates may be used individually or as a mixture of two or more. Furthermore, before mixing the polyisocyanate compound with the polyol composition, known additives that are incorporated into polyisocyanate compounds may be added as appropriate.

[0059] Furthermore, it is preferable that the volume of the polyol composition and the polyisocyanate compound mixed with the polyol composition are substantially the same. Specifically, the volume ratio of the polyisocyanate compound to the polyol composition is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05.

[0060] <Isocyanate Index> There are no particular restrictions on the isocyanate index in the urethane resin composition of the present invention, but a value of 150 or higher is preferred. When the isocyanate index is above the lower limit, the amount of polyisocyanate compound relative to the polyol compound becomes excessive, making it easier to form isocyanurate bonds by the trimer of the polyisocyanate compound, resulting in improved flame retardancy of the polyurethane foam. It also becomes possible to impart flame retardancy. Furthermore, when the index is above the lower limit, in combination with the various catalysts described above, it is easier to produce a polyurethane foam with sufficient isocyanurate bonds, that is, a polyurethane foam that combines flame retardancy and heat insulation at a high level. From these viewpoints, an isocyanate index of 250 or higher is more preferred, and 300 or higher is even more preferred. Furthermore, the isocyanate index is preferably 1,000 or less, more preferably 800 or less, and even more preferably 600 or less. When the isocyanate index is below the above upper limit, flame retardancy that is sufficiently commensurate with the manufacturing cost can be obtained.

[0061] The isocyanate index can be calculated using the following method. Isocyanate Index = Equivalents of polyisocyanate compound ÷ (Equivalents of polyol compound + Equivalents of water) × 100 Here, each equivalent number can be calculated as follows: • Equivalent weight of polyisocyanate compound = Amount of polyisocyanate compound used (g) × NCO content (mass%) / Molecular weight of NCO (moles) × 100 • Equivalent weight of polyol compound = OHV × Amount of polyol compound used (g) ÷ Molecular weight of KOH (millimoles) OHV is the hydroxyl value (mgKOH / g) of a polyol compound. • Equivalent amount 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 moles, the molecular weight of KOH is 56,100 millimoles, the molecular weight of water is 18 moles, and the number of OH groups in water is 2.

[0062] <Method for manufacturing polyurethane foam> There are no particular restrictions on the method for producing polyurethane foam, but it is preferable to produce polyurethane foam by mixing a polyol composition with a polyisocyanate compound in a foaming machine or the like, and then reacting and foaming the resulting mixture (urethane resin composition). As the foaming machine, a spray device with a spray gun or the like is preferable. The polyol composition is supplied to a foaming machine and mixed with polyisocyanate foam supplied from another container inside the machine. The resulting mixture (urethane resin composition) is then discharged from a nozzle such as a spray gun, and polyurethane foam is formed using the discharged urethane resin composition.

[0063] This manufacturing method is preferably applicable to spray applications. Therefore, the mixed liquid discharged from the foaming machine is sprayed onto the surface to be treated at a constant discharge pressure and foamed to form a polyurethane foam on the surface to be treated.

[0064] <Application> The uses of the urethane resin composition of the present invention and the polyurethane foam formed from the composition are not particularly limited, but they can be used to fill cavities in structures such as buildings, furniture, automobiles, trains, and ships, or to spray onto such structures. In particular, they are preferably used for spraying onto structures, i.e., for spraying, and more preferably for spraying at construction sites of buildings. Spraying can be carried out using a spraying device (e.g., GRACO A-25) and a spray gun (e.g., Gasmar D-gun). Spraying is performed by temperature-controlled mixing of the polyol composition and polyisocyanate in separate containers within the spraying device, then causing them to collide and mix at the tip of the spray gun, and finally atomizing the mixture using air pressure. The spraying device and spray gun are well-known and commercially available. Furthermore, the stock solution temperature settings and pressure can be the same as those for spraying polyurethane foam. [Examples]

[0065] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0066] [Materials used]

[0067] <Polyisocyanate compounds> • 4,4'-Diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Manka Chemical Japan Co., Ltd., product name: PM200) <Polyol composition> (Polyol compounds) • p-phthalate polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g)

[0068] (catalyst) • Trimerization catalyst 1: Quaternary ammonium salt, tetramethylammonium 2,2-dimethylpropanoate (Air Products, product name: DABCO(registered trademark) TMR7), concentration 45-55% by mass • Trimerization catalyst 2: Metal catalyst, potassium 2-ethylhexanoate (Air Products, Inc., product name: DABCO(registered trademark) K-15), concentration 70-80% by mass • Resinization catalyst 1: Imidazole derivative, 1,2-dimethylimidazole (manufactured by Kao Corporation, product name: Kaolizer No. 390), concentration 65-75% by mass • Resinization catalyst 2: Transition metal salt, bismuth 2-ethylhexanoate (manufactured by Nitto Chemical Co., Ltd., product name: Bi28), concentration 81-90% by mass • Resinization catalyst 3: Transition metal salt, dioctyl (2-ethylhexyl) suzubatesate (manufactured by Nitto Chemical Co., Ltd., product name: Neostan U-830), concentration approximately 99% by mass

[0069] (Foaming agent) • Hydrofluoroolefin (HFO), trans-1-chloro-3,3,3-trifluoropropene (manufactured by Honeywell Japan, product name: Soltis LBA) ·water

[0070] (Phosphate ester (liquid flame retardant)) • Tris(β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)

[0071] (Filler) • Solid flame retardant 1: Red phosphorus (manufactured by Phosphorus Chemical Industry Co., Ltd., product name: Nova Excel 140) • Solid flame retardant 2: Zinc borate (manufactured by Hayakawa Shoji Co., Ltd., product name: FirebrakeZB) • Solid flame retardant 3: Ethylenebis(pentabromophenyl) (manufactured by Albemarle, product name: SAYTEX 8010) • Inorganic filler 1: Barium sulfate (manufactured by Kinsei Matec Co., Ltd., product name: Precipitating barium sulfate D-0.6) • Inorganic filler 2: Calcium carbonate (manufactured by Hayashi Chemical Co., Ltd., product name: Heavy calcium carbonate KS-1300)

[0072] (Thickening agent) • Fumed silica (manufactured by Aerosil Japan, product name: Aerosil R976S)

[0073] [Manufacturing of polyurethane foam] A polyol composition was prepared by mixing each component according to the formulations shown in Table 1. A polyurethane foam was produced using this polyol composition and a polyisocyanate compound under the following conditions. <Manufacturing conditions> • Spraying machine: Graco H-25 spraying device • Settings (heater and pressure settings) Isocyanate heater: 38℃ Premix heater (for heating polyol compositions): 38℃ Hose heater (for pre-mixing heating of polyisocyanate and polyol-containing compositions): 38°C Pressure: Adjust as needed to create a circular mist. • Substrate temperature (temperature of the surface to be sprayed): 20℃±1℃

[0074] [Methods for evaluating each physical property] 1. Contraction evaluation In each example and comparative example, the polyol composition and polyisocyanate compound prepared according to the formulations described in Table 1 were introduced into a spraying apparatus. After adjusting the temperature within the apparatus, a urethane resin composition consisting of a mixture of the polyol composition and the polyisocyanate compound was sprayed onto a gypsum board (300 mm x 300 mm) using a spray gun to form a 10 mm thick first layer of polyurethane foam. At this time, the temperature of the spraying apparatus's pump and hose was adjusted to 38°C, and the pressure was set to 5 MPa. The isocyanate index of the urethane resin composition is shown in Table 1. Similarly, a second layer of polyurethane foam with a thickness of 20 mm was formed on the first layer of polyurethane foam, and then a third layer of polyurethane foam with a thickness of 20 mm was formed on the second layer of polyurethane foam to obtain a three-layer polyurethane foam structure. A test specimen measuring 100 mm in length, 100 mm in width, and 30 mm in thickness, including the intermediate skin between the second and third layers, was cut from the second and third layers of polyurethane foam. The test specimens were subjected to a shrinkage acceleration test in an oven at 95% humidity and 40°C for 5 days, and the volume change rate was calculated from the volume after the test and the volume before the test. The volume of the test specimen was calculated by taking the average of four equally spaced measurements of the length, width, and thickness of the specimen. The volume change rate was calculated using the following formula (1). Volume change rate (%) = 100 × [(Volume of the specimen before testing - Volume of the specimen after testing) / Volume of the specimen before testing] ... Equation (1) (Evaluation Criteria) ◎...Volume change rate less than 5% ○...Volume change rate is 5% or more but less than 15% ×...Volume change rate is 15% or more

[0075] 2.Cohesiveness In each example and comparative example, 400 mL of the polyol composition prepared according to the formulations listed in Table 1 was placed in a cup (inner diameter × outer diameter × height (mm): 89 × 101 × 111), stored in a 55°C oven for 3 days, and then evaluated for caking (cohesiveness) based on the following drop evaluation. <Drop Evaluation> I judged the state of the caking when I dropped the spatula into the mixture. ◎: It reached the bottom of the cup without any effort. ○: When force was applied, it reached the bottom of the cup. ×: Even with force applied, it did not reach the bottom of the cup.

[0076] [Table 1] *The catalyst content in Table 1 is in parts by mass of the product.

[0077] As is clear from the above examples, the polyol composition satisfying the requirements of the present invention suppressed caking, and the polyurethane foam made from the composition as a raw material had a suppressed shrinkage rate. In contrast, the polyol composition prepared in Comparative Example 1 had too much filler, resulting in poor cohesiveness and an inability to properly disperse the filler within the composition. Furthermore, the polyol compositions prepared in Comparative Examples 2 and 3 had too little filler, and as a result, the polyurethane foams made from these compositions could not adequately suppress volume changes due to shrinkage.

Claims

1. A polyol composition for obtaining a polyurethane foam by reacting with a polyisocyanate, The polyol composition contains a polyol compound, a catalyst, a blowing agent, and a filler. The filler comprises a solid flame retardant and an inorganic filler. The solid flame retardant is one or more selected from the group consisting of phosphate-containing flame retardants, red phosphorus-based flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, metal hydroxides, and needle-shaped fillers. The inorganic filler is calcium carbonate and / or barium sulfate, The content of the filler is 20 to 140 parts by mass per 100 parts by mass of the polyol compound. A polyol composition in which the ratio of the solid flame retardant to the inorganic filler (solid flame retardant / inorganic filler) is 2 to 50.

2. The polyol composition according to claim 1, further comprising a liquid flame retardant.

3. The polyol composition according to claim 1 or 2, wherein the content of the solid flame retardant is 15 to 120 parts by mass per 100 parts by mass of the polyol compound.

4. The polyol composition according to claim 1 or 2, wherein the content of the inorganic filler is 1 to 35 parts by mass per 100 parts by mass of the polyol compound.

5. The polyol composition according to claim 1 or 2, wherein the catalyst comprises a trimerizing catalyst.

6. The polyol composition according to claim 1 or 2, wherein the catalyst comprises a bismuth compound or a tin compound.

7. A polyol composition according to claim 1 or 2, and a urethane resin composition containing a polyisocyanate compound.

8. The urethane resin composition according to claim 7, wherein the urethane resin composition is for spray application.

9. The urethane resin composition according to claim 7, wherein the isocyanate index is 150 or higher.

10. A polyurethane foam obtained by reacting and foaming the urethane resin composition described in claim 7.

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