Polyol liquid for filling, polyurethane composition for filling, and polyurethane foam

Abstract

To provide a polyol liquid agent capable of obtaining a polyurethane foam excellent in quality capable of forming a polyurethane foam with small fluctuation of density depending on a place and capable of obtaining a polyurethane foam excellent in quality obtained by sufficient progress of a reaction between polyol and polyisocyanate, because filling property when filling in a hollow part of a structure is excellent.SOLUTION: The present invention is a polyol liquid agent for filling containing a polyol, a catalyst and a filler, and a content of the catalyst of 0.3 to 5 mass%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyol liquid for filling, a polyurethane composition for filling containing the polyol liquid, and a polyurethane foam formed from the polyurethane composition.

Background Art

[0002] Conventionally, polyurethane foams have been used as heat insulating materials in vehicles such as automobiles and in furniture. Generally, a polyurethane foam is formed by discharging and mixing a polyol liquid and a polyisocyanate liquid filled in separate containers. It is known that a filler such as a solid flame retardant is contained in the polyol liquid in order to impart flame retardancy to the formed polyurethane foam. For example, in Patent Document 1, an invention related to a polyol composition (polyol liquid) for spray coating, which contains a polyol, a catalyst, a foaming agent, a foam stabilizer, and a flame retardant, and in which the amount of the catalyst is 10 parts by weight to 56 parts by weight with respect to 100 parts by weight of the polyol, is disclosed.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The above polyol liquid for spray coating is used for the purpose of forming a polyurethane foam by spraying it onto the surface of a structure such as furniture together with a polyisocyanate liquid for the purpose of on-site repair or the like. Therefore, from the viewpoint of preventing dripping of the liquid after spraying and improving workability, a high reactivity between the polyol and the polyisocyanate is required. In contrast, a method of forming polyurethane foam in the cavities of structures such as panels and flat decks is known, from the perspective of improving the thermal insulation and flame retardancy of such structures. In this case, it is necessary to fill the cavities of the structure with a polyol liquid agent together with a polyisocyanate liquid agent. However, when using the polyol liquid agent for spray painting mentioned above, for example, foam may form immediately near the filling opening after filling, and it may not be possible to fill the cavities to their ends. Furthermore, even if some filling is achieved, the density of the formed polyurethane foam may differ significantly between the area near the filling opening and the edges of the cavities, resulting in variations in density depending on the location and causing quality inconsistencies. This problem was particularly pronounced when fillers were included in the polyol liquid agent for the purpose of improving flame retardancy. Furthermore, when the foam formation rate was slowed to improve the ability to fill cavities in the structure, problems arose with the quality of the polyurethane foam, such as the separation of the two liquids before foaming and hardening, or the difficulty in the urethaneization and trimerization reactions, resulting in a decrease in the flame retardancy of the formed polyurethane foam.

[0005] Therefore, the object of the present invention is to provide a polyol liquid for filling that has excellent filling properties when filling cavities in a structure, thereby forming a polyurethane foam with little variation in density depending on the location, and that yields a high-quality polyurethane foam in which the reaction between the polyol and polyisocyanate has proceeded sufficiently. [Means for solving the problem]

[0006] The inventors of the present invention have found that the above problems can be solved by a polyol liquid for filling that contains a polyol, a catalyst, and a filler, wherein the content of the catalyst is within a certain range, and have completed the present invention. In other words, the present invention is as follows [1] to

[12] . [1] A polyol liquid for filling, comprising a polyol, a catalyst, and a filler, wherein the catalyst content is 0.3 to 5% by mass. [2] The polyol liquid for filling described in [1] above, further containing a foaming agent. [3] The polyol liquid for filling according to [1] or [2] above, wherein the polyol comprises at least one selected from polyester polyols and polyether polyols. [4] A polyol liquid for filling according to any one of [1] to [3] above, wherein the catalyst comprises a resinification catalyst and a trimerization catalyst. [5] A polyol liquid filler according to any one of [1] to [4] above, wherein the filler contains a solid flame retardant. [6] A polyol liquid for filling according to any of [1] to [5] above, further containing a foam stabilizer. [7] A polyol liquid for filling according to any of [1] to [6] above, further containing a settling inhibitor. [8] A polyol liquid for filling according to any one of [1] to [7] above, wherein the viscosity of the mixed components other than the foaming agent in the polyol liquid at 25°C is 3,000 mPa·s or more and 60,000 mPa·s or less. [9] A polyurethane composition for filling comprising a polyol liquid and a polyisocyanate liquid as described in any of [1] to [8] above.

[10] The polyurethane filler composition according to [9] above, wherein the isocyanate index is 200 to 600.

[11] A polyurethane filling composition according to [9] or

[10] above, wherein the gel time at a liquid temperature of 40°C is 4 to 60 seconds.

[12] A polyurethane foam formed from any of the polyurethane compositions described in [9] to

[11] above. [Effects of the Invention]

[0007] The polyol liquid formulation of the present invention exhibits excellent filling properties when used together with the isocyanate liquid formulation to fill cavities in structures, enabling the formation of polyurethane foam with minimal density variations depending on the location. Furthermore, by using the polyol liquid formulation of the present invention, a high-quality polyurethane foam can be obtained in which the reaction with polyisocyanate has proceeded sufficiently. [Modes for carrying out the invention]

[0008] [Polyol liquid for filling] The polyol liquid for filling according to the present invention contains a polyol, a catalyst, and a filler, wherein the catalyst content is 0.3 to 5% by mass. Here, "for filling" means that it is used for filling cavities in a structure, unlike the use method of forming polyurethane foam on the surface of a structure such as building fixtures by spraying on site. More specifically, it means that it is used for filling cavities inside a finished structure by providing an injection port, or for filling cavities in an unfinished structure during the manufacturing stage as part of the manufacturing process (part of the production line). The cavities in the structure have a certain shape, and when a polyurethane composition containing a polyol liquid and a polyisocyanate liquid is filled into the cavities, the polyol composition is filled along the inner wall of the cavity from near the filling port toward the edge of the cavity, foaming and hardening to form a polyurethane foam that corresponds to the shape of the cavity. The polyol liquid for filling of the present invention has excellent filling properties when filled into cavities in the structure together with the isocyanate liquid, and can form a polyurethane foam with little variation in density depending on the location. The resulting polyurethane foam is a high-quality polyurethane foam in which the urethaneization reaction and trimerization reaction have proceeded sufficiently.

[0009] [catalyst] The polyol liquid filler of the present invention (hereinafter also simply referred to as the polyol liquid) contains a catalyst, the catalyst content of which is 0.3 to 5% by mass. If the catalyst content is less than 0.3% by mass, the reaction between the polyol and polyisocyanate will be insufficient, making it difficult to obtain a polyurethane foam with excellent flame retardancy. Furthermore, if the catalyst content exceeds 5% by mass, the reactivity between the polyol and polyisocyanate will be too high, and when filling the cavity of the structure with the polyurethane composition, polyurethane foam will form in a short time near the filling opening, making it difficult to fill the entire cavity of the structure with the composition. In addition, the density of the formed polyurethane foam will vary greatly depending on the location, resulting in non-uniform physical properties. From the viewpoint of forming a polyurethane foam with little variation in density depending on the location and obtaining a high-quality polyurethane foam in which the reaction has proceeded sufficiently, the catalyst content is preferably 0.4 to 3% by mass, and more preferably 0.6 to 2% by mass. The catalyst amounts mentioned above are based on the total amount of the polyol liquid. While catalysts are often sold as products dissolved in a solvent, the catalyst amount in this invention does not include the amount of solvent in which the catalyst is dissolved; it refers to the amount of the catalyst itself (i.e., the solute) dissolved in the solvent.

[0010] Furthermore, as will be described later, a polyol liquid and a polyisocyanate liquid are mixed to form a polyurethane composition. The amount of catalyst in the polyurethane composition (amount of catalyst based on the total amount of polyurethane composition) is preferably 0.2 to 3% by mass, more preferably 0.3 to 1.5% by mass, and even more preferably 0.4 to 1% by mass. If the amount of catalyst is below these upper limits, the polyurethane composition is easier to fill into the cavities of the structure, resulting in a polyurethane foam with less density variation. If the amount of catalyst is above these lower limits, it becomes easier to obtain a polyurethane foam of superior quality in which the reaction has proceeded sufficiently.

[0011] Examples of the catalysts mentioned above include resinification catalysts and trimerization catalysts. From the viewpoint of appropriately carrying out the urethaneization reaction and trimerization reaction and obtaining a polyurethane foam with excellent flame retardancy, it is preferable that the catalyst contains both a resinification catalyst and a trimerization catalyst.

[0012] <Resin-based catalyst> Resin-based catalysts are catalysts that promote the reaction between polyols and polyisocyanates. Examples of resin-based catalysts include amine-based catalysts such as imidazole compounds and piperazine compounds, and metal-based catalysts. Examples of imidazole compounds include tertiary amines in which the secondary amine at the 1-position of the imidazole ring is substituted with an alkyl group, an alkenyl group, etc. Specifically, N-methylimidazole, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, 1-isobutyl-2-methylimidazole, etc. can be mentioned. Also, imidazole compounds in which the secondary amine in the imidazole ring is substituted with a cyanoethyl group can also be mentioned. Examples of piperazine compounds include tertiary amines such as N-methyl-N',N'-dimethylaminoethylpiperazine and trimethylaminoethylpiperazine. Examples of amine-based catalysts include various tertiary amines such as pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinobis(2-dimethylaminoethyl)ether, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl)ether, N,N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine, tripropylamine, etc., in addition to imidazole compounds and piperazine compounds.

[0013] Examples of metal-based catalysts include metal salts such as lead, tin, bismuth, copper, zinc, cobalt, nickel, etc., and preferably metal organic acid salts such as lead, tin, bismuth, copper, zinc, cobalt, nickel, etc. More preferably, organotin acid salts such as dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin versatate, etc., and bismuth organic acid salts such as bismuth trioctoate, bismuth tris(2-ethylhexanoate), etc. can be mentioned, and among them, bismuth organic acid salts are preferred. The resinification catalyst may be used alone or in combination of two or more. As the resinification catalyst, at least one selected from amine-based catalysts and metal-based catalysts is preferred, and it is preferable to use an amine-based catalyst and a metal-based catalyst in combination.

[0014] The content of the resinification catalyst in the polyol liquid is preferably 0.1 to 4% by mass, more preferably 0.3 to 3% by mass. When the content of the resinification catalyst is within such a range, the reaction between the polyol and the isocyanate appropriately proceeds easily. Further, when the resinification catalyst and the trimerization catalyst are used in combination, by adjusting the content of the resinification catalyst within the above range and adjusting the content of the trimerization catalyst to a predetermined range described later, the filling property into the cavity portion of the structure of the polyurethane composition is improved, and physical properties such as the flame retardancy of the formed polyurethane foam are also good.

[0015] <Trimerization catalyst> The trimerization catalyst is a catalyst that reacts and trimerizes the isocyanate groups contained in the polyisocyanate to promote the formation of an isocyanurate ring. Examples of the trimerization catalyst include nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; alkali metal carboxylates such as potassium acetate, potassium 2-ethylhexanoate, and potassium octylate; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt; quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetraphenylammonium salt, triethylmonomethylammonium salt, and quaternary ammonium carboxylate salts. Suitable specific examples of the carboxylic acid in the above quaternary ammonium carboxylate salt include at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. The trimerization catalyst may be used alone or in combination of two or more, but it is preferable to use two or more in combination. As the trimerization catalyst, at least one selected from the group consisting of alkali metal carboxylates and quaternary ammonium carboxylate salts is preferable, and it is preferable to use a combination of an alkali metal carboxylate and a quaternary ammonium carboxylate salt.

[0016] The content of the trimerizing catalyst in the polyol liquid formulation is preferably 0.05 to 2% by mass, and more preferably 0.1 to 1.5% by mass. When the trimerizing catalyst content is within this range, the trimerizing reaction can proceed appropriately. Furthermore, when the resinification catalyst and the trimerizing catalyst are used in combination, adjusting the content of the resinification catalyst and the trimerizing catalyst to the predetermined ranges described above improves the filling ability of the voids in the structure of the polyurethane composition, and also improves the physical properties of the formed polyurethane foam, such as flame retardancy.

[0017] [Polyol] Examples of polyols contained in polyol liquid formulations include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, polyester polyols, polymer polyols, and polyether polyols.

[0018] Examples of polylactone polyols include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Examples of polycarbonate polyols include polyols obtained by the de-alcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, etc.

[0019] Examples of aromatic polyols include bisphenol A, bisphenol F, phenol novolac, and cresol novolac. Examples of alicyclic polyols include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.

[0020] Examples of polyester polyols include polymers obtained by dehydrating and condensing a polybasic acid and a polyhydric alcohol, and condensates of hydroxycarboxylic acids and the aforementioned polyhydric alcohols. Examples of polybasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), and succinic acid. Examples of polyhydric alcohols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol. Examples of hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

[0021] Examples of polymer polyols include polymers obtained by graft polymerization of ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate onto aromatic polyols, alicyclic polyols, aliphatic polyols, and polyester polyols, as well as polybutadiene polyols, or hydrogenated versions thereof.

[0022] Examples of polyether polyols include polymers obtained by ring-opening polymerization of at least one alkylene oxide such as ethylene oxide, propylene oxide, or tetrahydrofuran in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogen atoms. Examples of low molecular weight active hydrogen compounds having two or more active hydrogen atoms include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol, triols such as glycerin and trimethylolpropane, amines such as ethylenediamine, and butylenediamine.

[0023] The polyol used in the present invention preferably contains at least one selected from polyester polyols and polyether polyols, and preferably contains at least a polyester polyol. More preferably, it contains a polyester polyol obtained by dehydrating and condensing an aromatic ring-containing polybasic acid such as isophthalic acid (m-phthalic acid) or terephthalic acid (p-phthalic acid) with a dihydric alcohol such as bisphenol A, ethylene glycol, and 1,2-propylene glycol.

[0024] The hydroxyl value of the polyol is preferably 20 to 300 mg KOH / g, more preferably 30 to 275 mg KOH / g, and even more preferably 50 to 250 mg KOH / g. When the hydroxyl value of the polyol is below the upper limit, the viscosity of the polyol liquid does not become excessively high, which is preferable from the viewpoint of handling and other factors. On the other hand, when the hydroxyl value of the polyol is above the lower limit, the crosslinking density of the polyurethane foam increases, resulting in higher strength. The hydroxyl value of polyols can be measured according to JIS K 1557-1:2007.

[0025] [Filler] The polyol liquid formulation contains a filler. By including a filler, the polyurethane foam can be given functions according to the type of filler. Preferably, the filler contains a flame retardant. By using a flame retardant as a filler, the polyurethane foam can be given high flame retardant performance. The flame retardant used as a filler is a solid flame retardant. In this invention, the flame retardancy can be more effectively enhanced by using a solid flame retardant. A solid flame retardant is a flame retardant that becomes solid at room temperature (23°C) and normal pressure (1 atmosphere).

[0026] From the viewpoint of more effectively enhancing flame retardancy, the solid flame retardant is preferably at least one selected from the group consisting of red phosphorus-based flame retardants, boron-containing flame retardants, bromine-containing flame retardants, phosphate-containing flame retardants, chlorine-containing flame retardants, antimony-containing flame retardants, metal hydroxides, and needle-shaped fillers.

[0027] <Red phosphorus-based flame retardant> Red phosphorus-based flame retardants may consist of pure red phosphorus, but they may also be red phosphorus coated with a resin, metal hydroxide, metal oxide, etc., or red phosphorus mixed with a resin, metal hydroxide, metal oxide, etc. The resin used to coat or mix with red phosphorus is not particularly limited, but examples include thermosetting resins such as phenolic resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, aniline resins, and silicone resins. From the viewpoint of flame retardancy, metal hydroxides are preferred as the compound used for coating or mixing. The metal hydroxides described later may be appropriately selected and used.

[0028] The amount of red phosphorus-based flame retardant added is preferably 3 to 60 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 20 to 45 parts by mass, per 100 parts by mass of polyol. By setting the amount of red phosphorus-based flame retardant above these lower limits, the effect of the red phosphorus-based flame retardant is more easily achieved. On the other hand, by setting it below the upper limit, foaming is not inhibited by the red phosphorus-based flame retardant.

[0029] <Boron-containing flame retardant> Examples of boron-containing flame retardants include borax, boron oxide, boric acid, and borates. Examples of boron oxides include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide. Examples of borates include alkali metals, alkaline earth metals, elements from groups 4, 12, and 13 of the periodic table, and ammonium borates. Specifically, 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. Boron-containing flame retardants may be used alone or in combination of two or more types. The boron-containing flame retardant is preferably a borate, and more preferably zinc borate.

[0030] The amount of boron-containing flame retardant is not particularly limited, but is preferably 3 to 45 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 25 parts by mass per 100 parts by mass of polyol. By setting the amount of boron-containing flame retardant above these lower limits, the effect of the boron-containing flame retardant is more easily exerted, and flame retardancy is enhanced. On the other hand, by setting it below the upper limit, foaming is not inhibited by the boron-containing flame retardant.

[0031] <Bromine-containing flame retardant> Bromine-containing flame retardants are not particularly limited as long as they contain bromine in their molecular structure and are solid at room temperature and pressure, but examples include aromatic compounds containing brominated aromatic rings. Examples of brominated aromatic ring-containing aromatic compounds include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

[0032] Furthermore, the brominated aromatic ring-containing aromatic compound may also be a brominated polymer. Specifically, examples include polycarbonate oligomers produced using brominated bisphenol A as a raw material, brominated polycarbonates such as copolymers of this polycarbonate oligomer and bisphenol A, and diexo compounds produced by the reaction of brominated bisphenol A and epichlorohydrin. In addition, examples include brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, poly(brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A and cyanuryl chloride condensates, brominated polystyrene such as brominated (polystyrene), poly(brominated styrene), and 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 individually or in combination of two or more. Among the above, brominated aromatic ring-containing aromatic compounds are preferred, and among these, monomer-based organic bromine compounds such as ethylenebis(pentabromophenyl) are preferred.

[0033] The amount of bromine-containing flame retardant added is preferably 3 to 60 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 20 to 45 parts by mass, per 100 parts by mass of polyol. By setting the amount of bromine-containing flame retardant above these lower limits, the effect of the bromine-containing flame retardant is more easily achieved. On the other hand, by setting it below the upper limit, foaming is not inhibited by the bromine-containing flame retardant.

[0034] <Phosphate-containing flame retardant> Examples of phosphate-containing flame retardants include phosphates comprising salts of various phosphoric acids with at least one metal or compound selected from metals of groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. Phosphates are not particularly limited, but examples include monophosphates, pyrophosphates, and polyphosphates. Examples of metals in groups IA through IVB of the periodic table include lithium, sodium, calcium, barium, iron(II), iron(III), and aluminum. Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and piperazine. Examples of aromatic amines include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, and 3-(trifluoromethyl)aniline. Examples of heterocyclic compounds containing nitrogen in the ring include pyridine, triazine, and melamine.

[0035] Specific examples of phosphate-containing flame retardants include monophosphates such as trialuminum phosphate, pyrophosphates, and polyphosphates. Here, the polyphosphate is not particularly limited, but examples include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, and aluminum polyphosphate. One or more of the above-mentioned phosphate-containing flame retardants may be used.

[0036] The amount of phosphate-containing flame retardant is not particularly limited, but is 3 to 40 parts by mass, more preferably 5 to 35 parts by mass, and even more preferably 10 to 30 parts by mass, per 100 parts by mass of polyol. By setting the amount of phosphate-containing flame retardant above these lower limits, the effect of the phosphate-containing flame retardant is more easily achieved. On the other hand, by setting it below the upper limit, foaming is not inhibited by the phosphate-containing flame retardant.

[0037] <Chlorine-containing flame retardant> Examples of chlorine-containing flame retardants include those commonly used in flame-retardant resin compositions, such as polychlorinated naphthalene, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene, which is sold under the trade name "Dechloran Plus." The amount of chlorine-containing flame retardant is not particularly limited, but is preferably 3 to 40 parts by mass, more preferably 5 to 35 parts by mass, and even more preferably 10 to 30 parts by mass per 100 parts by mass of polyol. By setting the amount of chlorine-containing flame retardant above these lower limits, the effect of the chlorine-containing flame retardant is more easily achieved. On the other hand, by setting it below the upper limit, foaming is not inhibited by the chlorine-containing flame retardant.

[0038] <Antimony-containing flame retardant> Examples of antimony-containing flame retardants include antimony oxide, antimonate salts, and pyroantimonate salts. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimonate salts include sodium antimonate and potassium antimonate. Examples of pyroantimonate salts include sodium pyroantimonate and potassium pyroantimonate. Antimony-containing flame retardants may be used alone or in combination of two or more types. The preferred antimony-containing flame retardant used in this invention is antimony trioxide.

[0039] The amount of antimony-containing flame retardant is not particularly limited, but is preferably 1 to 40 parts by mass, more preferably 2 to 35 parts by mass, and even more preferably 3 to 30 parts by mass per 100 parts by mass of polyol. By setting the amount of antimony-containing flame retardant above these lower limits, the effect of the antimony-containing flame retardant is more easily exerted, and flame retardancy is enhanced. On the other hand, by setting it below the upper limit, foaming is not inhibited by the antimony-containing flame retardant.

[0040] <Metal hydroxide> Examples of metal hydroxides used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, and tin hydroxide. A single metal hydroxide may be used, or two or more may be used in combination.

[0041] The amount of metal hydroxide added is, for example, 0.1 to 50 parts by mass, preferably 0.2 to 30 parts by mass, more preferably 0.3 to 20 parts by mass, and even more preferably 0.5 to 15 parts by mass, per 100 parts by mass of polyol. By setting the amount of metal hydroxide above these lower limits, the effects of the metal hydroxide are more easily exhibited, and flame retardancy is enhanced. On the other hand, by setting it below the upper limit, foaming is not inhibited by the metal hydroxide.

[0042] <Needle-shaped filler> Examples of needle-shaped fillers include potassium titanate whiskers, aluminum borate whiskers, magnesium-containing whiskers, silicon-containing whiskers, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fibers, carbon fibers, graphite fibers, metal fibers, slag fibers, gypsum fibers, silica fibers, alumina fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, stainless steel fibers, and the like. These needle-shaped fillers can be used individually or in combination of two or more types.

[0043] The aspect ratio (length / diameter) of the needle-shaped filler used in the present invention is preferably in the range of 5 to 50, and more preferably in the range of 10 to 40. This aspect ratio can be determined by observing the needle-shaped filler with a scanning electron microscope and measuring its length and width.

[0044] The amount of needle-shaped filler added is, for example, 10 to 100 parts by mass, preferably 20 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 40 to 70 parts by mass, per 100 parts by mass of polyol. By setting the amount of needle-shaped filler above these lower limits, the shape of the polyurethane foam after combustion is more easily maintained. On the other hand, by setting the amount below these upper limits, foaming is less likely to be inhibited by the needle-shaped filler.

[0045] Among the solid flame retardants mentioned above, red phosphorus-based flame retardants, boron-containing flame retardants, and bromine-containing flame retardants are preferred. Furthermore, it is preferable to use multiple solid flame retardants in combination. In this case, it is preferable to use a combination of red phosphorus-based flame retardants, boron-containing flame retardants, and bromine-containing flame retardants. Combining these makes it easier to further improve flame retardancy.

[0046] <Amount of solid flame retardant> The amount of solid flame retardant is not particularly limited, but is, for example, 10 to 200 parts by mass, preferably 20 to 150 parts by mass, and more preferably 40 to 120 parts by mass, per 100 parts by mass of polyol. By setting the amount of solid flame retardant to be above these lower limits, appropriate flame retardancy can be imparted to the polyurethane foam. By setting the amount of solid flame retardant to be below these upper limits, the polyurethane composition becomes easier to fill into the interior of the structure, and it becomes easier to obtain a polyurethane foam with less density variation depending on the location.

[0047] As fillers, inorganic fillers other than the flame retardants mentioned above may be included. As inorganic fillers, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, 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 sulfide, silicon carbide, various magnetic powders, fly ash, etc. can be used as appropriate. Inorganic fillers may be used individually or in combination of two or more types.

[0048] The filler content in the polyol liquid formulation 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, per 100 parts by mass of polyol. By setting the filler content above these lower limits, it becomes easier to impart functions to the polyurethane foam according to the type of filler. By setting the filler content below these upper limits, it becomes easier to fill the inside of the structure with the polyurethane composition, and it becomes easier to obtain a polyurethane foam with less density variation depending on the location.

[0049] [Liquid flame retardant] Polyol liquid formulations may contain liquid flame retardants. Liquid flame retardants are flame retardants that become liquid at room temperature (23°C) and atmospheric pressure (1 atm). A specific example of a liquid flame retardant is phosphate ester. Unlike solid flame retardants, liquid flame retardants are less likely to form precipitates during storage and are easy to handle.

[0050] As the phosphate ester, it is preferable to use monophosphate esters, condensed phosphate esters, etc. Examples of monophosphate esters include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tri(2-ethylhexyl) phosphate; halogen-containing phosphate esters such as tris(β-chloropropyl) phosphate; trialkoxy phosphates such as tributoxyethyl phosphate; aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, cresyldiphenyl phosphate, and diphenyl(2-ethylhexyl) phosphate; and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate.

[0051] Examples of condensed phosphate esters include aromatic condensed phosphate esters such as trialkyl polyphosphates, resorcinol polyphenyl phosphates, bisphenol A polycresyl phosphates, and bisphenol A polyphenyl phosphates. Examples of commercially available condensed phosphate esters include "CR-733S," "CR-741," and "CR747" from Daihachi Chemical Industry Co., Ltd., and "ADEKA Stab PFR" and "FP-600" from ADEKA Corporation.

[0052] Liquid flame retardants may be used individually from the above-mentioned types, or two or more types may be used in combination. Among these, monophosphate esters are preferred, and tris(β-chloropropyl) phosphate is more preferred, from the viewpoint of facilitating the manufacture of polyurethane foam and improving the flame retardancy of polyurethane foam.

[0053] If a liquid flame retardant is included, the amount is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, and even more preferably 20 to 60 parts by mass, per 100 parts by mass of polyol.

[0054] [Settling inhibitor] The polyol solution may contain a settling inhibitor. The settling inhibitor suppresses the settling of fillers dispersed in the polyol solution during long-term storage at room temperature or low temperature, and makes it easier to uniformly disperse the fillers by simply shaking the solution by hand. Settling inhibitors are generally solid at room temperature and atmospheric pressure, and usually become solid components (insoluble components) in the solution.

[0055] There are no particular limitations on the settling inhibitor. Specific examples of settling inhibitors include powdered silica, organic clay, carbon black, hydrogenated castor oil wax, and fatty acid amide wax. One or more of these may be used. As powdered silica, fumed silica, colloidal silica, silica gel, etc., can be used. Among these, fumed silica is preferred, and hydrophobic fumed silica is particularly preferred. As fumed silica, Aerosil (registered trademark) from Nippon Aerosil Co., Ltd. can be used. Organic clays such as organic affinity phyllosilicates can be used. Carbon black manufactured using methods such as the furnace process, channel process, or thermal process can be used. Commercially available carbon black can be selected and used as appropriate. Hydrogenated castor oil wax, fatty acid amide wax, etc., form a swollen gel structure in a liquid. These are generally sold under names such as thixotropic agents, thickeners, anti-settling agents, and anti-dripping agents, and commercially available products can be selected and used as appropriate.

[0056] Preferred settling inhibitors are those having a thickening effect, and among these, those containing Si as a constituent element are more preferred. Specific examples of settling inhibitors having a thickening effect are fumed silica and organic affinity phyllosilicates, with fumed silica being more preferred.

[0057] If a settling inhibitor is included, its content is not particularly limited, but is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of polyol. By setting the content of the settling inhibitor to above the lower limit, the polyol liquid is thickened, the settling of the filler is suppressed, and its dispersibility can be improved. Furthermore, by setting the content of the settling inhibitor to below the upper limit, a decrease in handling ease due to excessively high viscosity of the liquid is prevented.

[0058] [Foaming agent] The polyol liquid formulation of the present invention preferably contains a foaming agent. The foaming agent allows the polyol liquid formulation and the polyisocyanate liquid formulation to be mixed and foamed to form a polyurethane foam. The foaming agent is contained in at least one of the polyol liquid formulation and the polyisocyanate liquid formulation described later, but it is preferable that it be contained in the polyol liquid formulation. While not particularly limited, examples of blowing agents include organic blowing agents such as hydrocarbon compounds, chlorinated aliphatic hydrocarbon compounds, hydrofluorocarbons, hydrochlorofluorocarbon compounds, and hydrofluoroolefins, and inorganic blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Among these, the use of organic blowing agents is preferred.

[0059] Examples of the above hydrocarbon compounds include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane. Examples of the above-mentioned chlorinated aliphatic hydrocarbon compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. Examples of the above-mentioned hydrofluorocarbons include CHF3, CH2F2, and CH3F.

[0060] Examples of the above hydrochlorofluorocarbon compounds include dichloromonofluoroethane (e.g., HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)), HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane), and others.

[0061] Examples of the above-mentioned hydrofluoroolefins include fluoroalkenes having 3 to 6 carbon atoms. Furthermore, the hydrofluoroolefin may also be a hydrochlorofluoroolefin containing a chlorine atom, and therefore may be a chlorofluoroalkene having 3 to 6 carbon atoms. Hydrofluoroolefins with 3 or 4 carbon atoms are preferred. More specifically, examples include trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorotrifluoropropene such as HFO-1233, chlorodifluoropropene, chlorotrifluoropropene, and chlorotetrafluoropropene. More specifically, 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,1-trifluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 1,1,1,3,3,3-hexafluorobut-2-ene, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yez), (E)-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)), Examples include (Z)-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(Z)), (Z)-1,1,1,4,4,4-hexafluorobuto-2-ene (HFO-1336mzz(Z)), (E)-1,1,1,4,4,4-hexafluorobuto-2-ene (HFO-1336mzz(E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), trifluoroethylene (HFO-1123), (E)-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)), (Z)-2,3,3,3-tetrafluoro-1-chloropropene (HCFO-1224yd(Z)), etc.

[0062] From the viewpoint of achieving good foam formation and reducing environmental impact, it is preferable to use hydrofluoroolefin as a foaming agent.

[0063] The content of the blowing agent is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, and even more preferably 20 to 60 parts by mass, per 100 parts by mass of polyol. If the content of the blowing agent is above the lower limit, foaming is promoted and the density of the resulting polyurethane foam can be reduced. On the other hand, if the content of the blowing agent is below the upper limit, excessive foaming can be suppressed.

[0064] Furthermore, from the viewpoint of preventing degradation due to coexistence with catalysts and other components, it is preferable to add the foaming agent to the polyol liquid immediately before use. That is, it is preferable to prepare and store a polyol liquid consisting of mixed components other than the foaming agent, and to add the foaming agent to the polyol liquid consisting of the mixed components immediately before use. The mixed components must include polyol, catalyst, and filler, and may also include various additives such as foam stabilizers and sedimentation inhibitors as needed. The viscosity of the mixed components other than the foaming agent in the polyol liquid, i.e., the polyol liquid before the foaming agent is added, at 25°C is preferably 3,000 mPa·s or more and 60,000 mPa·s or less. By setting the viscosity to 3,000 mPa·s or more, it is possible to suppress the precipitation of fillers contained in the polyol liquid composed of the mixed components and the formation of hard caking. By setting the viscosity to 60,000 mPa·s or less, it becomes easier to adjust the viscosity of the polyol liquid when the foaming agent is added to a predetermined range described later, and it becomes possible to efficiently mix it with the polyisocyanate liquid. The viscosity of the mixed components other than the foaming agent in the polyol liquid is more preferably 3,500 mPa·s or more and 50,000 mPa·s or less, and even more preferably 4,000 mPa·s or more and 40,000 mPa·s or less.

[0065] After the foaming agent is added, that is, the viscosity of the polyol liquid containing the foaming agent at 25°C is preferably 2500 mPa·s or less, more preferably 2000 mPa·s or less, and even more preferably 1500 mPa·s or less. The viscosity of the mixed components other than the foaming agent in the polyol liquid, and the viscosity of the polyol liquid containing the foaming agent, are measured by the method described in the examples.

[0066] [water] The polyol liquid may contain water. The inclusion of water improves the foaming properties when forming polyurethane foam. The amount of water added is, for example, 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, and more preferably 0.3 to 3 parts by mass, per 100 parts by mass of polyol. By keeping the amount of water within this range, the polyurethane composition becomes easier to foam appropriately.

[0067] [Foam stabilizer] The polyol solution preferably contains a foam stabilizer. The foam stabilizer improves the foaming properties of the polyurethane composition obtained from the polyol solution and the polyisocyanate solution. Examples of foam stabilizers include polyoxyalkylene-based foam stabilizers such as polyoxyalkylene alkyl ethers, and surfactants such as silicone-based foam stabilizers such as organopolysiloxanes. These foam stabilizers may be used individually or in combination of two or more types. The amount of foam stabilizer added 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 polyol. If the amount of foam stabilizer is above these lower limits, the polyurethane composition becomes easier to foam, and a homogeneous polyurethane foam is easier to obtain. If the amount of foam stabilizer is below these upper limits, a good balance is achieved between manufacturing costs and the effects obtained.

[0068] (Other ingredients) The polyol liquid formulation may, as necessary and within the limits that do not impair the objectives of the present invention, contain one or more additives selected from phenolic, amine, and sulfur-based antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, tackifying resins, polybutene, petroleum resins, and other tackifying agents.

[0069] [Polyurethane composition for filling] The polyurethane filler composition of the present invention (hereinafter also simply referred to as the polyurethane composition) comprises the polyol liquid agent and the polyisocyanate liquid agent described above. The polyurethane foam of the present invention is formed from the polyurethane composition. Specifically, it is a reaction product obtained by reacting and foaming a polyurethane composition obtained by mixing the polyol liquid agent and the polyisocyanate liquid agent. The polyurethane composition used in the present invention is generally a two-component type. A polyurethane foam is obtained by mixing the polyol liquid and polyisocyanate liquid of the present invention, which have been stored separately, and then reacting and foaming them. The polyisocyanate liquid may contain, as needed, other components besides polyisocyanate, such as the fillers, foaming agents, catalysts, and other components mentioned above.

[0070] (Polyisocyanate) The polyisocyanate liquid formulation contains a polyisocyanate. As the polyisocyanate, known polyisocyanates used for forming polyurethane foams can be used, such as 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.

[0071] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0072] Examples of aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0073] Among these, aromatic polyisocyanates are preferred from the viewpoint of ease of use and availability, and diphenylmethane diisocyanate is more preferred. Polyisocyanates may be used individually or in combination of two or more types.

[0074] (Isocyanate Index) There are no particular limitations on the isocyanate index of the polyurethane composition of the present invention, but 200 to 600 is preferred, and 350 to 550 is more preferred. If the isocyanate index is above the lower limit, the amount of polyisocyanate relative to the polyol becomes excessive, making it easier to form isocyanurate bonds by the trimer of polyisocyanate, resulting in improved flame retardancy of the polyurethane foam. Furthermore, if the index is above the lower limit, it is easier to manufacture polyurethane foam having isocyanurate bonds, i.e., polyurethane foam that combines flame retardancy and heat insulation at a high level. Also, if the isocyanate index is below the upper limit, a good balance is achieved between the flame retardancy of the resulting polyurethane foam and the manufacturing cost.

[0075] The isocyanate index can be calculated using the following method. Isocyanate Index = Equivalents of polyisocyanate ÷ (Equivalents of polyol + Equivalents of water) × 100 Here, each equivalent number can be calculated as follows: • Equivalent weight of polyisocyanate = Amount of polyisocyanate used (g) × NCO content (mass%) / Molecular weight of NCO (moles) × 100 • Equivalent weight of polyol = OHV × Amount of polyol used (g) ÷ Molecular weight of KOH (millimoles) OHV is the hydroxyl value (mgKOH / g) of a polyol. • Equivalent amount of water = Amount of water used (g) / Molecular weight of water (moles) × Number of OH groups in water In the above formulas, the molecular weight of NCO is 42 moles, the molecular weight of KOH is 56100 millimoles, the molecular weight of water is 18 moles, and the number of OH groups in water is 2.

[0076] Furthermore, when mixing the polyol liquid and the polyisocyanate liquid, the volume ratio of the two (polyol liquid / polyisocyanate liquid) should be, for example, in the range of 1 / 1.4 to 1.4 / 1, preferably 1 / 1.2 to 1.2 / 1.

[0077] (Geltime) The gel time of the polyurethane composition of the present invention is preferably 4 to 60 seconds, and more preferably 10 to 45 seconds. If the gel time is below these upper limits, the urethane reaction proceeds appropriately, and the performance of the polyurethane foam is good. If the gel time is above the lower limit, when filling the cavities of a structure with the polyurethane composition, poor filling and density variations are less likely to occur. Here, the gel time is the value obtained when the liquid temperature of the polyurethane composition is adjusted to 40°C. The gel time is the time (in seconds) from the start of stirring after mixing the polyol liquid and the polyisocyanate liquid, until the foam begins to form a string when a rod is inserted into the foam during foaming. For example, when using a spray gun, the start of stirring (0 seconds) means the time the trigger is pulled.

[0078] [Use of polyol compositions and polyurethane compositions] The polyol liquid filler and polyurethane filler composition containing the same of the present invention are used for filling cavities in structures. The structure may be a finished structure manufactured through a series of processes in a factory or the like, or it may be an unfinished structure before the manufacture of a finished structure. Filling cavities in a completed structure with a polyurethane composition primarily involves filling cavities surrounded by components that make up the completed structure. For example, an injection port is provided in a part of the completed structure for filling. Filling cavities in an unfinished structure is a filling process performed as one of the manufacturing steps before forming the completed structure, and involves filling cavities that are at least partially open. Specifically, in the manufacturing process, an unfinished structure with open cavities is manufactured, a polyurethane composition is filled into the cavities from the open portion to form a polyurethane foam, and then the open portion is closed. The open portion can be closed by bonding or welding the open portion. Alternatively, it may be closed by providing a component that covers the open portion.

[0079] The finished structure is not limited to anything that has a cavity, and may be a component used in buildings or a component used in vehicles such as automobiles. Specific examples of finished structures include plate-like members and frame members. Examples of plate-like members include panels and flat decks. The panel is not particularly limited as long as it has a cavity, and may be any shape when viewed from the front, such as a rectangle, square, or triangle. The entire interior of the panel may be hollow, or multiple components may be provided inside the panel, with a portion of the internal cavity being an elongated cavity. A flat deck can be obtained, for example, by roll forming a metal sheet such as a steel plate. Flat decks are used in floor or roof structures, for example, as formwork for pouring concrete onto the upper surface. The flat deck has a flat section with a flat top surface, and on the underside of the flat section, multiple Several reinforcing ribs are provided. Each reinforcing rib is a hollow projection running longitudinally. They are positioned extending along the line, with both ends in the longitudinal direction being crushed and closed. The cavities in the reinforcing ribs are elongated cavities. The cross-sectional shape of the reinforcing ribs in the flat deck is not particularly limited as long as cavities are formed inside, and may be triangular, square, or any other shape. In the flat deck, the polyurethane composition is filled into the cavities of the reinforcing ribs, and the reinforcing ribs are provided with injection holes for filling them with the polyurethane composition.

[0080] A frame material has a long, narrow cavity inside and is a component that constitutes part or all of the frame surrounding an opening in a building fixture such as a window or door. For example, a frame consists of a pair of side frame sections, an upper frame section, and a lower frame section, but the frame material only needs to constitute a small portion of these frame sections.

[0081] An unfinished structure is a structure in the manufacturing stage of a finished structure, such as the plate-like members or frame materials mentioned above, in which part is open. An example of an unfinished structure is a flat deck, in which a metal plate such as a steel plate has multiple recesses with openings formed by a roll molding machine or the like. After filling the recesses of the structure with a polyurethane resin composition from the openings, the openings are closed by means of welding or the like to form reinforcing ribs and thus the flat deck can be manufactured. Another example of an unfinished structure is a structure in which part of the side surface constituting the panel is not provided, resulting in a partially open structure. After filling the open portion with a polyurethane resin composition, the open portion is closed with the member constituting the side surface to manufacture the panel.

[0082] The polyurethane composition containing the polyol liquid of the present invention has excellent filling properties, allowing it to fill even elongated cavities to the very edges, and forming a high-quality polyurethane foam with minimal density differences from location to location. A slender cavity is one in which the length in the longitudinal direction is, for example, twice or more, preferably 2.5 times or more, the length in the longitudinal direction relative to the cross-sectional dimension. Here, the cross-sectional dimension is the part with the longest length in the cross-section of the cavity; for example, it is the major axis in the case of an ellipse, and the length of the diagonal in the case of a rectangle or square. If the size of the cross-sectional shape (i.e., the cross-sectional dimension) changes along the longitudinal direction, the maximum cross-sectional dimension in the part where it changes should be used as the above cross-sectional dimension. In the case of a structure having an elongated cavity, it may be either a completed or uncompleted structure, but in the case of a completed structure, it is preferable to fill the end of the elongated cavity or the inside of the cavity through the injection hole as described above with the polyurethane composition. Even in such cases, the polyurethane composition described above can be used to fill the cavity all the way to the end.

[0083] The method for filling the cavities of a polyurethane composition structure is not particularly limited, but for example, a polyol liquid and a polyisocyanate liquid may be prepared in advance, mixed to form a polyurethane composition, and then filled into the cavities using a spray gun. More specifically, it is preferable to use a foaming apparatus equipped with a spray gun, mix the polyol liquid and the polyisocyanate liquid in the foaming apparatus, and then fill the mixture into the spray gun. The polyurethane composition, sprayed by a spray gun, fills the cavities in the structure, and the polyol and polyisocyanate react and foam, forming a polyurethane foam. As described above, the polyurethane composition uses a specific polyol liquid agent, making it easy to fill cavities in structures, resulting in properly formed polyurethane foam with minimal density variations and superior quality. [Examples]

[0084] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The components used in the examples and comparative examples are shown below.

[0085] <Polyol> (1) Polyester polyol (Maximol RLK-087, manufactured by Kawasaki Chemical Industries, Ltd., hydroxyl value 200 mg KOH / g) (2) Polyester polyol (PHANTOL SV-208, manufactured by Hitachi Chemical Co., Ltd., hydroxyl value 235 mg KOH / g)

[0086] <Catalyst> (1) Trimerization catalyst: Quaternary ammonium carboxylic acid salt (DABCO TMR-7, manufactured by Evonik Japan Co., Ltd.), concentration 45-55% by mass (2) Trimerization catalyst: Potassium 2-ethylhexanoate (manufactured by Air Products, product name: DABCO K-15), concentration 70~80% by mass (3) Resinization catalyst (metal type): Bismuth 2-ethylhexanoate (manufactured by Nitto Chemical Co., Ltd., product name: Bi28), concentration 81-90% by mass (4) Resinization catalyst (amine type): 1,2-dimethylimidazole (TOYOCAT-DM70 manufactured by Tosoh Corporation), concentration 65-75% by mass (5) Resinization catalyst (amine type): 1,2-dimethylimidazole (manufactured by Kao Corporation, product name: Kaolizer No. 390), concentration 65-75% by mass

[0087] <Foam stabilizer> • Polyoxyalkylene-based foam stabilizer (SH-193, manufactured by Toray Dow Corning Co., Ltd.)

[0088] <Liquid Flame Retardant> • Tris(β-chloropropyl) phosphate (TMCPP, manufactured by Daihachi Chemical Co., Ltd.)

[0089] <Foaming agent> • HFO-1233zd(E) (Solstice LBA manufactured by Central Glass Co.)

[0090] <Filler> (1) Needle-shaped filler: Wollastonite (SH-1250, manufactured by Kinsei Matec Co., Ltd.) (2) Red phosphorus-based flame retardant (Nova Excel 140 manufactured by Phosphorus Chemical Industry Co., Ltd., metal hydroxide coating, red phosphorus content 94% by mass or more) (3) Zinc borate (Firebrake ZB, manufactured by Hayakawa Shoji Co., Ltd.) (4) Ethylene bis(pentabromophenyl) (SAYTEX 8010, manufactured by Albemarle)

[0091] <Settling inhibitor> • Fumed silica (Aerosil R976S manufactured by Nippon Aerosil Co., Ltd.) <Water> ·water

[0092] <Polyisocyanate> Polyisocyanate (MDI, manufactured by Sumitomo Chemical Co., Ltd., product name: Sumijoule 44V20)

[0093] The method for measuring viscosity is as follows: <Viscosity> Of the components of the polyol liquid formulation shown in Table 1, the components excluding the foaming agent were mixed in 300 mL of polypropylene cups in the proportions shown in Table 1 to obtain the mixed component (polyol liquid formulation excluding the foaming agent). The viscosity of this mixed component was measured using a B-type viscometer at a liquid temperature of 25°C under the condition of 1 rpm, and the value measured 1 minute after the start of rotation was taken as the viscosity of the mixed component (polyol liquid formulation excluding the foaming agent). Separately, all components of the polyol liquid preparation shown in Table 1 were mixed in 300 mL of a polypropylene cup in the proportions shown in Table 1 to prepare a polyol liquid preparation containing a foaming agent. The components were added by first introducing all components except the foaming agent into the cup and stirring, then introducing the foaming agent and mixing further. The viscosity of the polyol liquid preparation containing the foaming agent was measured using a B-type viscometer at a liquid temperature of 25°C and under conditions of 60 rpm. The value measured 1 minute after the start of rotation was defined as the viscosity of the polyol liquid preparation containing the foaming agent.

[0094] [Examples 1-11, Comparative Examples 1-2] Polyol and polyisocyanate liquid formulations with the formulations shown in Table 1 were prepared, and the following evaluations were performed using a foaming device (Graco HFR) and a spray gun (Graco EP gun).

[0095] The prepared polyol and polyisocyanate liquids were introduced into a foaming apparatus and the liquid temperature was adjusted to 40°C. Then, the polyurethane composition, a mixture of both liquids, was dispensed using a spray gun at a discharge rate of 100 cc / second to form polyurethane foam weighing between 200 g and 400 g. The gel time and tack-free time were then evaluated as follows.

[0096] (Geltime) The measurement start time (0 seconds) was defined as the moment the spray gun trigger was pulled, and the gel time (in seconds) was defined as the time it took for the foam to become stringy when a rod was inserted into the foam during foaming. If the gel time is too short, the polyurethane composition will begin to harden during extrusion, which can easily lead to poor filling and density variations when filling the cavities of the structure with the polyol composition. Also, if the gel time is too short, the urethane reaction will not proceed sufficiently, which can easily result in poor performance of the polyurethane foam. Therefore, a gel time of 4 to 60 seconds is preferred, and 10 to 45 seconds is more preferred.

[0097] (Tack Free Time) The timing of pulling the spray gun trigger was defined as the measurement start time (0 seconds), and the time until the surface of the polyurethane foam became tack-free was defined as the tack-free time. The following criteria were used for evaluation. If the tack-free time is too long, the urethane reaction will not proceed sufficiently, resulting in poor performance of the polyurethane foam. 〇··Tack free time is less than 150 seconds △··Tack free time is 150 seconds or more but less than 300 seconds ×...Tack free time is 300 seconds or more

[0098] (Density variation) A metal cylinder (cross-section 40mm x 30mm, length 1400mm) with a long, narrow cavity and a mold release agent coated on its inner surface was prepared. A polyol liquid and a polyisocyanate liquid were introduced into a foaming apparatus, and the liquid temperature was adjusted to 40°C. Then, 100g of the polyurethane composition, which was a mixture of both liquids, was sprayed from the longitudinal center of the metal cylinder at a discharge rate of 50cc / second using a spray gun, filling the cavity of the metal cylinder and forming a 1400mm long polyurethane foam corresponding to the shape of the cavity. 200mm was cut off from both ends of the obtained polyurethane foam, and the remaining 1000mm long polyurethane foam was cut into 200mm lengths to obtain five test pieces. The density of these five test pieces was measured, and the density variation was evaluated. The average density of the five test pieces was calculated as A kg / m³. 3 The evaluation was based on the range within which the density of each test specimen was contained. ○··A ±10% kg / m 3 △··A ±20% kg / m 3 ×··A±20% or more kg / m 3

[0099] (comprehensive evaluation) ◎··Gel time was 10-45 seconds, and both tuck-free time and density variability were evaluated as good. ○ Gel time is in the range of 4-60 seconds, and both tuck-free time and density variability are evaluated as ○ (except in cases where ◎ is selected). △··Gel time is in the range of 4-60 seconds, and one of the evaluations of tuck-free time and density variability is ○, while the other is △. × Gel time is less than 4 seconds or more than 60 seconds, or at least one of the evaluations of tuck-free time and density variability is ×

[0100] [Table 1]

[0101] In each embodiment using a polyol liquid agent that satisfies the requirements of the present invention, the gel time was at an appropriate value, the polyurethane composition could be filled into the entire cavity of the structure, the formed polyurethane foam had little density difference, and the tack-free time was below a certain level, resulting in excellent performance as a polyurethane foam. In contrast, in each comparative example using a polyol liquid that did not satisfy the requirements of the present invention, the gel time was outside the appropriate range, resulting in a large density difference in the formed polyurethane foam or a long tack-free time, thus resulting in inferior performance as a polyurethane foam.

Claims

1. It contains a polyol, a catalyst, a blowing agent, and a filler, wherein the catalyst content is 0.3 to 5% by mass. The polyol includes a polyester polyol, The catalyst comprises a resinification catalyst and a trimerization catalyst, wherein the resinification catalyst content is 0.1 to 4% by mass, and the trimerization catalyst content is 0.05 to 2% by mass. The blowing agent contains a hydrofluoroolefin, and the amount of the blowing agent is 5 to 80 parts by mass per 100 parts by mass of the polyol. The content of the filler is 10 to 300 parts by mass per 100 parts by mass of the polyol. A polyol liquid agent for forming polyurethane foam having a viscosity of 2000 mPa·s or less at 25°C, A polyisocyanate solution is included, The aforementioned polyisocyanate liquid preparation consists solely of polyisocyanate. A polyurethane foam-forming polyurethane composition for filling cavities in a structure, wherein the polyol liquid and polyisocyanate liquid are mixed in a foaming apparatus equipped with a spray gun.

2. The polyurethane composition for forming polyurethane foam according to claim 1, wherein the filler contains a solid flame retardant.

3. The polyurethane foam forming polyurethane composition according to claim 1 or 2, wherein the polyol liquid agent for forming polyurethane foam further contains a foam stabilizer.

4. The polyurethane foam forming polyurethane composition according to any one of claims 1 to 3, wherein the polyol liquid agent for forming polyurethane foam further contains a sedimentation inhibitor.

5. A polyurethane composition for forming polyurethane foam according to any one of claims 1 to 4, wherein the isocyanate index is 200 to 600.

6. A polyurethane composition for forming polyurethane foam according to any one of claims 1 to 5, wherein the gel time at a liquid temperature of 40°C is 4 to 60 seconds.

7. A polyurethane foam filling a cavity in a structure formed from a polyurethane composition for forming polyurethane foam according to any one of claims 1 to 6.

Images