Polyol composition, flame-retardant urethane resin composition, and polyurethane foam

Abstract

To provide a polyol composition that exhibits low viscosity and reduced caking.SOLUTION: A polyol composition for obtaining a polyurethane foam by reaction with a polyisocyanate, the polyol composition containing a polyol, a catalyst, a blowing agent, a flame retardant, and a filler composed of a pulverized mineral.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyol composition, a flame-retardant 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 insulating and preventing condensation 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 flame-retardant 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. Therefore, in order to enhance the flame retardancy of polyurethane foams, filler components such as flame retardants and inorganic fillers are sometimes blended into the raw materials. For example, in Patent Document 1, at least red phosphorus is blended as an additive into a flame-retardant urethane resin composition. In Patent Document 2, a red phosphorus-based flame retardant, a phosphate-containing flame retardant, or the like is blended into a polyol-containing composition. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6200435 [Patent Document 2] Japanese Patent Publication No. 2022-123400 Summary of the Invention [Problem to be solved by the invention]

[0005] When a filler component is blended into the raw materials for polyurethane foam, the filler components may aggregate, separate from the non-filler components, precipitate, and become difficult to redisperse in the raw materials, which is known as caking. One way to prevent caking is to increase the viscosity of the raw materials, but increasing the viscosity too much can deteriorate the workability during spraying.

[0006] Therefore, an object of the present invention is to provide a polyol composition that has a low viscosity and is suppressed from caking. [Means for solving the problem]

[0007] As a result of extensive research, the present inventors have found that the above problems can be solved by blending a filler made of pulverized minerals in a polyol composition. That is, the present invention provides the following [1] to

[14] .

[0008] [1] A polyol composition for reacting with a polyisocyanate to produce a polyurethane foam, the polyol composition comprising a polyol, a catalyst, a blowing agent, a flame retardant, and a ground mineral filler. [2] The polyol composition according to [1], wherein the filler obtained by crushing a mineral contains at least one selected from calcium carbonate, barium sulfate, silica, silicon-based compounds other than silica, talc, mica, clay, wollastonite, apatite, and acicular alumina. [3] The polyol composition according to [1] or [2], wherein the filler obtained by pulverizing the mineral has an average particle size of 50 μm or less. [4] The polyol composition according to any one of [1] to [3], wherein the content of the crushed mineral filler is 3 parts by mass or more per 100 parts by mass of the polyol. [5] The polyol composition according to any one of [1] to [4], wherein the viscosity of the polyol composition is 1300 mPa·s or less. [6] The polyol composition according to any one of [1] to [5], wherein the catalyst contains an organic acid bismuth salt. [7] The polyol composition according to any one of [1] to [6], wherein the catalyst contains a heterocyclic compound having a nitrogen atom. [8] The polyol composition according to any one of [1] to [7], wherein the catalyst contains a quaternary ammonium salt. [9] The polyol composition according to any one of [1] to [8], wherein the catalyst contains a potassium salt.

[10] The polyol composition according to any one of [1] to [9], wherein the flame retardant contains a solid phosphorus-based compound.

[11] A flame-retardant urethane resin composition comprising the polyol composition according to any one of [1] to

[10] and a polyisocyanate.

[12] The flame-retardant urethane resin composition according to

[11] , wherein the flame-retardant urethane resin composition has an isocyanate index of 250 or more.

[13] A polyurethane foam formed by foaming the flame-retardant urethane resin composition according to

[11] or

[12] .

[14] The polyurethane foam according to

[13] , which is formed by spray foaming the flame-retardant urethane resin composition. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a polyol composition which has a low viscosity and is inhibited from caking. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Polyol composition] The polyol composition of the present invention is a polyol composition for producing a polyurethane foam by reacting with a polyisocyanate, and includes a polyol, a catalyst, a blowing agent, a flame retardant, and a ground mineral filler. Each component of the polyol composition will be described in detail below.

[0011] <Pulverized filler> The polyol composition of the present invention contains a filler obtained by pulverizing a mineral (hereinafter also referred to as a "pulverized filler"). The mineral may be a natural mineral or a synthetic mineral. Generally, chemically synthesized fillers often have a symmetrical shape, and when such fillers are used, caking of the polyol composition is likely to occur. On the other hand, ground fillers have a distorted and asymmetrical shape, and each particle has a different shape, so caking of the polyol composition can be suppressed. Although the mechanism behind this is unclear, it is presumed that when ground fillers aggregate, other ground filler particles tend to enter the gaps between ground filler particles. The ground filler preferably contains at least one selected from calcium carbonate, barium sulfate, silica, silicon compounds other than silica, talc, mica, clay, wollastonite, apatite, and acicular alumina. Among these, it is more preferable to contain at least one selected from calcium carbonate, wollastonite, and barium sulfate, and from the viewpoint of production costs, it is even more preferable to contain at least one selected from calcium carbonate and barium sulfate. The use of these ground fillers makes it easier to suppress caking of the polyol composition. The pulverized filler may be used alone or in combination of two or more kinds.

[0012] The average particle diameter of the pulverized filler (hereinafter simply referred to as "average particle diameter") is preferably 50 μm or less, more preferably 35 μm or less, even more preferably 20 μm or less, and even more preferably 10 μm or less. When the average particle diameter is equal to or less than the upper limit, caking of the polyol composition is easily suppressed. Furthermore, the average particle diameter is not particularly limited, but in practice it is, for example, 0.7 μm or more, preferably 1 μm or more. The average particle size can be measured using a laser diffraction particle size distribution analyzer. The average particle size is calculated by determining the particle size (d50) of aggregated particles when the cumulative volume is 50%.

[0013] The content of the pulverized filler is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 7 parts by mass or more, relative to 100 parts by mass of the polyol. By containing a certain amount of pulverized filler or more, caking of the polyol composition can be easily suppressed. Furthermore, the content of the pulverized filler is preferably 35 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 15 parts by mass or less. By setting the content of the pulverized filler to a certain amount or less, the viscosity of the polyol composition can be easily set to a certain amount or less, and the handleability, such as the workability, of the polyol composition can be easily improved.

[0014] The content of the pulverized filler is preferably 5 to 35 parts by mass, more preferably 7 to 30 parts by mass, and even more preferably 10 to 25 parts by mass, relative to 100 parts by mass of the total content of the pulverized filler and the solid flame retardant described below. By adjusting the content of the pulverized filler within the above range, it becomes easier to appropriately suppress caking while maintaining the viscosity at a certain level or below.

[0015] <Flame retardant> The polyol composition of the present invention contains a flame retardant. The flame retardant may be, for example, a solid flame retardant other than the above-mentioned ground filler, or a liquid flame retardant.

[0016] (Solid flame retardant) A solid flame retardant is one that becomes solid at room temperature (25°C) and normal pressure (1 atmosphere). Specific examples of solid flame retardants include phosphate-containing flame retardants, solid phosphorus-based compounds such as red phosphorus-based flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, and metal hydroxides. 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 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, and may be a monophosphoric acid such as phosphorous acid or hypophosphorous acid, or may be pyrophosphoric acid, polyphosphoric acid, or the like. 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 the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, etc. Examples of the aromatic amine include aniline, o-toliidine, 2,4,6-trimethylaniline, anisidine, 3-(trifluoromethyl)aniline, etc. Examples of the heterocyclic compound containing nitrogen in the ring include pyridine, triazine, melamine, etc.

[0017] Specific examples of phosphate-containing flame retardants include monophosphates such as aluminum phosphite and aluminum triphosphate, pyrophosphates, polyphosphates, etc. Here, the polyphosphates are not particularly limited, but examples include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate. The phosphate-containing flame retardant may be one or more of the above-mentioned compounds, and in the present invention, aluminum triphosphate is preferred.

[0018] 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 that coats the red phosphorus or is mixed with the 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 to be coated or mixed. The metal hydroxide to be used may be appropriately selected from those described below.

[0019] The bromine-containing flame retardant is not particularly limited as long as it contains bromine in its molecular structure and is a compound that is solid at room temperature and normal pressure, and examples thereof include brominated aromatic ring-containing aromatic compounds. Examples of the brominated aromatic ring-containing aromatic compound include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

[0020] The brominated aromatic ring-containing aromatic compound may also be a bromine compound polymer. Specific examples include brominated polycarbonates such as polycarbonate oligomers produced using brominated bisphenol A as a raw material, copolymers of the polycarbonate oligomers with bisphenol A, and diepoxy compounds produced by reacting brominated bisphenol A with epichlorohydrin. Further examples include brominated epoxy compounds such as monoepoxy compounds obtained by reacting brominated phenols with epichlorohydrin, poly(brominated benzyl acrylate), brominated phenol condensates of brominated polyphenylene ether, brominated bisphenol A, and cyanuric chloride, brominated (polystyrene), poly(brominated styrene), brominated polystyrenes such as crosslinked brominated polystyrene, and crosslinked or non-crosslinked brominated poly(methylstyrene). Furthermore, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may also be used. These bromine-containing flame retardants may be used alone or in combination of two or more. Among the above, brominated aromatic ring-containing aromatic compounds are preferred, and monomeric organic bromine compounds such as hexabromobenzene are particularly preferred.

[0021] Examples of the boron-containing flame retardant used in the present invention include borax, boron oxide, boric acid, borate salts, etc. Examples of the 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-containing flame retardants 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, more preferably zinc borate.

[0022] 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 retardant may be used alone or in combination of two or more. The preferred antimony-containing flame retardant for use in the present invention is antimony trioxide.

[0023] 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. The metal hydroxides may be used alone or in combination of two or more. The preferred metal hydroxide used in the present invention is aluminum hydroxide.

[0024] The solid flame retardants used in the present invention may be used alone or in combination of two or more. When two or more are used in combination, for example, two or more solid flame retardants of the same category may be used, such as a boron-containing flame retardant containing borax and zinc borate, or one or more solid flame retardants of different categories may be used, such as a red phosphorus-based flame retardant and a boron-containing flame retardant. The polyol composition of the present invention preferably contains, as the solid flame retardant, at least one of a solid phosphorus-based compound, a bromine-containing flame retardant, and a boron-containing flame retardant, more preferably a solid phosphorus-based compound, and even more preferably a red phosphorus-based flame retardant.

[0025] The content of the 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 relative to 100 parts by mass of the polyol. Increasing the amount of the solid flame retardant makes it easier to impart high flame retardancy. On the other hand, decreasing the amount of the solid flame retardant makes it easier to suppress the occurrence of caking and also prevents an increase in viscosity.

[0026] (liquid flame retardant) A liquid flame retardant is one that becomes liquid at room temperature (25° C.) and normal pressure (1 atmosphere). There are no particular limitations on the liquid flame retardant, but phosphate ester flame retardants are preferred.

[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 composition to an appropriate level and 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.

[0030] 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. When the content of the phosphate ester-based flame retardant is equal to or greater than these lower limits, flame retardancy can be easily imparted to the polyurethane foam without excessively increasing the viscosity of the polyol composition or the content of the solid flame retardant. On the other hand, when the content of the phosphate ester-based flame retardant is equal to or less than these upper limits, foaming is not inhibited, and polyurethane foam can be easily produced.

[0031] <Catalyst> The catalyst is not particularly limited, but examples thereof include a trimerization catalyst and a resinification catalyst.

[0032] (trimerization catalyst) The trimerization catalyst is a catalyst that promotes trimerization to form isocyanurate bonds in a flame-retardant urethane resin composition. By promoting trimerization in this manner, the flame retardancy and flame spread resistance of the polyurethane foam are improved. The trimerization catalyst preferably contains at least one selected from quaternary ammonium salts and potassium salts.

[0033] Quaternary ammonium salts Examples of quaternary ammonium salts include quaternary ammonium carboxylates. The carboxylic acid in the quaternary ammonium carboxylate may have one or more carbon atoms, but preferably has two or more carbon atoms. The carboxylic acid is preferably an aliphatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may have, for example, 20 or less carbon atoms, preferably 12 or less, and more preferably 8 or less carbon atoms. The carboxylic acid may be linear or may have a branched structure, but preferably has a branched structure. If the carboxylic acid has a branched structure, steric hindrance tends to reduce the reactivity with a blowing agent such as hydrofluoroolefin, thereby improving the stability of the polyol composition.

[0034] Specific examples of suitable carboxylic acids in the quaternary ammonium carboxylate include 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, formic acid, etc. Among these, at least one selected from acetic acid and 2,2-dimethylpropanoic acid is preferred, and 2,2-dimethylpropanoic acid is more preferred.

[0035] The quaternary ammonium ion in the quaternary ammonium carboxylate is preferably a tetraalkylammonium ion or a hydroxyalkyltrialkylammonium ion, and more preferably a tetraalkylammonium ion.

[0036] Each alkyl group in the tetraalkylammonium ion is, for example, an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms, and more preferably a methyl group. Specific examples of the tetraalkylammonium ion include a tetramethylammonium ion and a triethylmethylammonium ion.

[0037] Each alkyl group in the hydroxyalkyltrialkylammonium ion is, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group, an ethyl group, or a butyl group. The hydroxyalkyl group is an alkyl group in which one of the hydrogen atoms has been substituted with a hydroxy group, and has, for example, 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms, and more preferably 3 or 4 carbon atoms. Examples of the hydroxyalkyl group include a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. Specific examples of the hydroxyalkyltrialkylammonium ion include a hydroxybutyltrimethylammonium ion, a hydroxypropyltrimethylammonium ion, and a hydroxyethyltrimethylammonium ion.

[0038] The ammonium ion in the quaternary ammonium carboxylate is preferably at least one selected from the group consisting of triethylmethylammonium ion, tetramethylammonium ion, hydroxybutyltrimethylammonium ion, and hydroxypropyltrimethylammonium ion, more preferably at least one selected from the group consisting of triethylmethylammonium ion, tetramethylammonium ion, and hydroxybutyltrimethylammonium ion, and even more preferably a tetramethylammonium ion.

[0039] Specific preferred examples of the quaternary ammonium carboxylate include tetramethylammonium acetate, tetramethylammonium 2,2-dimethylpropanoate, triethylmethylammonium 2-ethylhexanoate, and hydroxybutyltrimethylammonium 2-ethylhexanoate. Among these, from the viewpoint of facilitating the formation of an isocyanurate bond by a trimer of polyisocyanate and imparting excellent flame retardancy to the polyurethane foam, at least one selected from tetramethylammonium acetate and tetramethylammonium 2,2-dimethylpropanoate is preferred, and tetramethylammonium 2,2-dimethylpropanoate is more preferred. In the present invention, the quaternary ammonium carboxylates may be used alone or in combination of two or more.

[0040] Potassium salt Examples of potassium salts include potassium carboxylate salts. The carboxylic acid in the potassium carboxylate salt may have one or more carbon atoms, preferably five or more carbon atoms. The carboxylic acid is preferably an aliphatic carboxylic acid, more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may have, for example, 20 or less carbon atoms, preferably 12 or less, and more preferably 8 or less carbon atoms. The carboxylic acid may be linear or may have a branched structure, but preferably has a branched structure. If the carboxylic acid has a branched structure, steric hindrance tends to reduce the reactivity with a blowing agent such as hydrofluoroolefin, thereby improving the stability of the polyol composition.

[0041] Among them, the potassium carboxylate is preferably a potassium carboxylate represented by the following general formula (1): The potassium carboxylate represented by the following general formula (1) has an appropriate degree of steric hindrance, and therefore can suppress the reaction that decomposes the blowing agent and can also prevent a decrease in catalytic activity.

[0042] [ka] (In general formula (1), R 1 and R 2 each independently represents an alkyl group, and R 3 represents a hydrogen atom or an alkyl group. + represents potassium ions.)

[0043] R in general formula (1) 1 and R 2 are each independently an alkyl group, and specifically, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and an alkyl group having 1 to 2 carbon atoms is even more preferable. The alkyl group may be linear or may have a branched structure. R 1 , R 2 If the number of carbon atoms in R is equal to or greater than the lower limit, the steric hindrance becomes large, and the reaction of decomposing the hydrofluoroolefin can be suppressed. 1 , and R2 When the number of carbon atoms is not more than the upper limit, the steric hindrance is not too large, and the reactivity can be prevented from slowing down. Also, R 3 represents a hydrogen atom or an alkyl group, and preferably a hydrogen atom. 3 When is an alkyl group, the alkyl group preferably has 1 to 6 carbon atoms, more preferably has 1 to 4 carbon atoms, and even more preferably has 1 or 2 carbon atoms.

[0044] A preferred example of the carboxylic acid in the potassium carboxylate is at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. Also preferred are carboxylic acids as shown in the general formula (1), and among these, 2,2-dimethylpropanoic acid and 2-ethylhexanoic acid are more preferred. In the present invention, the potassium carboxylates may be used alone or in combination of two or more.

[0045] The content of the trimerization catalyst in the polyol composition is preferably 2 to 20 parts by mass, more preferably 2.5 to 15 parts by mass, and even more preferably 3 to 12 parts by mass, per 100 parts by mass of the polyol. When the content of the trimerization catalyst is equal to or greater than the lower limit, trimerization of the polyisocyanate occurs more easily, and the flame retardancy of the resulting polyurethane foam is improved. On the other hand, when the content of the trimerization catalyst is equal to or less than the upper limit, the reaction is more easily controlled. The trimerization catalyst contained in the polyol composition of the present invention may be used alone or in combination of two or more.

[0046] Furthermore, although only one of the above-mentioned quaternary ammonium salt and potassium salt may be contained, it is also preferable to contain both of them. The content of the quaternary ammonium salt is preferably from 1 to 10 parts by mass, more preferably from 1.2 to 8 parts by mass, and even more preferably from 1.5 to 7 parts by mass, relative to 100 parts by mass of the polyol. The content of the potassium salt is preferably from 1 to 10 parts by mass, more preferably from 1.3 to 8 parts by mass, and even more preferably from 1.5 to 5 parts by mass, relative to 100 parts by mass of the polyol.

[0047] (resinification catalyst) The catalyst used in the present invention preferably contains a metal catalyst as a resinification catalyst. This metal catalyst is generally called a resinification metal catalyst. In the present invention, the inclusion of the resinification metal catalyst promotes the reaction between the polyol and the polyisocyanate, and in particular, can increase the initial reaction rate. Furthermore, the inclusion of the resinification metal catalyst makes it easier to appropriately control the reaction rate between the polyol and the polyisocyanate. From the viewpoint of foamability, the resinification metal catalyst is preferably a bismuth compound containing bismuth or a tin compound containing tin, and more preferably a bismuth compound. Bismuth compounds have low reactivity with HFOs and high storage stability. Furthermore, they tend to improve the initial activity without reducing the flame retardancy of the polyurethane foam.

[0048] The resinified metal catalyst is preferably a metal salt selected from bismuth and tin, more preferably a bismuth salt. The metal salt is preferably an organic acid metal salt, more preferably a metal salt of a carboxylic acid having 5 or more carbon atoms. When the carboxylic acid has 5 or more carbon atoms, stability to blowing agents, particularly hydrofluoroolefins, is improved. Furthermore, from the viewpoint of catalytic activity, the number of carbon atoms in 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 resinified metal catalyst 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.

[0049] The polyol composition of the present invention also preferably contains a heterocyclic compound having a nitrogen atom (hereinafter also referred to as a "nitrogen-containing heterocyclic compound") as a resinification catalyst. By containing a nitrogen-containing heterocyclic compound as a resinification catalyst, stability to hydrofluoroolefins is improved, thereby preventing decomposition of hydrofluoroolefins and improving foamability. In addition, the reaction rate can be made to be at least a certain level, making it possible to improve the workability when spraying the flame-retardant urethane resin composition. Among nitrogen-containing heterocyclic compounds, it is more preferable to contain an imidazole derivative. As described above, 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 composition. Therefore, by including the imidazole derivative in the polyol composition, 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 (2).

[0050] [ka] (In general formula (2), R 4 and R 5 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.

[0051] R in general formula (2) 4 and R 5 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 4 and R 5 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. 4 and R 5 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 4 and R 5 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.

[0052] Examples of the imidazole derivative represented by general formula (2) include 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. Among them, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferred from the viewpoint of improving the activity of the catalyst in the presence of hydrofluoroolefin and promoting the reaction rapidly. Furthermore, 1,2-dimethylimidazole is even more preferred from the viewpoint of further enhancing stability.

[0053] The content of the resinified metal catalyst in the polyol composition is not particularly limited, but is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 2 to 5 parts by mass, per 100 parts by mass of the polyol. When the content of the resinified metal catalyst is equal to or greater than the lower limit, the reaction rate between the polyol and the polyisocyanate is increased, making it easier to form a high-quality polyurethane foam. When the content of the resinified metal catalyst is equal to or less than the upper limit, the reaction rate between the polyol and the polyisocyanate can be appropriately controlled. The content of the nitrogen-containing heterocyclic compound in the polyol composition is not particularly limited, but is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 8 parts by mass, per 100 parts by mass of the polyol. When the content of the nitrogen-containing heterocyclic compound is equal to or greater than the lower limit, urethane bond formation is more likely to occur, the reaction proceeds rapidly, and foaming properties are improved. On the other hand, when the content of the nitrogen-containing heterocyclic compound is equal to or less than the upper limit, the reaction rate can be more easily controlled, which is preferable. The total content of the resinification catalyst in the polyol composition is not particularly limited, but is preferably 0.5 to 25 parts by mass, more preferably 2 to 18 parts by mass, and even more preferably 4 to 13 parts by mass, per 100 parts by mass of the polyol.

[0054] <Polyol> The polyol is not particularly limited, but examples thereof include polyether polyols and polyester polyols. From the viewpoint of improving the flame retardancy of the polyurethane foam, the polyol preferably includes a polyester polyol. Also, from the viewpoint of improving the flame retardancy, it is preferable to use a halogen-containing polyol or a phosphorus-containing polyol. From this viewpoint, for every 100 parts by mass of polyol, it is preferable to use polyester polyol in an amount of 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.

[0055] The average hydroxyl value of the polyol used in the present invention is preferably from 100 to 500 mgKOH / g, more preferably from 150 to 450 mgKOH / g, and even more preferably from 180 to 400 mgKOH / g, from the viewpoint of improving the flame retardancy of the polyurethane foam. When one type of polyol is used, the average hydroxyl value is the hydroxyl value of that one type of polyol, and when two or more types of polyols are used, it is the average value of the hydroxyl groups in accordance with the blending ratio of the two or more types of polyols. For example, when two types of polyols, polyol (d1) and polyol (d2), are used as polyols, the hydroxyl value of polyol (d1) is X1, the blending ratio is m1, and the hydroxyl value of polyol (d2) is X2, the blending ratio is m2, the average hydroxyl value is expressed by the following formula: Note that the blending ratio is based on mass. Average hydroxyl value (mgKOH / g)=X1×(m1 / (m1+m2))+X2×(m2 / (m1+m2)) The hydroxyl value is a value measured in accordance with JIS K1557-1:2007.

[0056] (polyester polyol) The polyester polyol may be a polyester polyol having an aromatic ring or an aliphatic polyester polyol, but when the flame retardancy of the resulting polyurethane foam is taken into consideration, 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, it is preferable for the polyol to contain a phthalic acid-based polyester polyol, which is a condensate of phthalic acid and a glycol, and it is more preferable for the polyol to contain a p-phthalic acid-based polyester polyol, which is a condensate of p-phthalic acid and a glycol. The glycol is not particularly limited, but it is preferable to use low molecular weight aliphatic glycols known as constituent components of polyester polyols, such as ethylene glycol, propylene glycol, and diethylene glycol.

[0057] (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. Specific examples of the initiator include aliphatic polyhydric alcohols (e.g., glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, and cyclohexanedimethanol; triols such as trimethylolpropane and glycerin; tetrafunctional alcohols such as pentaerythritol; and highly functional alcohols such as sucrose and sorbitol), aliphatic amines (e.g., alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine; alkanolamines such as monoethanolamine and diethanolamine), and aromatic amines (e.g., aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, and Mannich condensation products). Among 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, Mannich-based polyether polyols, etc. can be preferably used.

[0058] The tolylenediamine-based polyether polyol is a tolylenediamine-based polyether polyol produced using tolylenediamine as an initiator. The Mannich polyether polyol is a polyether polyol obtained by utilizing the Mannich reaction, which is a Mannich condensation product having two or more hydroxyl groups in the molecule, or a polyether polyol obtained by adding an alkylene oxide to such a Mannich condensation product. More specifically, it is a Mannich condensation product obtained by the Mannich reaction of at least one of phenol and its alkyl-substituted derivatives, formaldehyde, and alkanolamine, or a polyether polyol obtained by ring-opening addition polymerization of this compound with at least one of ethylene oxide and propylene oxide.

[0059] <Foaming agent> The blowing agent promotes foaming of the flame-retardant urethane resin composition. Examples of the blowing agent include organic physical blowing agents such as low-boiling hydrocarbons such as water, 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, and mixtures of these compounds, and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Among these, it is preferable to use hydrofluoroolefin (HFO), which has high stability as a blowing agent, is less likely to decrease in catalytic activity, and has a low environmental impact.

[0060] Examples of suitable HFO blowing agents include fluoroalkenes having about 3 to 6 carbon atoms. HFOs may also be hydrochlorofluoroolefins having chlorine atoms, and therefore may be chlorofluoroalkenes having about 3 to 6 carbon atoms. Examples of HFOs include trifluoropropene, tetrafluoropropenes such as HFO-1234, pentafluoropropenes such as HFO-1225, chlorodifluoropropene, chlorotrifluoropropenes 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)), trans-1,2,3,3,3-tetrafluoropropene Examples of suitable fluoropropenes include 1,2,3,3,3-pentafluoropropene (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-hexafluorobut-2-ene (HFO-1336mzz). Of these, HFO-1233zd(E) is preferred.

[0061] The content of the blowing agent is not particularly limited, and is preferably 20 to 57 parts by mass, more preferably 25 to 52 parts by mass, and even more preferably 30 to 46 parts by mass, per 100 parts by mass of the polyol. When the content of the blowing agent is equal to or greater than the lower limit, foaming is promoted, resulting in good foamability and a reduced density of the polyurethane foam. On the other hand, when the content of the blowing agent is equal to or less than the upper limit, excessive foaming can be prevented. Furthermore, by controlling the content of the blowing agent within the above range, the gel time of the flame-retardant urethane resin composition can be easily adjusted within a predetermined range.

[0062] The above-mentioned blowing agents can be used alone or in combination with two or more other blowing agents. In the urethane resin composition of the present invention, it is preferable to use the above-mentioned HFO in combination with another blowing agent. For example, HFO may be used in combination with water, oxygen gas, or carbon dioxide gas, which is easy to handle. Water is particularly preferable from the viewpoints of adjusting the isocyanate index and ease of handling. The content of HFO is preferably from 20 to 55 parts by mass, more preferably from 25 to 50 parts by mass, and even more preferably from 30 to 45 parts by mass, relative to 100 parts by mass of the polyol compound. The content of water is preferably from 0.1 to 2 parts by mass, more preferably from 0.2 to 1.5 parts by mass, and even more preferably from 0.5 to 1 part by mass, relative to 100 parts by mass of the polyol compound.

[0063] <Foam stabilizer> The polyol composition of the present invention may contain a foam stabilizer. As the foam stabilizer, a compound having a polar portion and a non-polar portion in the molecule and having a surfactant effect can be suitably used. The foam stabilizer is not particularly limited, but examples thereof include surfactants such as polyoxyalkylene foam stabilizers (e.g., polyoxyalkylene alkyl ethers) and silicone foam stabilizers (e.g., organopolysiloxanes). Silicone foam stabilizers may also be graft copolymers of polyoxyalkylene glycols, which are polymers of ethylene oxide or propylene oxide, with polydimethylsiloxane. Commercially available products may also be used, including SH-193 (manufactured by Dow Corning Toray Co., Ltd.), S-824-02 (Nippon Unicar Co., Ltd.), SZ-1704 (Nippon Unicar Co., Ltd.), F501 (Shin-Etsu Chemical Co., Ltd.), and SF-2937F (manufactured by Dow Toray Co., Ltd.). The content of the 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.

[0064] <Anti-settling agent> The polyol composition of the present invention may contain an anti-settling agent. By using an anti-settling agent, the viscosity of the polyol composition can be adjusted to an appropriate range, and in combination with the above-mentioned filler, it becomes easier to suppress caking of the polyol composition. It also makes it easier to uniformly disperse solid components such as fillers. Anti-settling agents generally become solid at room temperature and normal pressure, and usually become solid components (insoluble components) in the mixed liquid. Note that the anti-settling agent is other than the above-mentioned pulverized filler and solid flame retardant.

[0065] The anti-settling agent is not particularly limited, but it is preferable to use one or more selected from, for example, carbon black, powdered silica, organic clay, etc., and among these, powdered silica is more preferable. The carbon black used in the anti-settling agent can be produced by a furnace method, a channel method, a thermal method, etc. Commercially available carbon black may be appropriately selected and used. As the powdered silica, fumed silica, colloidal silica, silica gel, etc. can be used. Of these, fumed silica is preferred. As the fumed silica, Aerosil (registered trademark) from Nippon Aerosil Co., Ltd. can be used.

[0066] When the polyol composition contains an anti-settling agent, the content of the anti-settling agent is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 5 parts by mass, relative to 100 parts by mass of the polyol compound. By setting the content of the anti-settling agent within the above range, it is possible to prevent the settling of solid components without increasing the solid content more than necessary, and further to improve the dispersibility of the solid components. Furthermore, by setting the content below the above upper limit, it is easy to reduce the viscosity.

[0067] <Other ingredients> In addition to the above, the polyol composition of the present invention may contain, as necessary within the scope of the object, one or more additives selected from the group consisting of pulverized fillers, solid flame retardants, and inorganic fillers other than anti-settling agents, phenolic, amine, sulfur-based antioxidants, heat stabilizers, metal inhibitors (metal deactivators), antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, plasticizers, pigments, and tackifying resins, and tackifiers such as polybutene and petroleum resins.

[0068] <Viscosity> The viscosity of the polyol composition of the present invention is preferably 1300 mPa·s or less, more preferably 1200 mPa·s or less, and even more preferably 1000 mPa·s or less. When the viscosity of the polyol composition is equal to or less than the above upper limit, the handleability, such as workability, of the polyol composition is easily improved. On the other hand, the viscosity of the polyol composition is not particularly limited, but from the viewpoint of easily suppressing caking, it is preferably 200 mPa·s or more, more preferably 300 mPa·s or more, and even more preferably 340 mPa·s or more. The viscosity of the polyol composition can be measured by the measurement method described in the Examples.

[0069] [Flame-retardant urethane resin composition] The present invention also provides a flame-retardant urethane resin composition, which contains a polyisocyanate in addition to a polyol, a catalyst, a blowing agent, a flame retardant, and a ground filler. Furthermore, the flame-retardant urethane resin composition may contain a foam stabilizer, an anti-settling agent, and other components, if necessary. The details of each component contained in the flame-retardant urethane resin composition are as described above, and therefore further explanation will be omitted.

[0070] The flame-retardant urethane resin composition of the present invention preferably contains the polyol composition and a polyisocyanate, and is obtained by mixing them. The polyurethane foam of the present invention is a reaction product obtained by reacting and foaming the flame-retardant urethane resin composition.

[0071] <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).

[0072] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0073] Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0074] 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 typically added to polyisocyanates may be appropriately added to the polyisocyanate before it is mixed with the polyol composition.

[0075] The polyol composition and the polyisocyanate mixed with the polyol composition preferably have substantially the same volume. Specifically, the volume ratio of the polyisocyanate 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.

[0076] <Isocyanate Index> The isocyanate index of the flame-retardant urethane resin composition of the present invention is not particularly limited, but is preferably 250 or higher. When the isocyanate index is equal to or higher 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 higher 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 viewpoints, the isocyanate index is more preferably 300 or higher, and even more preferably 350 or higher. 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.

[0077] 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.

[0078] <Method for producing polyurethane foam> The method for producing the polyurethane foam is not particularly limited, but it is preferable to produce the polyurethane foam by mixing the polyol composition with the polyisocyanate in a foaming machine or the like, and reacting and foaming the resulting mixed liquid (flame-retardant urethane resin composition). The foaming machine may be a spray device having a spray gun. Therefore, it is preferable to form the polyurethane foam by spray-foaming the flame-retardant urethane resin composition. The polyol composition is preferably fed to a foaming machine and mixed by collision inside the foaming machine with a polyisocyanate foam fed from another container, etc. The mixed liquid (urethane resin composition) is then discharged from a discharge port of a spray gun, etc., and a polyurethane foam is formed from the discharged flame-retardant urethane resin composition. The crushed filler to be blended into the polyol composition may be a commercially available product in which the mineral has been crushed in advance, or the mineral may be crushed in a crushing device such as a ball mill or roller mill before being blended into the polyol composition, and the crushed mineral may be blended.

[0079] The present production method is preferably applicable to spray applications, and therefore, the mixed liquid discharged from the foaming machine is preferably sprayed onto a target surface at a certain discharge pressure to cause foaming, thereby forming a polyurethane foam on the target surface.

[0080] <Application> The flame-retardant urethane resin composition of the present invention and the polyurethane foam formed from the composition are not particularly limited in their applications, and they can be used to fill cavities in structures such as buildings, furniture, automobiles, trains, ships, etc., or to be sprayed onto such structures. Among these, spraying onto structures, i.e., spray applications, is preferred, and spraying at building construction sites is more preferred. Spraying can be carried out using a spraying device (e.g., A-25 manufactured by GRACO) and a spray gun (e.g., D-gun manufactured by Gasmar). Spraying can be carried out by adjusting the temperature of the polyol composition and polyisocyanate contained in separate containers in the spraying device, causing them to collide and mix at the tip of the spray gun, and then turning the mixed liquid into a mist using air pressure. Spraying devices and spray guns are well known, and commercially available products can be used. Furthermore, the temperature settings and pressure of the raw liquid can be set according to general spraying conditions for polyurethane foam. [Example]

[0081] The present invention will be explained in more detail below using examples, but the present invention is not limited to these examples.

[0082] [Materials used]

[0083] <Polyisocyanate> 4,4'-Diphenylmethane diisocyanate (4,4'-MDI) (Manka Chemical Japan Co., Ltd., product name: PM200) <Polyol composition> (Polyol) p-Phthalic acid polyester polyol (Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g)

[0084] (Flame retardant) Phosphate ester: Tris(β-chloropropyl)phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP) Red phosphorus (Rinkagaku Kogyo Co., Ltd., product name: Nova Excel 140) Zinc borate (Hayakawa Shoji Co., Ltd., product name: FirebrakeZB)

[0085] (foaming agent) Hydrofluoroolefin (HFO), trans-1-chloro-3,3,3-trifluoropropene (Honeywell Japan, product name: Soltis LBA) ·water

[0086] (catalyst) Trimerization catalyst 1: Metal catalyst, potassium 2-ethylhexanoate (manufactured by Air Products, product name: DABCO (registered trademark) K-15) concentration 70 to 80% by mass Trimerization catalyst 2: quaternary ammonium salt, 2,2-dimethylpropanoic acid tetramethylammonium salt (Air Products, product name: DABCO (registered trademark) TMR7) concentration: 45 to 55% by mass Resinification catalyst 1: Metal catalyst, bismuth trioctate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600), concentration 55-58% by mass Resinification catalyst 2: Amine catalyst, 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-DM70) concentration 65 to 75% by mass

[0087] (Anti-settling agent) Fumed silica (manufactured by Nippon Aerosil Co., Ltd., product name: Aerosil R976S)

[0088] (filler) ·Barium sulfate 1 (chemically synthesized product, average particle size: 0.6 μm, manufactured by Shaanxi Fuhua Chemical Co., Ltd., product name: DC-0.6) Calcium carbonate 1 (ground product, average particle size: 1.5 μm, manufactured by Kalfin Co., Ltd., product name: KS-1300) Calcium carbonate 2 (ground product, average particle size: 30 μm, manufactured by Kalfin Co., Ltd., product name: KS-500) Barium sulfate 2 (ground product, manufactured by Takehara Chemical Industry Co., Ltd., average particle size: 1.5 μm, product name: W-1) Wollastonite (pulverized product, manufactured by Kinseimatec, average particle size: 30 μm, product name: SH-1250)

[0089] [Measurement and evaluation methods for each physical property] <Flame retardancy> For each of the Examples and Comparative Examples, polyurethane foams were produced using the polyol composition and polyisocyanate according to the formulations shown in Table 1. The production conditions were as follows: <Production conditions> Spraying machine: Graco H-25 spraying machine Settings (heater settings) Isocyanate heater: 38℃ Premix heater (for heating polyol composition): 38°C Hose heater (for heating polyisocyanate and polyol compositions before mixing): 38°C Base material: gypsum board Base material temperature (temperature of the surface to be sprayed): 20°C ± 1°C

[0090] From the polyurethane foam prepared as described above, a sample measuring 10 cm long, 10 cm wide, and 3.5 cm thick was cut out so as to include the gypsum board. Therefore, part of the cut sample was the gypsum board, and of the 3.5 cm thickness, the thickness of the gypsum board was 1.25 cm and the thickness of the polyurethane foam was 2.25 cm. The cone calorimeter test sample obtained as described above was subjected to a radiant heat intensity of 50 kW / m in accordance with the ISO-5660 test method. 2 Total calorific value (MJ / m) when heated for 10 minutes 2 ) was measured, and the flame retardancy was evaluated based on the following evaluation criteria. 〇: Total heat output for 10 minutes is 8MJ / m 2 It was as follows. ×: Total heat generation for 10 minutes is 8MJ / m 2 It was super.

[0091] <Viscosity> In each Example and Comparative Example, 300 mL of a polyol composition prepared according to the formulation in Table 1 was placed in a 300 mL polypropylene cup, the liquid temperature of the polyol composition was adjusted to 25°C, and the viscosity was measured using a Brookfield DV2T viscometer. The viscosity was measured using a spindle LV-03 at a rotation speed of 60 rpm. The viscosity was then evaluated based on the following evaluation criteria. ○: Viscosity is 1300 mPa·s or less ×: Viscosity over 1300 mPa·s

[0092] <Caking> For each example and comparative example, a polyol composition was prepared by mixing the components shown in Table 1. 400 g of the polyol composition was placed in a 500 ml plastic airtight container and sealed, and then a load of 4000 minutes was applied to the polyol composition (hereinafter also referred to as "sample") in the sealed container at a rotation speed of 310 rpm in a centrifuge. Thereafter, the sample was removed from the centrifuge, and a spoon was gently lowered onto the sample. If the spoon reached the bottom of the sealed container under its own weight without applying force, it was evaluated as "◎", if it reached the bottom of the sealed container with force applied, it was evaluated as "◯", and if it hit a hard layer midway and did not reach the bottom of the sealed container even with force applied, it was evaluated as "×". Note that in Comparative Example 1, since neither filler nor solid flame retardant was contained, caking did not occur in the first place and caking evaluation was not performed, so the evaluation result was "-".

[0093] <Verdict> The physical properties of the polyol composition and the polyurethane foam were evaluated based on the following evaluation criteria. Good: The evaluation results for flame retardancy, viscosity, and caking were all "good" or better. ×: The evaluation result was "×" in one or more of flame retardancy, viscosity, and caking.

[0094] [Table 1]

[0095] As is clear from the above examples, polyol compositions satisfying the requirements of the present invention had low viscosity and suppressed caking. Furthermore, polyurethane foams formed from the compositions had excellent flame retardancy. In contrast, the polyol compositions prepared in Comparative Examples 1 to 4 did not contain a crushed mineral filler and therefore were unable to suppress caking. Furthermore, the polyol composition prepared in Comparative Example 4 had too high a viscosity, resulting in poor handling.

Claims

1. 1. A polyol composition for reaction with a polyisocyanate to obtain a polyurethane foam, comprising: A polyol composition comprising a polyol, a catalyst, a blowing agent, a flame retardant, and a ground mineral filler.

2. 2. The polyol composition according to claim 1, wherein the crushed mineral filler comprises at least one selected from calcium carbonate, barium sulfate, silica, silicon-based compounds other than silica, talc, mica, clay, wollastonite, apatite, and acicular alumina.

3. The polyol composition according to claim 1 or 2, wherein the filler obtained by crushing a mineral has an average particle size of 50 μm or less.

4. The polyol composition according to claim 1 or 2, wherein the content of the crushed mineral filler is 3 parts by mass or more relative to 100 parts by mass of the polyol.

5. The polyol composition according to claim 1 or 2, wherein the viscosity of the polyol composition is 1300 mPa·s or less.

6. The polyol composition according to claim 1 or 2, wherein the catalyst comprises an organic acid bismuth salt.

7. The polyol composition according to claim 1 or 2, wherein the catalyst comprises a heterocyclic compound having a nitrogen atom.

8. The polyol composition of claim 1 or 2, wherein the catalyst comprises a quaternary ammonium salt.

9. The polyol composition of claim 1 or 2, wherein the catalyst comprises a potassium salt.

10. The polyol composition of claim 1 or 2, wherein the flame retardant comprises a solid phosphorus-based compound.

11. A flame-retardant urethane resin composition comprising the polyol composition according to claim 1 or 2 and a polyisocyanate.

12. The flame-retardant urethane resin composition according to claim 11, wherein the flame-retardant urethane resin composition has an isocyanate index of 250 or more.

13. A polyurethane foam formed by foaming the flame-retardant urethane resin composition according to claim 11.

14. The polyurethane foam according to claim 13, which is formed by spray foaming the flame-retardant urethane resin composition.

Images