Polyol composition and urethane resin composition

Abstract

To provide a polyol composition that can form polyurethane foam less prone to increased density at low temperatures and having high dimensional stability.SOLUTION: A polyol composition contains a polyol, a filler, a foamer, a resinification catalyst and a trimerization catalyst, where the content of the foamer is 35-60 pts.mass relative to the polyol 100 pts.mass.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyol composition and a urethane resin composition for forming a polyurethane foam.

Background Art

[0002] Conventionally, polyurethane foams have been used as heat insulating materials in vehicles such as automobiles and furniture. Generally, a polyurethane foam is formed by discharging and mixing a polyol composition and a polyisocyanate composition filled in separate containers.

[0003] A polyurethane foam is generally formed by foaming with a foaming agent contained in a polyol composition. As the foaming agent, water, hydrofluoroolefin, etc. are generally used However, various foaming agents have been studied from the viewpoint of improving the physical properties of the polyurethane foam. For example, in Patent Documents 1 to 4, at the production site of a polyurethane foam, a method of producing a polyurethane foam by adding a certain amount of carbon dioxide (supercritical, subcritical or liquid carbon dioxide) as a foaming agent to at least one of a polyol composition and a polyisocyanate composition is disclosed. According to this method, it is described that a polyurethane foam having flame retardancy and uniform density distribution can be produced.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

[0005] In the above-described conventional method, a spraying foaming method is mainly used in which a polyol composition and a polyisocyanate composition are sprayed onto an adherend by a spray gun or the like, and foamed and cured to form a polyurethane foam. The polyurethane foam formed by the spraying foaming method has an environment in use that is substantially equal to the outside air temperature, and its density changes under the influence of the outside air temperature. For example, when the temperature is low, the growth of cells is inhibited, so the density of the polyurethane foam increases. At extremely low temperatures, the curing rate slows down, so the blowing agent easily escapes as a gas, and as a result, the density tends to further increase. Thus, in the case of a low-temperature environment (for example, -5 to 10°C), a polyurethane foam with a higher density than the intended density is formed, and there is a problem that more raw materials are required when forming a polyurethane foam with a predetermined thickness.

[0006] Therefore, an object of the present invention is to provide a polyol composition capable of forming a polyurethane foam that can suppress high densification in a low-temperature environment and has excellent dimensional stability, and a urethane resin composition containing the polyol composition. [Means for Solving the Problems]

[0007] As a result of intensive studies, the present inventors have found that the above problems can be solved by a polyol composition containing a polyol, a filler, a blowing agent, a resinification catalyst, and a trimerization catalyst, with the content of the blowing agent being in a specific range, and a urethane resin composition containing the polyol composition, and have completed the present invention. That is, the present invention is as follows in [1] to

[11] .

[0008] [1] A polyol composition containing a polyol, a filler, a blowing agent, a resinification catalyst, and a trimerization catalyst, wherein the content of the blowing agent is 35 to 60 parts by mass with respect to 100 parts by mass of the polyol. [2] The polyol composition according to [1] above, wherein the blowing agent is at least one selected from the group consisting of water and hydrofluoroolefin. [3] A urethane resin composition containing the polyol composition according to [1] or [2] above and a polyisocyanate composition containing a polyisocyanate. [4] The urethane resin composition according to [3] above, wherein the core density of the formed polyurethane foam is 25 to 45 kg / m 3 3. [5] The urethane resin composition according to [3] or [4] above, containing critical, subcritical or liquid carbon dioxide. [6] The urethane resin composition according to any one of [3] to [5] above, wherein the resinification catalyst contains at least one metal-based resinification catalyst selected from the group consisting of bismuth-based catalysts and tin-based catalysts. [7] The urethane resin composition according to [6] above, wherein the content of the metal-based resinification catalyst is 0.1 to 12 parts by mass with respect to 100 parts by mass of the polyol. [8] The urethane resin composition according to any one of [3] to [7] above, wherein the trimerization catalyst contains a quaternary ammonium salt. [9] The urethane resin composition according to any one of [3] to [8] above, wherein the trimerization catalyst contains a quaternary ammonium salt and an alkali metal carboxylate, and the weight ratio (quaternary ammonium salt / alkali metal carboxylate) is 1 / 1 to 6 / 1.

[10] The urethane resin composition according to any one of [3] to [9] above, wherein the content of the trimerization catalyst is 1 to 30 parts by mass with respect to 100 parts by mass of the polyol.

[11] A method for producing a polyurethane foam by foaming and curing the urethane resin composition according to any one of [3] to

[10] above, having a step of adding critical, subcritical or liquid carbon dioxide to at least one of the polyol composition and the polyisocyanate composition, wherein the addition amount of the carbon dioxide is 0.1 to 4 parts by mass with respect to 100 parts by mass of the polyol, and the reaction proceeds after the addition of the carbon dioxide. A method for producing a polyurethane foam. [Advantages of the Invention]

[0009] According to the present invention, it is possible to provide a polyol composition capable of suppressing densification in a low-temperature environment and forming a polyurethane foam excellent in dimensional stability, and a urethane resin composition containing the polyol composition.

Mode for Carrying Out the Invention

[0010] The polyol composition of the present invention is a polyol composition containing a polyol, a filler, a blowing agent, a resinification catalyst, and a trimerization catalyst, wherein the content of the blowing agent is 35 to 60 parts by mass with respect to 100 parts by mass of the polyol. Hereinafter, the present invention will be described in detail.

[0011] [Polyol Composition] The polyol composition of the present invention contains a polyol, a filler, a blowing agent, a resinification catalyst, and a trimerization catalyst.

[0012] [Blowing Agent] The polyol composition contains a blowing agent. The content of the blowing agent is 35 to 60 parts by mass with respect to 100 parts by mass of the polyol. When the content of the blowing agent is less than 35 parts by mass, the foamability decreases, and a polyurethane foam having a high density is formed in a low-temperature environment. On the other hand, when the content of the blowing agent exceeds 60 parts by mass, the dimensional stability of the formed polyurethane foam decreases, and problems such as dropping off from the adherend are likely to occur. From such a viewpoint, the content of the blowing agent with respect to 100 parts by mass of the polyol is preferably 38 to 55 parts by mass, more preferably 40 to 50 parts by mass.

[0013] The blowing agent is not particularly limited, but preferably includes, for example, water, hydrocarbon compounds, chlorinated aliphatic hydrocarbon compounds, hydrofluorocarbons, hydrochlorofluorocarbon compounds, hydrofluoroolefins, etc. Among them, from the viewpoints of good foam formation and reduction of environmental load, the blowing agent is preferably at least one selected from the group consisting of water and hydrofluoroolefins. By containing hydrofluoroolefins, when using the fillers described later, the dispersibility of the fillers in the foam becomes good. Also, from the viewpoint of improving foamability, the blowing agent preferably contains water, and more preferably contains both water and hydrofluoroolefins.

[0014] Examples of the hydrofluoroolefins contained in the blowing agent include fluoroalkenes having 3 to 6 carbon atoms. Further, the hydrofluoroolefin may be a hydrochlorofluoroolefin having a chlorine atom, and thus may be a chlorofluoroalkene having 3 to 6 carbon atoms. The hydrofluoroolefin preferably has 3 or 4 carbon atoms.

[0015] The hydrofluoroolefin used as the blowing agent preferably has a boiling point exceeding 0°C at 1 atm. Examples thereof include (E)-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)), (Z)-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(Z)), (Z)-1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz(Z)), (E)-1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz(E)), (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HFO-1224yd(Z)), etc.

[0016] The content of the hydrofluoroolefin used as the blowing agent is preferably 35 to 55 parts by mass, more preferably 38 to 53 parts by mass, and even more preferably 40 to 50 parts by mass with respect to 100 parts by mass of the polyol, from the viewpoint of suppressing the densification of the polyurethane foam under low-temperature environments and improving the dimensional stability.

[0017] The content of water used as the blowing agent is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the polyol, from the viewpoint of making the density of the polyurethane foam within a desired range.

[0018] <Catalyst> The polyol composition contains a resinification catalyst and a trimerization catalyst. The resinification catalyst is a catalyst that promotes the reaction between the polyol and the polyisocyanate, and the trimerization catalyst is a catalyst that reacts with the isocyanate groups contained in the polyisocyanate to trimerize them and promotes the formation of the isocyanurate ring.

[0019] (Resinification catalyst) Examples of the resinification catalyst include metal-based resinification catalysts and amine-based resinification catalysts. Among them, from the viewpoint of suppressing the densification of the formed polyurethane foam under low-temperature environments, the resinification catalyst preferably contains at least one metal-based resinification catalyst selected from the group consisting of bismuth-based catalysts and tin-based catalysts, and more preferably contains a metal-based resinification catalyst composed of a bismuth-based catalyst.

[0020] The bismuth-based catalyst is preferably a bismuth salt of a carboxylic acid having 5 or more carbon atoms. More specifically, the bismuth-based catalyst is preferably a bismuth salt of a carboxylic acid such as bismuth octylate such as bismuth 2-ethylhexanoate, bismuth neodecanoate, bismuth naphthenate, etc., and among them, bismuth 2-ethylhexanoate is more preferable. As the tin-based catalyst, a tin salt of a carboxylic acid having 5 or more carbon atoms is preferable. More specifically, as the tin-based catalyst, tin acetate, tin 2-ethylhexanoate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dineodecanoate, dioctyltin dineodecanoate, dioctyltin dilaurate, etc. are preferable, and among them, dioctyltin dineodecanoate is more preferable.

[0021] The content of the metal-based resinification catalyst is preferably 0.1 to 12 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 2 to 8 parts by mass with respect to 100 parts by mass of the polyol.

[0022] Examples of the amine-based resinification catalyst include imidazole compounds, pentamethyldiethylenetriamine, triethylamine, N-methylmorpholine bis(2-dimethylaminoethyl) ether, bis(2-dimethylaminoethyl) ether, N,N,N’,N”,N”-pentamethyldiethylenetriamine, N,N,N’-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl) ether, N-methyl-N’,N’-dimethylaminoethylpiperazine, N,N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylethylenediamine, tetramethylhexamethylenediamine, trimethylaminoethylpiperazine, tripropylamine, and their acid-blocked forms, etc. Among the amine-based resinification catalysts, imidazole compounds are preferable from the viewpoints of catalyst activity, etc.

[0023] The imidazole compound is a compound having an imidazole skeleton, and is preferably an imidazole derivative in which at least one of the 1-position and 2-position of imidazole is substituted with an alkyl group having 8 or less carbon atoms or an alkenyl group having 8 or less carbon atoms. The imidazole compound is more preferably a compound in which at least one of the 1-position and the 2-position is substituted with an alkyl group, and still more preferably a compound in which both the 1-position and the 2-position are substituted with alkyl groups (1,2-dialkylimidazole). The alkyl groups substituting the 1-position and the 2-position may be the same or different. Further, the number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 1 to 4. Preferable specific examples of the imidazole compound include 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. Among them, from the viewpoints of improving the activity of the catalyst in the presence of hydrofluoroolefin and allowing the reaction to proceed rapidly, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferable. Further, from the viewpoint of further enhancing the storage stability, 1,2-dimethylimidazole is more preferable. The amine-based resinification catalyst may be used alone or in combination of two or more.

[0024] The content of the resinification catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 1 to 12 parts by mass with respect to 100 parts by mass of the polyol.

[0025] (Trimerization catalyst) Examples of the trimerization catalyst include alkali metal carboxylates, tertiary ammonium salts, quaternary ammonium salts, and nitrogen-containing aromatic compounds. Among them, from the viewpoint of suppressing the densification of the formed polyurethane foam in a low-temperature environment, it is preferable that the trimerization catalyst contains a quaternary ammonium salt, and it is more preferable that the trimerization catalyst contains a quaternary ammonium salt and an alkali metal carboxylate.

[0026] When the quaternary ammonium salt is used together with the critical, subcritical or liquid carbon dioxide described below, the foamability becomes particularly good, and it is easy to suppress the densification in a low-temperature environment. In addition, by using a quaternary ammonium salt and an alkali metal carboxylate in combination, the foamability is further improved by two-stage foaming or the like, and it becomes easier to suppress densification in a low-temperature environment.

[0027] The weight ratio of the quaternary ammonium salt to the alkali metal carboxylate (quaternary ammonium salt / alkali metal carboxylate) is preferably 1 / 1 to 6 / 1, more preferably 1.2 / 1 to 5 / 1, and even more preferably 1.5 / 1 to 3 / 1. When the weight ratio is at least the lower limit value, the foamability is improved and it becomes easier to suppress densification in a low-temperature environment. On the other hand, when the weight ratio is at most the upper limit value, the workability by spraying is improved.

[0028] The content of the quaternary ammonium salt is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the polyol. The content of the alkali metal carboxylate is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyol.

[0029] Examples of the alkali metal carboxylate include potassium 2-ethylhexanoate, potassium acetate, and the like. Examples of the quaternary ammonium salt include tetramethylammonium salt, tetraethylammonium salt, tetraphenylammonium salt, triethylmonomethylammonium salt, quaternary ammonium carboxylate, and the like. Preferable specific examples of the carboxylic acid in the quaternary ammonium carboxylate are at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. Examples of the tertiary ammonium salt include trimethylammonium salt, triethylammonium salt, triphenylammonium salt, and the like. Examples of nitrogen-containing aromatic compounds include tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine, and the like.

[0030] The content of the trimerization catalyst is preferably 0.2 to 35 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the polyol.

[0031] <Polyol> Examples of the polyol contained in the polyol composition include polycaprolactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, polyester polyol, polymer polyol, and polyether polyol.

[0032] Examples of the polycaprolactone polyol include polypropionolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Examples of the polycarbonate polyol include polyols obtained by a dealcoholization reaction of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, and the like.

[0033] Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolak, and cresol novolak. Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophorone diol, dicyclohexylmethane diol, and dimethyldicyclohexylmethane diol.

[0034] Examples of the polyester polyol include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, and condensates of hydroxycarboxylic acids and the polyhydric alcohols. Examples of the polybasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), and succinic acid. Examples of the polyhydric alcohols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, and neopentyl glycol. Examples of the hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

[0035] Examples of the polymer polyol include polymers obtained by graft polymerization of ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate to aromatic polyols, alicyclic polyols, aliphatic polyols, and polyester polyols, polybutadiene polyol, or hydrogenated products thereof.

[0036] Examples of the polyether polyol include polymers obtained by ring-opening polymerization of at least one alkylene oxide such as ethylene oxide, propylene oxide, and tetrahydrofuran in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogens. Examples of the low molecular weight active hydrogen compounds having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol, triols such as glycerin and trimethylolpropane, and amines such as ethylenediamine and butylenediamine.

[0037] As the polyol used in the present invention, it preferably contains at least one selected from polyester polyols and polyether polyols, and preferably contains at least a polyester polyol. Among them, it is more preferable to contain a polyester polyol obtained by dehydration condensation of a polybasic acid having an aromatic ring such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid), and a dihydric alcohol such as bisphenol A, ethylene glycol, and 1,2-propylene glycol. The content of the polyester polyol in 100 parts by mass of the polyol is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, and still more preferably 90 parts by mass or more.

[0038] The hydroxyl value of the polyol is preferably 20 to 300 mgKOH / g, more preferably 30 to 275 mgKOH / g, and still more preferably 50 to 250 mgKOH / g. When the hydroxyl value of the polyol is below the upper limit value, the viscosity of the polyol liquid agent does not become excessively large, which is preferable from the viewpoint of handleability and the like. On the other hand, when the hydroxyl value of the polyol is above the lower limit value, the crosslinking density of the polyurethane foam increases, resulting in higher strength. The hydroxyl value of the polyol can be measured according to JIS K 1557-1:2007.

[0039] <Filler> The polyol composition contains a filler. By containing a filler, a function according to the type of the filler can be imparted to the polyurethane foam. The filler preferably contains a flame retardant. By using a flame retardant as the filler, high flame retardant performance can be imparted to the polyurethane foam. The flame retardant used as the filler is preferably a solid flame retardant. By using a solid flame retardant, the flame retardancy can be enhanced more effectively. The solid flame retardant is a flame retardant that becomes solid at normal temperature (23°C) and normal pressure (1 atm). Examples of the solid flame retardant include a phosphorus-based flame retardant, a boron-containing flame retardant, a bromine-containing flame retardant, a phosphate-containing flame retardant, a chlorine-containing flame retardant, an antimony-containing flame retardant, a metal hydroxide, an acicular filler, a carbonate-based flame retardant, carbon black, and the like.

[0040] (Red phosphorus-based flame retardant) The red phosphorus-based flame retardant may be composed of red phosphorus alone, or may be one in which red phosphorus is coated with a resin, a metal hydroxide, a metal oxide, etc., or one in which red phosphorus is mixed with a resin, a metal hydroxide, a metal oxide, etc. The resin for coating or mixing with red phosphorus is not particularly limited, but examples thereof include thermosetting resins such as a phenol resin, an epoxy resin, an unsaturated polyester resin, a melamine resin, a urea resin, an aniline resin, and a silicone resin. From the viewpoint of flame retardancy, a metal hydroxide is preferable as the compound for coating or mixing. As the metal hydroxide, those described later may be appropriately selected and used.

[0041] (Boron-containing flame retardant) Examples of the boron-containing flame retardant include borax, boron oxide, boric acid, borate, etc. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, tetraboron pentoxide, etc. Examples of borate include borates of alkali metals, alkaline earth metals, elements of Group 4, Group 12, 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, etc. The boron-containing flame retardant may be used alone or in combination of two or more. The boron-containing flame retardant is preferably a borate, and more preferably zinc borate.

[0042] (Bromine-containing flame retardant) The bromine-containing flame retardant is not particularly limited as long as it contains bromine in its molecular structure and is a solid at normal temperature and pressure. Examples thereof include aromatic compounds containing brominated aromatic rings. Examples of the aromatic compound containing a brominated aromatic ring 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.

[0043] The aromatic compound containing a brominated aromatic ring may also be a bromine compound polymer. Specifically, brominated polycarbonates such as polycarbonate oligomers produced from brominated bisphenol A, copolymers of this polycarbonate oligomer and bisphenol A, diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin, etc. are included. Further, 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), crosslinked brominated polystyrene, etc., crosslinked or non-crosslinked brominated poly(-methylstyrene), etc. are included. Compounds other than aromatic compounds containing brominated aromatic rings such as hexabromocyclododecane may also be used. These bromine-containing flame retardants may be used alone or in combination of two or more. Among them, aromatic compounds containing brominated aromatic rings are preferred, and monomeric organic bromine compounds such as ethylene bis(pentabromophenyl) are particularly preferred.

[0044] (Phosphate-containing flame retardant) Examples of the phosphate-containing flame retardants include phosphates composed of salts of various phosphoric acids and at least one metal or compound selected from metals in Groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. The phosphoric acid is not particularly limited, and examples thereof include monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid. Examples of the 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 amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and piperazine. Examples of the aromatic amines include aniline, o-toluidine, 2,4,6-trimethylaniline, anisidine, and 3-(trifluoromethyl)aniline. Examples of the heterocyclic compounds containing nitrogen in the ring include pyridine, triazine, and melamine.

[0045] Specific examples of the phosphate-containing flame retardants include, for example, monophosphates such as aluminum orthophosphate, pyrophosphates, and polyphosphates. Here, the polyphosphates are not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate. One or more of the above-mentioned phosphate-containing flame retardants can be used.

[0046] (Chlorine-containing flame retardants) Examples of the chlorine-containing flame retardants include those commonly used in flame-retardant resin compositions, such as polychlorinated naphthalene, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene sold under the trade name "Dechlorane Plus".

[0047] (Antimony-containing flame retardants) Examples of the antimony-containing flame retardants include antimony oxides, antimonates, pyroantimonates, etc. Examples of the antimony oxides include antimony trioxide, antimony pentoxide, etc. Examples of the antimonates include sodium antimonate, potassium antimonate, etc. Examples of the pyroantimonates include sodium pyroantimonate, potassium pyroantimonate, etc. The antimony-containing flame retardant may be used alone or in combination of two or more. The preferred antimony-containing flame retardant used in the present invention is antimony trioxide.

[0048] (Metal hydroxide) Examples of the metal hydroxides include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, etc. The metal hydroxides may be used alone or in combination of two or more.

[0049] (Acicular filler) Examples of the acicular fillers include potassium titanate whisker, aluminum borate whisker, magnesium-containing whisker, silicon-containing whisker, wollastonite, sepiolite, zonolite, erestadite, boehmite, rod-shaped hydroxyapatite, glass fiber, carbon fiber, graphite fiber, metal fiber, slag fiber, gypsum fiber, silica fiber, alumina fiber, silica alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, stainless steel fiber, etc. One or more of these acicular fillers can be used.

[0050] The aspect ratio (length / diameter) of the acicular filler used in the present invention preferably ranges from 5 to 50, and more preferably ranges from 10 to 40. The aspect ratio can be determined by observing the acicular filler with a scanning electron microscope and measuring its length and width.

[0051] (Carbonate-based flame retardant) Examples of the carbonate-based flame retardant include calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, etc., and among them, calcium carbonate is preferred.

[0052] The blending amount of the solid flame retardant is not particularly limited, but for example, it is 10 to 200 parts by mass, preferably 20 to 150 parts by mass, and more preferably 40 to 120 parts by mass with respect to 100 parts by mass of the polyol. By setting the blending amount of the solid flame retardant to be not less than these lower limit values, appropriate flame retardancy can be imparted to the polyurethane foam. By setting the blending amount of the solid flame retardant to be not more than these upper limit values, it becomes easier to obtain a polyurethane foam with a small density difference depending on the location.

[0053] As the filler, an inorganic filler other than the above-mentioned flame retardant may be blended. As the inorganic filler, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, ferrites, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, mica, montmorillonite, bentonite, activated clay, imogolite, sericite, glass beads, aluminum nitride, boron nitride, silicon nitride, various metal powders, magnesium sulfate, lead zirconate titanate, molybdenum disulfide, silicon carbide, various magnetic powders, fly ash, etc. can be appropriately used. The inorganic filler may be used alone or in combination of two or more.

[0054] The content of the filler in the polyol composition is, for example, 10 to 300 parts by mass, preferably 20 to 150 parts by mass, and more preferably 40 to 120 parts by mass with respect to 100 parts by mass of the polyol. By setting the blending amount of the filler to be not less than these lower limit values, it becomes easier to impart a function corresponding to the type of filler to the polyurethane foam. By setting the blending amount of the filler to be not more than these upper limit values, it becomes easier to obtain a polyurethane foam with a small density difference depending on the location.

[0055] (Liquid flame retardant) The polyol composition may contain a liquid flame retardant. A liquid flame retardant is a flame retardant that is liquid at normal temperature (23°C) and normal pressure (1 atm). Specific examples of the liquid flame retardant include phosphate esters. Unlike solid flame retardants, liquid flame retardants are less likely to form precipitates during storage and are excellent in handleability.

[0056] As the phosphate ester, it is preferable to use a monophosphate ester, a condensed phosphate ester, etc. Examples of the monophosphate ester include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, 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, diphenyl(2-ethylhexyl) phosphate; acidic phosphate esters such as monoisodecyl phosphate, diisodecyl phosphate, etc.

[0057] Examples of the condensed phosphate ester include aromatic condensed phosphate esters such as trialkyl polyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, bisphenol A polyphenyl phosphate. Examples of commercially available products of the condensed phosphate ester include "CR-733S", "CR-741", "CR747" manufactured by Daihachi Chemical Industry Co., Ltd., "ADEKA STAB PFR", "FP-600" manufactured by ADEKA Corporation, etc.

[0058] The liquid flame retardant may be used alone or in combination of two or more. Among these, from the viewpoints of facilitating the production of the polyurethane foam and improving the flame retardancy of the polyurethane foam, the monophosphate ester is preferable, and tris(β-chloropropyl) phosphate is more preferable.

[0059] When containing a liquid flame retardant, the blending amount thereof is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, and still more preferably 20 to 60 parts by mass with respect to 100 parts by mass of the polyol.

[0060] (Blowing agent) The polyol composition may contain a blowing agent. The blowing agent improves the foamability of the urethane resin composition obtained by mixing the polyol composition and the polyisocyanate composition. Examples of the blowing agent include surfactants such as polyoxyalkylene-based blowing agents such as polyoxyalkylene alkyl ethers, and silicone-based blowing agents such as organopolysiloxanes. These blowing agents may be used alone or in combination of two or more. When using a blowing agent, the blending amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and still more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyol. When the blending amount of the blowing agent is at least these lower limit values, it becomes easier to foam the urethane resin composition and it becomes easier to obtain a homogeneous polyurethane foam. Also, when the blending amount of the blowing agent is at most these upper limit values, the balance between the production cost and the obtained effect becomes good.

[0061] (Other components) The polyol composition may contain one or more selected from antioxidants such as phenolic, amine-based, and sulfur-based antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, tackifier resins, etc., and tackifiers such as polybutene and petroleum resins, etc., as necessary within a range not impairing the object of the present invention.

[0062] [Urethane resin composition] The urethane resin composition of the present invention includes a polyol composition and a polyisocyanate composition containing a polyisocyanate. More specifically, the urethane resin composition is adjusted by mixing the polyol composition and the polyisocyanate composition, and then the polyol and the polyisocyanate react, foam, and cure to form a polyurethane foam.

[0063] (Polyisocyanate Composition) The polyisocyanate composition in the present invention contains polyisocyanate. As the polyisocyanate, known polyisocyanates used for forming polyurethane foams can be used, and examples thereof include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates. Examples of the aromatic polyisocyanate include phenylenediisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.

[0064] Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0065] Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0066] Among these, from the viewpoints of ease of use and availability, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred. The polyisocyanate may be used alone or in combination of two or more.

[0067] The polyisocyanate composition may contain the above-mentioned foaming agent, filler, etc., but preferably consists only of polyisocyanate.

[0068] (Isocyanate Index) The isocyanate index of the urethane resin composition of the present invention is not particularly limited, but is preferably from 120 to 500, more preferably from 150 to 400. When the isocyanate index is at least the above lower limit value, the amount of polyisocyanate relative to the polyol becomes excessive and an isocyanurate bond due to the trimer of the polyisocyanate is likely to be formed, resulting in improved flame retardancy of the polyurethane foam. Further, when the isocyanate index is at most the above upper limit value, the balance between the flame retardancy and the production cost of the resulting polyurethane foam becomes good.

[0069] Incidentally, the isocyanate index can be calculated by the following method. Isocyanate index = Equivalent number of polyisocyanate ÷ (equivalent number of polyol + equivalent number of water) × 100 Here, each equivalent number can be calculated as follows. · Equivalent number of polyisocyanate = Amount of polyisocyanate used (g) × NCO content (mass%) / Molecular weight of NCO (mol) × 100 · Equivalent number of polyol = OHV × Amount of polyol used (g) ÷ Molecular weight of KOH (mmol) OHV is the hydroxyl value (mgKOH / g) of the polyol. · Equivalent number of water = Amount of water used (g) / Molecular weight of water (mol) × Number of OH groups of water In the above formulas, the molecular weight of NCO is 42 (mol), the molecular weight of KOH is 56100 (mmol), the molecular weight of water is 18 (mol), and the number of OH groups of water is 2.

[0070] (Carbon dioxide) The urethane resin composition of the present invention preferably contains critical, subcritical or liquid carbon dioxide. By using the above-mentioned predetermined amount of foaming agent and the carbon dioxide in combination, foaming can be effectively promoted and the densification of the polyurethane foam in a low temperature environment can be suppressed. Supercritical, subcritical, or liquid carbon dioxide is carbon dioxide gas that has been brought into a supercritical state, subcritical state, or liquid state by pressurizing it at a predetermined temperature. Specifically, supercritical carbon dioxide is carbon dioxide in a fluid state where both the pressure and temperature exceed the critical point, which is the critical pressure and critical temperature or higher. Subcritical carbon dioxide refers to carbon dioxide in a liquid state where the pressure is at or above the critical pressure and the temperature is below the critical temperature, carbon dioxide in a liquid state where the pressure is below the critical pressure and the temperature is at or above the critical temperature, or carbon dioxide in a state where the temperature and pressure are below the critical point but close to it. Furthermore, liquid carbon dioxide is liquefied under temperature and pressure conditions above the triple point.

[0071] From the perspective of suppressing the high density of the polyurethane foam at low temperatures, the content of supercritical, subcritical, or liquid carbon dioxide in the urethane resin composition is preferably 0.1 to 4 parts by mass, more preferably 0.2 to 3 parts by mass, and even more preferably 0.3 to 2 parts by mass with respect to 100 parts by mass of the polyol.

[0072] Details will be described later, but supercritical, subcritical, or liquid carbon dioxide is added to at least one of the polyol composition and the polyisocyanate composition during the production of the polyurethane foam. After or simultaneously with the addition of the carbon dioxide, the polyol composition and the polyisocyanate composition are mixed, and the reaction between the polyol and the polyisocyanate proceeds, causing foaming and curing to form the polyurethane foam. Carbon dioxide may be added alone or as a mixture of carbon dioxide and a blowing agent, preferably as a mixture of carbon dioxide and a hydrofluoroolefin.

[0073] (Density) By foaming and curing the urethane resin composition, a polyurethane foam is formed. From the perspectives of achieving a low density and good dimensional stability, the core density of the formed polyurethane foam is preferably 25 to 45 kg / m 3and more preferably 33 to 40 kg / m 3 and even more preferably 33 to 36 kg / m 3 is. The urethane resin composition of the present invention is preferably a urethane resin composition in which the core density of the formed polyurethane foam is within the above range. The density of the polyurethane foam body can be measured in accordance with JIS K7222. In the present specification, the core density of the polyurethane foam means the density of the polyurethane foam without the skin layer. Specifically, it means the density of the internal polyurethane foam obtained by removing the 5 mm portion of the surface layer from the formed polyurethane foam.

[0074] [Method for Producing Polyurethane Foam] The method for producing a polyurethane foam in the present invention is a method for producing a polyurethane foam by foaming and curing the above-described urethane resin composition. Further, in this production method, it is preferable to have a step of adding critical, subcritical or liquid carbon dioxide to at least one of the polyol composition and the polyisocyanate composition. The addition amount of the carbon dioxide is preferably 0.1 to 4 parts by mass with respect to 100 parts by mass of the polyol, and the reaction proceeds after the addition of the carbon dioxide.

[0075] (Step of Adding Carbon Dioxide) Critical, subcritical or liquid carbon dioxide is preferably added to at least one of the polyol composition and the polyisocyanate composition before or simultaneously with the mixing of the polyol composition and the polyisocyanate composition. Considering the ease of foam formation, etc., it is preferably added to the polyol composition. When adding carbon dioxide simultaneously with the mixing of the polyol composition and the polyisocyanate composition, it is preferable that critical, subcritical or liquid carbon dioxide is supplied to the position where both compositions are mixed.

[0076] More specifically, in the manufacturing method of the present invention, at the manufacturing site for producing polyurethane foam, a flow path for supplying a polyol composition and a flow path for supplying a polyisocyanate are provided separately, and a flow path for supplying critical, subcritical or liquid carbon dioxide is provided, and it is preferable to produce polyurethane foam. In this way, by adding critical, subcritical or liquid carbon dioxide in a separate system from both compositions at the manufacturing site to produce polyurethane foam, the miscibility between the polyol composition and the polyisocyanate composition is improved, the density and the like tend to be uniform, and a polyurethane foam having excellent physical properties is formed.

[0077] When adding supercritical, subcritical or liquid carbon dioxide, it may be added as the carbon dioxide alone, or as a mixture of the carbon dioxide and a foaming agent, preferably as a mixture of the carbon dioxide and a hydrofluoroolefin. The mass ratio of the carbon dioxide to the foaming agent (carbon dioxide / hydrofluoroolefin) in the mixture is, from the viewpoint of enhancing the miscibility of the composition, for example, 0.05 to 5, preferably 0.1 to 2, and more preferably 0.2 to 1.

[0078] The addition amount of supercritical, subcritical or liquid carbon dioxide is preferably 0.1 to 4 parts by mass, more preferably 0.2 to 3 parts by mass, and still more preferably 0.3 to 2 parts by mass with respect to 100 parts by mass of the polyol. When the addition amount of carbon dioxide is within the above range, it is easy to suppress the increase in density of the polyurethane foam at low temperature.

[0079] After adding supercritical, subcritical or liquid carbon dioxide to at least one of the polyol composition and the polyisocyanate composition, or simultaneously with the addition, the polyol composition and the polyisocyanate composition are mixed to prepare a urethane resin composition. Thereafter, the polyol and the polyisocyanate react, and foam and cure to form a polyurethane foam.

[0080] In the present invention, when mixing a polyol composition and a polyisocyanate composition and foaming and curing them, various known production methods of polyurethane foams can be applied. For example, various methods such as coating, injection, spraying, etc. can be applied. Specifically, there are methods of applying a urethane resin composition obtained by mixing a polyol composition and a polyisocyanate composition to an adherend and foaming and curing it, a method of injecting the urethane resin composition into a structure having a cavity and foaming and curing it, a method of spraying the urethane resin composition onto an adherend, etc. In the present invention, since the densification of the formed polyurethane foam under a low-temperature environment can be suppressed, even if the adherend is at a low temperature, a desired polyurethane foam can be formed by spraying. For spraying, it is preferable to use a spraying device equipped with a carbon dioxide supply device. Specifically, the temperature of the polyol composition and the polyisocyanate composition contained in separate containers is adjusted in the spraying device, and after supplying critical, subcritical or liquid carbon dioxide to either composition by the carbon dioxide supply device, the two compositions are collided and mixed at the tip of a spray gun, and the mixed liquid is atomized by air pressure to carry out the spraying.

Examples

[0081] The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. The components used in the examples and comparative examples are shown below.

[0082] <Polyol> (A-1) Polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RFK-505, hydroxyl value = 250 mgKOH / g)

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

[0084] <Filler> (C-1) Ammonium polyphosphate (manufactured by Clariant Chemicals, product name: Exolit AP422) (C-2) Melamine polyphosphate (manufactured by Nissan Chemical Industries, product name: PHOSMEL-200) (C-3) Silicon acicular filler (manufactured by Kinsai Matric, product name: SH1250) (C-4) Zinc borate (manufactured by Hayakawa Trading Co., product name: Firebrake ZB) (C-5) Calcium carbonate (manufactured by Bihoku Powder Chemical Industry Co., product name: BF300) (C-6) Carbon black (manufactured by Tokai Carbon Co., product name: Thermax) (C-7) Ethylene bis(pentabromophenyl) (manufactured by Albemarle, product name: SAYTEX 8010) (C-8) Red phosphorus (manufactured by Phosphorus Chemical Industry Co., product name: Nova Excel 140)

[0085] <Blowing agent> (D-1) trans-1-Chloro-3,3,3-trifluoropropene (HFO-1233zd(E)) (manufactured by Honeywell, product name: Solstice LBA) (D-2) (Z)-1,1,1,4,4,4-Hexafluorobut-2-ene (HFO-1336mzz(Z)) (manufactured by Chemours, product name: Opteon 1100) (D-3) (Z)-1-Chloro-2,3,3,3,-tetrafluoropropene (HFO‐1224yd(Z)) (manufactured by Asahi Glass Co., product name: AMOLEA 1224yd) (D-4) Ion-exchanged water

[0086] <Carbon dioxide> (D-5) Liquid carbon dioxide (D-6) Mixture of liquid carbon dioxide and HFO-1234ze, manufactured by Tokyo Koki Yamazaki Co., liquid CO 2 :HFO-1234ze = 3:7 (weight ratio)

[0087] <Trimerization catalyst> (E-1) Quaternary ammonium salt Hydroxybutyltrimethylammonium 2-ethylhexanoate (manufactured by Kao Corporation, product name: Kao Resizer No. 420) at a concentration of approximately 100% by mass (E-2) Alkali metal carboxylate Potassium 2-ethylhexanoate (manufactured by Evonik Corporation, product name: DABCO K-15) at a concentration of approximately 74%

[0088] <Resinification catalyst> (F-1) Amine-based resinification catalyst 1,2-Dimethylimidazole (manufactured by Kao Corporation, product name: Kao Resizer No. 390) at a concentration of 65 - 75% by mass (F-2) Bismuth-based catalyst Bismuth 2-ethylhexanoate (manufactured by Nitto Kasei Co., Ltd., product name: Bi28), at a concentration of 81 - 90% by mass (F-3) Tin-based catalyst Dioctyltin dineodecanoate (manufactured by Nitto Kasei Co., Ltd., product name: Neo-Stann U-830) at a concentration of approximately 99% by mass

[0089] [Examples 1 - 5, 14 - 20, Comparative Examples 1 - 2] (Foam density evaluation) The polyol, liquid flame retardant, filler, foaming agent, trimerization catalyst, and resinification catalyst of the types described in Tables 1 - 3 were mixed in the compounding amounts described in the table to prepare a polyol composition. Separately, a polyisocyanate composition consisting of diphenylmethane diisocyanate (MDI) was prepared. These compositions were introduced into a spraying machine (Graco spraying device H-25) and mixed to form a urethane resin composition, which was sprayed onto a flexible board to form a polyurethane foam. The mixing ratio of the polyol composition and the polyisocyanate composition was 1:1 by volume, and the temperature of the flexible board was (0°C). The spraying was carried out in two steps (spraying again onto the once-formed foam to form a laminated foam). The skin layer on the surface was removed from the formed polyurethane foam to expose the core layer, and a 100 mm × 100 mm × 25 mm polyurethane foam was cut out. The core density was calculated from its mass and evaluated according to the following criteria. 〇: 45 kg / m 3 Less than ×: 45 kg / m 3 above

[0090] (Dimensional stability of the foam) From the polyurethane foam obtained by spraying as described above, a test piece having a size of 100 mm × 100 mm × 25 mm, including an inner skin layer (the skin layer formed by the first spraying), was cut out. The cut test piece was left standing in an environment of -30°C for 48 hours, and then the test piece was placed on a horizontal table, and the presence or absence of warping in the test piece was visually observed and evaluated according to the following criteria. 〇: No warping was observed ×: Warping was observed

[0091] (Foaming rate) A polyol composition and a polyisocyanate composition were prepared in the same manner as in the above-mentioned "Foam density evaluation". Then, a urethane resin composition obtained by mixing the polyol composition and the polyisocyanate composition at a volume ratio of 1:1 was discharged in a flexible board shape at 0°C, and the time T from the start of foaming until it became cloudy was measured. The evaluation was made according to the following criteria based on the time T. "3" or more was regarded as passing according to the following criteria. 5: The time T is less than 4 seconds 4: The time T is 4 seconds or more and less than 8 seconds 3: The time T is 8 seconds or more and less than 12 seconds 2: The time T is 12 seconds or more and less than 16 seconds 1: The time T is 16 seconds or more

[0092] [Examples 6 to 13, Comparative Example 3] (Foam density evaluation) A polyol composition was prepared by mixing polyols, liquid flame retardants, fillers, blowing agents, trimerization catalysts, and resinification catalysts of the types described in Tables 1 to 3 in the compounding amounts shown in the tables. The polyol composition was introduced into an on-site foaming spraying device equipped with a liquefied carbon dioxide supply device (manufactured by Asahi Organic Materials Co., Ltd., product name: AYK-1000 series). In the flow path of the polyol composition, carbon dioxide of the types and compounding amounts shown in each table was supplied to and mixed with the polyol composition. The polyol composition mixed with the carbon dioxide and a polyisocyanate composition composed of polyisocyanate (MDI) were contact-mixed to form a urethane resin composition. This was sprayed onto a flexible board to form a polyurethane foam. The mixing ratio of the polyol composition and the polyisocyanate composition was 1:1 by volume, and the temperature of the flexible board was (0°C). The spraying was carried out in two steps (spraying again onto the once-formed foam to form a laminated foam). The measurement and evaluation criteria for the foam density were the same as in Example 1.

[0093] (Dimensional stability of the foam) Using the polyurethane foams prepared in the "Foam density evaluation" in Examples 6 to 13 and Comparative Example 3, the dimensional stability of the foam was evaluated by the same method and criteria as in Example 1.

[0094] (Foaming rate) For the urethane resin compositions in the "Foam density evaluation" in Examples 6 to 13 and Comparative Example 3, after discharging them in the shape of a flexible board at 0°C, the time T from the start of foaming until it became cloudy was measured. The evaluation criteria for the foaming rate were the same as in Example 1.

[0095] (Comprehensive judgment) In each example and comparative example, the comprehensive judgment was carried out according to the following criteria. 〇: Both the evaluations of the foam density and the dimensional stability are 〇. ×: At least one of the evaluations of the foam density and the dimensional stability is ×.

[0096]

Table 1

[0097]

Table 2

[0098]

Table 3

[0099] From the results of each example, it was found that the polyol composition of the present invention and the urethane resin composition containing the polyol composition can suppress densification in a low-temperature environment and can form a polyurethane foam having excellent dimensional stability. On the other hand, it was found that the polyurethane foam formed from the polyol composition of each comparative example has a high density or is inferior in dimensional stability.

Claims

1. A polyol composition comprising a polyol, a filler, a foaming agent, a resinification catalyst and a trimerization catalyst, the content of the foaming agent being 35 to 60 parts by mass per 100 parts by mass of the polyol.

2. The polyol composition according to claim 1, wherein the blowing agent is at least one selected from the group consisting of water and hydrofluoroolefins.

3. A urethane resin composition comprising the polyol composition according to claim 1 or 2 and a polyisocyanate composition containing a polyisocyanate.

4. The core density of the resulting polyurethane foam is 25 to 45 kg / m ３ The urethane resin composition according to claim 3 ,

5. The urethane resin composition according to claim 3 or 4, which contains critical, subcritical or liquid carbon dioxide.

6. The urethane resin composition according to any one of claims 3 to 5, wherein the resinification catalyst comprises at least one metal-based resinification catalyst selected from the group consisting of bismuth-based catalysts and tin-based catalysts.

7. The urethane resin composition according to claim 6, wherein the content of the metal-based resinification catalyst is 0.1 to 12 parts by mass per 100 parts by mass of the polyol.

8. The urethane resin composition according to any one of claims 3 to 7, wherein the trimerization catalyst comprises a quaternary ammonium salt.

9. The urethane resin composition according to any one of claims 3 to 8, wherein the trimerization catalyst contains a quaternary ammonium salt and an alkali metal carboxylate, and the weight ratio thereof (quaternary ammonium salt / alkali metal carboxylate) is 1 / 1 to 6 / 1.

10. The urethane resin composition according to any one of claims 3 to 9, wherein the content of the trimerization catalyst is 1 to 30 parts by mass per 100 parts by mass of the polyol.

11. A method for producing a polyurethane foam by foaming and curing the urethane resin composition according to any one of claims 3 to 10, comprising the steps of: The method includes a step of adding critical, subcritical or liquid carbon dioxide to at least one of a polyol composition and a polyisocyanate composition, the amount of carbon dioxide added being 0.1 to 4 parts by mass per 100 parts by mass of the polyol, A method for producing a polyurethane foam, wherein the reaction proceeds after the addition of carbon dioxide.

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