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

Abstract

To provide a polyol composition that prevents cells from getting coarse in the case where a foam stabilizer is not used and can give a polyurethane foam having excellent heat insulation.SOLUTION: A polyol composition contains a polyol compound, a flame retardant, a catalyst, and a foamer. The polyol composition is free of a foam stabilizer and the foamer contains water. The polyol composition has a moisture content of 1.8 mass% or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyol composition, a flame-retardant urethane resin composition, and a polyurethane foam.

Background Art

[0002] Polyurethane foams are utilized for heat insulation and dew condensation prevention of structures such as ceilings, roofs, and wall surfaces of buildings such as condominiums, single-family houses, and commercial buildings by taking advantage of their excellent heat insulation properties. A polyurethane foam is formed, for example, by spraying a urethane resin composition containing a polyol composition and a polyisocyanate composition onto the surface of each structure and causing it to foam and cure.

[0003] For example, Patent Document 1 describes an invention related to a spray heat insulating material made of a rigid polyurethane foam obtained by foaming a compounding liquid containing a polyisocyanate component, a polyol component, water, a catalyst, a foam stabilizer, a flame retardant, and a powder. And it has been shown that the spray heat insulating material is excellent in flame retardancy and dimensional stability.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] When a polyurethane foam is formed using a composition containing a foam stabilizer as in Patent Document 1 described above, bleeding out in which the foam stabilizer oozes out on the surface of the foam easily occurs, and for this reason, problems such as the object to be used being contaminated or the obtained foam being easily combustible may occur. On the one hand, from the perspective of solving bleeding-out and flammability problems, it is conceivable to produce polyurethane foam without using a foam stabilizer. However, when not using a foam stabilizer, it has been found that some of the cells forming the polyurethane foam are likely to crack, resulting in coarser cells and a tendency for the resulting heat insulation performance to deteriorate. Therefore, an object of the present invention is to provide a polyol composition that can suppress the coarsening of cells and obtain a polyurethane foam with excellent heat insulation performance when not using a foam stabilizer.

Means for Solving the Problems

[0006] As a result of intensive studies, the present inventors have found that a polyol composition containing a polyol compound, a flame retardant, a catalyst, and a polyol composition containing a catalyst, wherein the polyol composition does not contain a foam stabilizer and the moisture content of the polyol composition is 1.8% by mass or less, can solve the above problems, and thus completed the present invention. That is, the present invention provides the following [1] to [8]. [1] A polyol composition containing a polyol compound, a liquid flame retardant, a catalyst, and a blowing agent, wherein the polyol composition does not contain a foam stabilizer and the moisture content of the polyol composition is 1.8% by mass or less. [2] The polyol composition according to [1], wherein the catalyst contains a metal-based urethanization catalyst. [3] The polyol composition according to any one of [1] or [2], wherein the catalyst contains a trimerization catalyst. [4] The polyol composition according to any one of [1] to [3], wherein the polyol composition contains a filler. [5] A flame-retardant urethane resin composition prepared by mixing the polyol composition according to any one of [1] to [4] with a polyisocyanate composition containing a polyisocyanate compound, wherein the flame-retardant urethane resin composition does not contain a foam stabilizer. [6] The flame-retardant urethane resin composition according to [5], wherein the cream time of the flame-retardant urethane resin composition is 10 seconds or less. [7] The flame-retardant urethane resin composition according to [5] or [6], which is for spraying applications. [8] A polyurethane foam formed by foaming the flame-retardant urethane resin composition according to any one of [5] to [7].

Advantages of the Invention

[0007] Since the present invention is a polyol composition that does not use a foam stabilizer, it suppresses the bleed-out of the foam stabilizer on the surface of the formed polyurethane foam. Also, by removing the foam stabilizer component that can be a combustion element, it is possible to prevent the polyurethane foam from being easily combustible. In addition, it suppresses the coarsening of cells and obtains a polyurethane foam excellent in heat insulation properties.

Embodiments for Carrying Out the Invention

[0008] [Polyol Composition] The present invention is a polyol composition containing a polyol compound, a liquid flame retardant, a catalyst, and a foaming agent, which does not contain a foam stabilizer and has a moisture content of 1.8% by mass or less.

[0009] [Foam Stabilizer] The polyol composition of the present invention does not contain a foam stabilizer. By not containing a foam stabilizer, it suppresses the bleed-out of the foam stabilizer on the surface of the polyurethane foam formed when, for example, a silicone-based foam stabilizer is used. Also, by removing the foam stabilizer component that can be a combustion element, it is possible to prevent the polyurethane foam from being easily combustible. Here, the foam stabilizer has a foam stabilizing function in polyurethane foaming and means a foam stabilizer generally used in the production of polyurethane foams. Examples of the foam stabilizer include silicone-based foam stabilizers and non-silicone-based foam stabilizers. Silicone foam stabilizers are compounds having a polysiloxane chain and a polyoxyalkylene chain, and may have a block structure of a polysiloxane chain and a polyoxyalkylene chain, or a structure in which a polyoxyalkylene chain is grafted as a side chain to the polysiloxane chain of the main chain. Specific product names of the silicone foam stabilizers include, for example, SH-193, SF-2937F, SF-2945F, etc. manufactured by Toray Dow Corning Co., Ltd. Non-silicone foam stabilizers refer to foam stabilizers other than silicone foam stabilizers, and examples include acrylic surfactants, etc. The acrylic surfactants include, for example, acrylic polymers having a polar group in the side chain, etc.

[0010] <Foaming agent> Specific examples of the foaming agent include, for example, water, low-boiling hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, hydrofluoroolefins, etc. Further, as the foaming agent, organic physical foaming agents such as mixtures of these compounds, and inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas, carbon dioxide gas, etc. are included. Examples of the above low-boiling hydrocarbons include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, etc. Examples of the above chlorinated aliphatic hydrocarbon compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, etc. Examples of the above fluorine compounds include CHF3, CH2F2, CH3F, etc. Examples of the above hydrochlorofluorocarbon compounds include trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)), etc. Examples of the hydrofluorocarbon include HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane), and the like. Examples of the ether compound include diisopropyl ether and the like. Examples of the hydrofluoroolefin include HFO-1233zd(E) (trans-1-chloro-3,3,3-trifluoropropene), HFO-1234yf (2,3,3,3-tetrafluoro-1-propene), HFO-1336mzz(Z) (cis-1,1,1,4,4,4-hexafluorobut-2-ene), HFO-1224yd(Z), and the like.

[0011] Among the above, as the blowing agent, hydrofluoroolefins, water, etc. are preferable, and it is more preferable to use hydrofluoroolefins and water in combination.

[0012] From the viewpoint of making the density of the polyurethane foam fall within a desired range, the amount of the hydrofluoroolefin used as the blowing agent is preferably 3 to 60 parts by mass, more preferably 8 to 57 parts by mass, and still more preferably 19 to 49 parts by mass with respect to 100 parts by mass of the polyol compound. As the water used as the blowing agent, for example, ion-exchanged water, distilled water, etc. can be appropriately used. From the viewpoints of adjusting the isocyanate index to a certain level or more and adjusting the density of the polyurethane foam to a desired range, the amount of water with respect to 100 parts by mass of the polyol compound is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.2 to 2.5 parts by mass.

[0013] <Moisture content> The moisture content in the polyol composition of the present invention is 1.8% by mass or less. When the moisture content exceeds 1.8% by mass, the cells in the polyurethane foam become partially cracked, etc., resulting in coarser cells and a tendency for the heat insulation property to deteriorate. From such a viewpoint, the above moisture content is preferably 1.3% by mass or less, and more preferably 1% by mass or less. Regarding the lower limit of the above moisture content, there is no particular limitation. However, when the polyol composition is mixed with the polyisocyanate composition, it is preferably contained with a certain amount or more of moisture from the viewpoint of ensuring good foamability and sprayability. The moisture content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more. The moisture content is a value measured using a Karl Fischer moisture measuring device for the polyol composition.

[0014] <Polyol compound> The polyol compound is not particularly limited. For example, polyether polyol, polyester polyol, etc. may be mentioned. From the viewpoint of improving the flame retardancy of the polyurethane foam, the polyol compound preferably contains polyester polyol. Also, from the viewpoint of improving the flame retardancy, the use of halogen-containing polyol, phosphorus-containing polyol, etc. is also preferable. From such a viewpoint, among 100 parts by mass of the polyol compound, it is preferably 20 parts by mass or more of polyester polyol, more preferably 50 parts by mass or more, further preferably 80 parts by mass or more, and particularly preferably 100 parts by mass.

[0015] When using two or more types of polyol compounds, as the hydroxyl value of the polyol compound, the average hydroxyl value according to the blending ratio of the two or more types of polyol compounds may be used. For example, when using two types of polyols (d1) and polyol (d2) as the polyol compound, if the hydroxyl value of polyol (d1) is X1, the blending ratio is m1, the hydroxyl value of polyol (d2) is X2, and the blending ratio is m2, the average hydroxyl value is represented by the following formula. The blending ratio is based on mass. Average hydroxyl value (mgKOH / g) = X1 × (m1 / (m1 + m2)) + X2 × (m2 / (m1 + m2)) From the viewpoint of improving the flame retardancy of the polyurethane foam, the average hydroxyl value of the polyol compound used in the present invention is preferably 100 to 500 mgKOH / g, more preferably 150 to 450 mgKOH / g, and even more preferably 200 to 400 mgKOH / g. The hydroxyl value is a value measured in accordance with JIS K1557-1:2007.

[0016] (Polyester polyol) The polyester polyol may be an aromatic ring-containing polyester polyol or an aliphatic polyester polyol. However, considering the flame retardancy of the resulting polyurethane foam, it is preferable to use an aromatic ring-containing polyester polyol. The aromatic ring-containing polyester polyol is preferably a condensate of an aromatic dicarboxylic acid such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), naphthalenedicarboxylic acid, and glycol. Among them, from the viewpoint of enhancing the flame retardancy of the polyurethane foam, the polyol compound preferably contains a phthalic acid-based polyester polyol that is a condensate of phthalic acid and glycol, and more preferably contains a p-phthalic acid-based polyester polyol that is a condensate of p-phthalic acid and glycol. The glycol is not particularly limited, but it is preferable to use a low molecular weight aliphatic glycol known as a constituent component of polyester polyols such as ethylene glycol, propylene glycol, and diethylene glycol.

[0017] The hydroxyl value of the polyester polyol is preferably 100 to 500 mgKOH / g, more preferably 150 to 450 mgKOH / g, and even more preferably 200 to 400 mgKOH / g.

[0018] (Polyether polyol) Polyether polyol is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of alkylene oxide to an initiator having two or more active hydrogen atoms. Specific examples of the initiator include aliphatic polyhydric alcohols (such as glycols like ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, cyclohexanedimethanol, etc., triols like trimethylolpropane, glycerin, etc., tetrafunctional alcohols like pentaerythritol, high-functional alcohols like sucrose and sorbitol), aliphatic amines (such as alkylene diamines like ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, etc., alkanolamines like monoethanolamine, diethanolamine), aromatic amines (such as aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, Mannich condensates, etc.). Among these, the polyether polyol produced using an initiator having an aromatic ring is a polyether polyol having an aromatic ring. For example, the polyether polyol produced using an aromatic amine as an initiator is a polyether polyol having an aromatic ring. Among the polyether polyols having an aromatic ring, tolylenediamine-based polyether polyols, Mannich-based polyether polyols, etc. can be preferably used.

[0019] Tolylenediamine-based polyether polyol is a tolylenediamine-based polyether polyol produced using tolylenediamine as an initiator. The above-mentioned Mannich polyether polyol is obtained by using the Mannich reaction and is a Mannich condensate having two or more hydroxyl groups in the molecule or a polyether polyol obtained by adding an alkylene oxide to such a Mannich condensate. More specifically, it is a polyether polyol obtained by the Mannich reaction of at least one of phenol and its alkyl-substituted derivatives, formaldehyde, and alkanolamine, or by ring-opening addition polymerization of at least one of ethylene oxide and propylene oxide to this compound.

[0020] The hydroxyl value of the polyether polyol is preferably 200 to 2000 mgKOH / g, more preferably 300 to 1000 mgKOH / g.

[0021] <Catalyst> The polyol composition contains a catalyst. Examples of the catalyst include urethanization catalysts, trimerization catalysts, foaming catalysts, etc. The trimerization catalyst is a catalyst that promotes the trimerization to form an isocyanurate bond. From the viewpoint of improving the flame retardancy of the polyurethane foam and the foamability of the flame-retardant urethane resin composition described later, it is preferable that the catalyst contains a trimerization catalyst.

[0022] (Trimerization catalyst) As the trimerization catalyst, nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine, potassium acetate, potassium 2-ethylhexanoate, alkali metal carboxylates such as potassium octylate, tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt, quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetraphenylammonium salt, triethylmonomethylammonium salt, and quaternary ammonium carboxylates can be used. Preferable specific examples of the carboxylic acid in the above 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. 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 carboxylates is preferable, and it is preferable to use an alkali metal carboxylate and a quaternary ammonium carboxylate in combination.

[0023] The content of the trimerization catalyst in the polyol composition is preferably 1 to 30 parts by mass, more preferably 2 to 15 parts by mass, and still more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the polyol compound.

[0024] (Urethanization catalyst) In addition, in the present invention, the catalyst may contain a urethanization catalyst. In that case, it is more preferable to include both the above-described trimerization catalyst and urethanization catalyst. The urethanization catalyst is a catalyst that promotes the reaction between the polyol compound and the polyisocyanate compound. Specifically, amino compounds, metal-based urethanization catalysts, etc. can be mentioned, and among them, metal-based urethanization catalysts are preferable.

[0025] Examples of amino compounds include imidazole compounds such as 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group, 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. Among the amino compounds, imidazole compounds are preferred.

[0026] Examples of metal-based urethanization catalysts include tin compounds, bismuth compounds, and acetylacetone metal salts. Among these, from the perspective of enhancing the activity at the initial stage of the reaction between the polyol compound and the polyisocyanate compound, one or more selected from bismuth compounds and tin compounds are preferred, and bismuth compounds are more preferred.

[0027] Examples of tin compounds include stannous octylate, dibutyltin diacetate, dibutyltin dilaurate, etc. Examples of bismuth compounds include bismuth neodecanoate, bismuth 2-ethylhexanoate, etc. Examples of acetylacetone metal salts include aluminum acetylacetonate, iron acetylacetonate, copper acetylacetonate, zinc acetylacetonate, beryllium acetylacetonate, chromium acetylacetonate, indium acetylacetonate, manganese acetylacetonate, molybdenum acetylacetonate, titanium acetylacetonate, cobalt acetylacetonate, vanadium acetylacetonate, zirconium acetylacetonate, etc. From the viewpoint of reacting the polyol composition and the polyisocyanate composition at an appropriate rate, the catalyst in the present invention preferably contains the above-mentioned bismuth compound.

[0028] The content of the urethanization catalyst in the polyol composition is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, still more preferably 0.05 to 3 parts by mass, and particularly preferably 0.07 to 1 part by mass with respect to 100 parts by mass of the polyol compound. When the content of the urethanization catalyst is not less than the above lower limit value, the formation of urethane bonds is likely to occur, the reaction proceeds rapidly, and the foamability is good. On the other hand, when the content of the urethanization catalyst is not more than the above upper limit value, it is preferable because the reaction rate is easy to control.

[0029] (Foaming catalyst) The catalyst used in the polyol composition of the present invention may contain a foaming catalyst. Therefore, the catalyst may contain a trimerization catalyst, a urethanization catalyst, and a foaming catalyst. By using a foaming catalyst, the urethane resin composition foams and the foamability becomes good. Examples of the foaming catalyst include amine-based foaming catalysts. The amine-based foaming catalyst is preferably a compound having two or more nitrogen atoms in the molecule, or a compound having at least one nitrogen atom and at least one oxygen atom in the molecule, and more preferably a guanidine derivative.

[0030] The guanidine derivative is a compound having a guanidine skeleton, and specific examples thereof include tetraalkylguanidine. Tetraalkylguanidine is N,N,N’,N’-tetraalkylguanidine in which a total of four hydrogen atoms bonded to the nitrogen atoms at the 1st and 3rd positions are each independently substituted with an alkyl group. Specific examples of tetraalkylguanidine include compounds represented by the following general formula (1).

[0031] [Chemical formula] (In general formula (1), R1, R2, R3, and R4 each independently represent an alkyl group.)

[0032] The alkyl groups of R1, R2, R3, and R4 are, for example, alkyl groups having 1 to 16 carbon atoms, preferably 1 to 4 carbon atoms. The alkyl group may be linear, branched, or have a cyclic structure. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, isopentyl group, sec-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, etc. Among these, from the viewpoints of stability and foamability, the methyl group is preferred, and N,N,N',N'-tetramethylguanidine in which all of the above four alkyl groups are methyl groups is more preferred. From the viewpoint of foamability, the content of the foaming catalyst in the polyol composition is preferably 0.02 to 10 parts by mass, more preferably 0.04 to 5 parts by mass, and still more preferably 0.06 to 2 parts by mass with respect to 100 parts by mass of the polyol compound.

[0033] <Liquid flame retardant> The polyol composition in the present invention contains a liquid flame retardant from the viewpoint of improving the flame retardancy of the obtained polyurethane foam. Among liquid flame retardants, phosphate ester-based flame retardants are particularly preferred. When a phosphate ester-based flame retardant is used, the flame retardancy of the polyurethane foam can be improved, and the viscosity of the polyol composition can be appropriately controlled even when a filler described later is used. Here, the liquid flame retardant is a flame retardant that is liquid at 23°C.

[0034] Examples of the phosphate ester-based flame retardant include monophosphate ester, condensed phosphate ester, etc. The monophosphate ester is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tris(β-chloropropyl) phosphate, and the like. The condensed phosphate ester is not particularly limited, and examples thereof include resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade name CR-741), aromatic condensed phosphate ester (trade name CR747), and the like.

[0035] From the viewpoints of flame retardancy and foamability, the content of the liquid flame retardant is preferably 5 to 100 parts by mass, more preferably 12 to 90 parts by mass, still more preferably 20 to 75 parts by mass, and even more preferably 30 to 60 parts by mass with respect to 100 parts by mass of the polyol compound.

[0036] <Filler> The polyol composition in the present invention may contain a filler. The filler is contained as a solid content in the polyol composition and is generally a component present in granular or powdery form. By containing the filler, various physical properties such as mechanical strength and flame retardancy can be improved depending on the type of the filler. The filler may be a solid at normal temperature (23°C) and normal pressure (1 atm) and may be a component that does not dissolve in the flame-retardant urethane resin composition.

[0037] It is preferable to contain a solid flame retardant as the filler. Preferred solid flame retardants include boron-based flame retardants, bromine-based flame retardants, phosphate-containing flame retardants, antimony-containing flame retardants, phosphinic acid-based flame retardants, metal hydroxide-based flame retardants, red phosphorus, and needle-like fillers. Among these, from the viewpoint of improving the flame retardancy of the polyurethane foam, red phosphorus, needle-like fillers, and the like are preferable.

[0038] (Boron-based flame retardant) As the boron-based flame retardant, specifically, there may be mentioned alkali metal borates such as lithium borate, sodium borate, potassium borate, cesium borate, etc., alkaline earth metal borates such as magnesium borate, calcium borate, barium borate, etc., zirconium borate, zinc borate, aluminum borate, ammonium borate, etc. Among them, zinc borate is preferred.

[0039] (Bromine-based flame retardant) The bromine-based flame retardant is not particularly limited as long as it is a compound containing bromine in its molecular structure, for example, aromatic brominated compounds and the like can be mentioned. Specific examples of the aromatic brominated compound include, for example, monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylene bis(pentabromophenyl), ethylene bis(tetrabromophthalimide), tetrabromobisphenol A, etc., brominated polycarbonates such as polycarbonate oligomers produced from brominated bisphenol A, copolymers of the said polycarbonate oligomer and bisphenol A, brominated epoxy compounds such as diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin, monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, poly(brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, condensates of cyanuric chloride and brominated phenols, brominated polystyrenes such as brominated (polystyrene), poly(brominated styrene), crosslinked brominated polystyrene, halogenated bromine compound polymers such as crosslinked or non-crosslinked brominated poly(α-methylstyrene). Among these, ethylene bis(pentabromophenyl), ethylene bis(tetrabromophthalimide), hexabromobenzene, etc. are preferred.

[0040] (phosphate-containing flame retardants) Examples of phosphate-containing flame retardants include those containing phosphoric acid and a metal of Groups IA to IVB of the periodic table, At least one metal or compound selected from ammonia, aliphatic amines, and aromatic amines Examples of suitable salts include phosphates, which are salts of phosphates with phosphate groups. There is no particular limitation on the phosphoric acid, but examples include various phosphoric acids such as monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid. It can be obtained. Examples of the metals of Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), aluminum, etc. Examples of the aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, etc. Examples of the aromatic amines include pyridine, triazine, melamine, etc. The above phosphate-containing flame retardants are treated with a silane coupling agent and coated with melamine resin. A known water resistance improving treatment such as the above may be applied.

[0041] Specific examples of phosphate-containing flame retardants include monophosphates, pyrophosphates, and polyphosphates. The monophosphate is not particularly limited, but examples thereof include ammonium phosphate and phosphate dihydrate. ammonium salts such as monoammonium and diammonium hydrogen phosphate, monosodium phosphate, Disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite sodium salts such as sodium hypophosphite, monopotassium phosphate, dipotassium phosphate, Potassium phosphate tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, potassium hypophosphite, etc. Lithium salts, monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite lithium salts such as lithium diphosphite and lithium hypophosphite, barium dihydrogen phosphate, Barium salts such as barium hydrogen phosphate, tribarium phosphate, and barium hypophosphite, monobasic magnesium phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium hypophosphite and other magnesium salts, calcium dihydrogen phosphate, calcium hydrogen phosphate, tribasic calcium phosphate, calcium hypophosphite and other calcium salts, zinc phosphate, zinc phosphite, zinc hypophosphite and other zinc salts, etc. are mentioned.

[0042] The polyphosphates are not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, aluminum polyphosphate, and the like. The phosphate-containing flame retardant may be used alone or in combination of two or more.

[0043] (Antimony-containing flame retardant) Examples of the antimony-containing flame retardant used in the present invention include antimony oxide, antimonate, pyroantimonate, and the like. Examples of antimony oxide include antimony trioxide, antimony pentoxide, and the like. Examples of antimonate include sodium antimonate, potassium antimonate, and the like. Examples of pyroantimonate include sodium pyroantimonate, potassium pyroantimonate, and the like. The antimony-containing flame retardant is preferably antimony oxide. The antimony-containing flame retardant may be used alone or in combination of two or more. It can be used.

[0044] (Phosphinic acid-based flame retardant) Examples of phosphinic acid-based flame retardants include phosphinic acid, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid, and the like.

[0045] (Metal hydroxide-based flame retardant) Examples of metal hydroxide-based flame retardants include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, and the like. The metal hydroxide-based flame retardants may be used alone or in combination of two or more.

[0046] (Red phosphorus) The red phosphorus may consist of red phosphorus alone, or may be a mixture or coating of red phosphorus with a resin, metal hydroxide, metal oxide, etc.

[0047] (Acicular filler) Examples of acicular fillers include potassium titanate whisker, aluminum borate whisker, magnesium-containing whisker, silicon-containing whisker, wollastonite, sepiolite, zonolite, elestaidite, 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, and the like. One or more of these acicular fillers can be used.

[0048] Further, as the filler, an inorganic filler other than the above-mentioned flame retardant may be used. Examples of the inorganic filler include 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, clay, mica, montmorillonite, bentonite, activated clay, imogolite, sericite, glass beads, silica balloon, aluminum nitride, boron nitride, silicon nitride, graphite, carbon balloon, charcoal powder, various metal powders, magnesium sulfate, lead zirconate titanate, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash, etc., which can be appropriately used. The inorganic filler may be used alone or in combination of two or more kinds.

[0049] The content of the filler is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, still more preferably 30 parts by mass or more, and preferably 90 parts by mass or less, more preferably 85 parts by mass or less, based on 100 parts by mass of the polyol compound. When the content of the filler is equal to or higher than these lower limit values, it becomes easier to exhibit the functions according to the type of the filler used. For example, when a solid flame retardant is used as the filler, the flame retardancy of the polyurethane foam is likely to be improved. When the content of the filler is equal to or lower than these upper limit values, clogging of the spraying device and the like are suppressed, and the sprayability can be improved.

[0050] The polyol composition may not contain the above-mentioned filler. When not containing the filler, sediment is less likely to occur during storage, the handleability is excellent, and wear of tools used during use can be suppressed.

[0051] <Other Components> The polyol composition can contain one or more selected from antioxidants such as phenolic, amine-based, and sulfur-based antioxidants, heat stabilizers, metal damage preventives (metal deactivators), antistatic agents, heat and light stabilizers, crosslinking agents, lubricants, softeners, plasticizers, pigments, dyes, tackifier resins, etc., within a range not impairing the object of the present invention, as well as tackifiers such as polybutene and petroleum resins.

[0052] <Method for producing polyol composition> There is no particular limitation on the method for producing the polyol composition of the present invention. For example, it can be produced by stirring each component at about 20 to 40 °C for about 30 seconds to 20 minutes using a homodisper or the like.

[0053] [Flame-retardant urethane resin composition] The flame-retardant urethane resin composition of the present invention contains a polyol composition containing the above-described polyol compound, flame retardant, catalyst, and foaming agent, and a polyisocyanate composition containing a polyisocyanate compound, and is obtained by mixing these. Further, the polyurethane foam of the present invention is a reaction product obtained by reacting and foaming the flame-retardant urethane resin composition.

[0054] <Polyisocyanate compound> As the polyisocyanate compound contained in the polyisocyanate composition of the present invention, various polyisocyanate compounds such as aromatic, alicyclic, and aliphatic polyisocyanate compounds having two or more isocyanate groups can be used. The polyisocyanate compound may be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use liquid diphenylmethane diisocyanate (MDI) because of its ease of handling, fast reaction speed, excellent physical properties of the resulting polyurethane foam, and low cost. Examples of the liquid MDI include crude MDI (also referred to as polymeric MDI). Specific commercially available products of the liquid MDI include "44V-10", "44V-20" (manufactured by Sumika Covestro Polyurethane Co., Ltd.), "Millionate MR-200" (Nippon Polyurethane Industry Co., Ltd.), and the like. Also, uretonimine-containing MDI (for example, commercially available product "Millionate MTL": manufactured by Nippon Polyurethane Industry Co., Ltd.) may be used. In addition, a part of the isocyanate active groups in the isopolyisocyanate compound may be reacted with a hydroxyl group-containing compound to perform a treatment for enhancing the affinity with the polyol in advance. In addition to the liquid MDI, other polyisocyanate compounds may be used in combination. As the polyisocyanate compound to be used in combination, polyisocyanate compounds known in the technical field of polyurethanes can be used without limitation. The polyisocyanate composition may consist only of the polyisocyanate compound, but may appropriately contain known additives used in combination with the polyisocyanate compound. However, like the polyol composition, the polyisocyanate composition does not contain a foam stabilizer. Therefore, the flame-retardant urethane resin composition also does not contain a foam stabilizer.

[0055] The mixing ratio of the polyol composition and the polyisocyanate composition of the present invention is preferably adjusted so that the isocyanate index of the flame-retardant urethane resin composition is as follows. When the flame-retardant urethane resin composition is used for spraying applications, the volume ratio of the polyisocyanate composition to the polyol composition (polyisocyanate composition / polyol composition) is not particularly limited, but is preferably 0.8 to 1.2, more preferably 0.9 to 1.1.

[0056] The isocyanate index of the flame-retardant urethane resin composition of the present invention is preferably from 150 to 700, more preferably from 200 to 600. When the isocyanate index is not less than these lower limit values, it is easy to obtain a polyurethane foam having high flame retardancy. When the isocyanate index is not more than these upper limit values, the foamability during foam formation can be improved. The isocyanate index (INDEX) is a value obtained by multiplying the value obtained by dividing the number of moles of isocyanate groups in the polyisocyanate by the total number of moles of active hydrogen groups of the hydroxyl groups of the polyol and water used as the blowing agent by 100, and is calculated by the following method.

[0057] INDEX = number of equivalents of isocyanate ÷ (number of equivalents of polyol + number of equivalents of water) × 100 Here, Number of equivalents of isocyanate = amount of polyisocyanate used × NCO content (%) × 100 / NCO molecular weight Number of equivalents of polyol = OHV × amount of polyol used ÷ molecular weight of KOH, where OHV is the hydroxyl value (mgKOH / g) of the polyol. Number of equivalents of water = amount of water used × number of OH groups of water / molecular weight of water In the above formulas, the unit of the amount used is weight (g), the molecular weight of the NCO group is 42, the NCO content is the ratio of the NCO group in the polyisocyanate compound expressed as mass%, and for convenience of unit conversion in the above formulas, the molecular weight of KOH is taken as 56100, the molecular weight of water is 18, and the number of OH groups of water is 2.

[0058] Since the flame-retardant urethane resin composition of the present invention cures by the reaction of a polyol compound and a polyisocyanate compound, its viscosity changes with time. Therefore, before using the composition, the polyol composition and the polyisocyanate composition should be stored separately to prevent the reaction and curing of the polyisocyanate and the polyol. And when manufacturing a urethane foam, it is advisable to mix the polyol composition and the polyisocyanate composition.

[0059] <Cream time> The flame-retardant urethane resin composition of the present invention preferably has a cream time of 10 seconds or less. When the cream time is 10 seconds or less, the polyol composition and the polyisocyanate compound react at an appropriate rate, and when the polyurethane foam is sprayed onto an object, it is possible to prevent the occurrence of dripping problems. In addition, the scattering of the low thermal conductivity foaming agent (for example, hydrofluoroolefin) contained in the resin composition can be reduced and confined in the foam, improving the heat insulation property. From these viewpoints, the cream time of the flame-retardant urethane resin composition is preferably 8 seconds or less, more preferably 7 seconds or less. The lower limit value of the cream time is not particularly limited, but is preferably 1 second or more, more preferably 2 seconds or more. The cream time can be adjusted to a desired value by adjusting the type and amount of the catalyst contained in the polyol composition. The cream time is a value measured by the cup foaming method. Specifically, it is measured as follows. Adjust the liquid temperatures of the polyol composition and the polyisocyanate composition constituting the flame-retardant urethane resin composition of the present invention to 10°C, respectively. Then, in a room at 23°C, the polyol composition and the polyisocyanate composition adjusted to 10°C are put into a 500 mL cup so as to form a mixed liquid with a total amount of 60 g at a predetermined mixing ratio. Thereafter, the mixed liquid is immediately stirred at 8000 rpm for 2 seconds with a lab disperser (Primix Corporation's high-speed disperser Homodisper 2.5 type). Using the time when stirring is started as the measurement start time (0 second), the time (seconds) until the mixed liquid changes color and the liquid surface starts to rise due to foaming is measured, and this is defined as the cream time. The above-mentioned predetermined mixing ratio means the mixing ratio of the polyol composition and the polyisocyanate composition when preparing the flame-retardant urethane resin composition of the present invention.

[0060] <Gel time> The gel time of the flame-retardant urethane resin composition of the present invention is not particularly limited, but it is preferably 20 seconds or less. When the gel time is 20 seconds or less, the balance between the urethane resin formation rate and the foam stabilizing power becomes good, and it is possible to effectively prevent the cells in the polyurethane foam from becoming coarse due to partial cracking of the cells, etc., and it becomes easier to maintain the heat insulation property. From the viewpoint of improving the heat insulation property of the formed polyurethane foam, the gel time of the flame-retardant urethane resin composition is more preferably 18 seconds or less, and even more preferably 15 seconds or less. The gel time can be adjusted to a desired value by adjusting the type and amount of the catalyst contained in the polyol composition, etc. The gel time is a value measured by the cup foaming method. Specifically, it is measured as follows. Adjust the liquid temperatures of the polyol composition and the polyisocyanate composition constituting the flame-retardant urethane resin composition of the present invention to 10 °C, respectively. Then, in a room at 23 °C, the polyol composition and the polyisocyanate composition adjusted to 10 °C are put into a 500 mL cup so as to form a mixed liquid with a total amount of 60 g at a predetermined mixing ratio. Thereafter, the mixed liquid is immediately stirred at 8000 rpm for 2 seconds with a Lab Disper (Homodisper 2.5 type, a high-speed disperser manufactured by PRIMIX). Using the time when stirring is started as the measurement start time (0 second), the time (seconds) until the foam draws a thread on a rod pierced into the foam during foaming is measured, and this is taken as the gel time. Note that the above-mentioned predetermined mixing ratio means the mixing ratio of the polyol composition and the polyisocyanate composition when preparing the flame-retardant urethane resin composition of the present invention.

[0061] [Polyurethane foam] The polyurethane foam of the present invention is formed from the above-mentioned flame-retardant urethane resin composition, and specifically, it is obtained by foaming and curing the flame-retardant urethane resin composition.

[0062] (Density) The density of the polyurethane foam is not particularly limited, but it is 20 to 200 kg / m 3Preferably, it is in the range of. By setting the density to 200 kg / m 3 or less, the polyurethane foam becomes lightweight and the workability for construction on structures is enhanced. Also, by setting it to 20 kg / m 3 or more, it becomes easier to exhibit the desired flame retardancy. From these viewpoints, the density of the polyurethane foam is preferably in the range of 20 to 100 kg / m 3 more preferably in the range of 23 to 80 kg / m 3 even more preferably in the range of. The density of the polyurethane foam can be measured in accordance with JIS K7222.

[0063] The polyurethane foam of the present invention can be obtained by mixing a polyol composition and a polyisocyanate composition to prepare a flame-retardant urethane resin composition and foaming this. The mixing and foaming of each component can be carried out by known methods. For example, it can be obtained using known apparatuses such as high-pressure foam machines, low-pressure foam machines, spray foam machines, and hand mixers.

[0064] (Use) The use of the flame-retardant urethane resin composition of the present invention and the polyurethane foam formed by foaming the composition is not particularly limited, but it can be used for filling cavities in structures such as buildings, furniture, automobiles, trains, ships, etc., or for spraying on the structures. Among them, it is preferably used for spraying on structures, that is, as a flame-retardant urethane resin composition for spraying. Spraying can be carried out using a spraying device (for example, A-25 manufactured by GRACO) and a spray gun (for example, D gun manufactured by Gasmer). Spraying can be carried out by adjusting the temperature of the polyol composition and the polyisocyanate composition contained in separate containers in the spraying device, causing the two to collide and mix at the tip of the spray gun, and atomizing the mixed liquid by air pressure. The volume ratio of the polyisocyanate composition to the polyol composition (polyisocyanate composition / polyol composition) in the mixed liquid is not particularly limited, but is usually 0.8 to 1.2, and more generally 0.9 to 1.1. Spraying devices and spray guns are well-known, and commercially available products can be used. Also, the setting of the stock solution temperature, pressure, etc. can adapt to the spraying conditions of general urethane foam.

Example

[0065] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

[0066] [Materials Used] Details of each component used in each example and comparative example are as follows. <Polyol Composition> (Polyol Compound) · p-Phthalic acid polyester polyol 1 (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RFK-505, hydroxyl value = 250 mgKOH / g) · p-Phthalic acid polyester polyol 2 (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mgKOH / g)

[0067] (Phosphate ester (liquid flame retardant)) · Tris(β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP) (Foam stabilizer) · Silicone-based foam stabilizer (Toray Dow Corning Co., Ltd. "SH-193")

[0068] (Catalyst) · Trimerization catalyst 1 Metal catalyst, potassium 2-ethylhexanoate (manufactured by Evonik Japan Co., Ltd., product name: DABCO® K-15) concentration 70 - 80 mass% · Trimerization catalyst 2 Quaternary ammonium salt, tetramethylammonium 2,2-dimethylpropanoate (manufactured by Evonik Japan Co., Ltd., product name: DABCO® TMR-7) concentration 45 - 55 mass% · Foaming catalyst N,N,N',N'-tetramethylguanidine (manufactured by Evonik Japan, product name "POLYCAT 201", a mixture with water and ethylene glycol (60% by mass of N,N,N',N'-tetramethylguanidine, 32% by mass of ethylene glycol, 8% by mass of water)) · Urethanization catalyst Transition metal salt, bismuth 2-ethylhexanoate (manufactured by Nitto Kasei Co., Ltd., product name: BI28) with a concentration of 81 - 90% by mass

[0069] (Filler) · Filler Red phosphorus (manufactured by Phosphorus Chemical Industry Co., Ltd., product name: Nova Excel 140), a solid flame retardant · Filler Wollastonite (SiO2·CaO) (manufactured by Kinsai Mateck Co., Ltd., product name: SH - 1250), a solid flame retardant

[0070] (Blowing agent) · Water · HFO - 1233zd <Hydrofluoroolefin> (manufactured by Honeywell, product name: Solstice LBA)

[0071] <Polyisocyanate compound> · Polymeric MDI (manufactured by Tosoh Corporation, product name: Millionate MR - 200)

[0072] The methods for measuring and evaluating each physical property of the polyurethane foam are as follows. [Moisture content] The polyol composition was measured using a Karl Fischer moisture measuring device (manufactured by Kyoto Electronics Industry Co., Ltd., product name: MKV - 710).

[0073] [Cream time (CT)] The liquid temperatures of the polyol composition having the composition described in Table 1 and the polyisocyanate composition comprising a polyisocyanate compound (MDI) were each adjusted to 10°C. Then, in a room at 23°C, the polyol composition and the polyisocyanate composition adjusted to 10°C were put into a 500 mL cup so as to form a mixed liquid with a total amount of 60 g at a mixing ratio such that the isocyanate index was as shown in the table. Thereafter, the mixed liquid was immediately stirred at 8000 rpm for 2 seconds using a Lab Dispa (homodisper 2.5 type, a high-speed disperser manufactured by PRIMIX). Using the time when stirring was started as the measurement start time (0 seconds), the time (seconds) until the liquid surface started to rise due to foaming and the mixed liquid changed color was measured, and this was defined as the cream time.

[0074] [Gel time (GT)] The liquid temperatures of the polyol composition having the composition described in Table 1 and the polyisocyanate composition comprising a polyisocyanate compound (MDI) were each adjusted to 10°C. Then, in a room at 23°C, the polyol composition and the polyisocyanate composition adjusted to 10°C were put into a 500 mL cup so as to form a mixed liquid with a total amount of 60 g at a mixing ratio such that the isocyanate index was as shown in the table. Thereafter, the mixed liquid was immediately stirred at 8000 rpm for 2 seconds using a Lab Dispa (homodisper 2.5 type, a high-speed disperser manufactured by PRIMIX). Using the time when stirring was started as the measurement start time (0 seconds), the time (seconds) until the foam on the stick pierced into the foam during foaming started to draw a thread was measured, and this was defined as the gel time.

[0075] [Observation of the cell state of the polyurethane foam] The polyurethane foams produced in each example and comparative example were visually observed, and when the cells were fine and there was no noticeable foam breakage, it was evaluated as "〇", and when the cells were cracked or in a rough state, it was evaluated as "×".

[0076] [External contamination (bleed)] A line was drawn on the surface of the obtained polyurethane foam with a magic marker (manufactured by Zebra, "Macky Ultra-Fine" oil-based black), and those that did not repel the magic ink were evaluated as "〇", and those that repelled it were evaluated as "×". When the magic ink is repelled, it means that a foam stabilizer or the like has bled out on the surface of the polyurethane foam, indicating that the object to be used is likely to be contaminated.

[0077] [Examples 1 to 4, Comparative Examples 1 to 2] A polyol composition obtained with the formulation shown in Table 1 and a polyisocyanate composition composed of a polyisocyanate compound were stirred at a liquid temperature of 10 °C and 8000 rpm for 2 seconds so that the total was 200 g to obtain a flame-retardant urethane resin composition. Then, the flame-retardant urethane resin composition was sprayed into a box having a size of 180 mm × 180 mm and a depth of 100 mm to form a polyurethane foam. Regarding the polyurethane foam thus formed, the above-mentioned "observation of the cell state of the polyurethane foam" and "external contamination (bleed)" were evaluated.

[0078]

Table 1

[0079] Note that the parts by mass of each catalyst are parts by mass as a product.

[0080] Since the polyol compositions of the respective examples did not contain a foam stabilizer, the obtained polyurethane foams had little bleed-out on the surface and were further difficult to burn. Also, despite not containing a foam stabilizer, the cell state was good, the thermal conductivity was low, and the heat insulation property was excellent. On the other hand, although the polyol composition of Comparative Example 1 did not contain a foam stabilizer, since the moisture content value exceeded 1.8% by mass, the cell state was rough and the heat insulation property was poor. Also, although the polyol composition of Comparative Example 2 had a moisture content value of 1.8% by mass or less, since it contained a foam stabilizer, the polyurethane foams obtained from the composition were all easily combustible, and furthermore, a large amount of bleed-out occurred on the surface.

Claims

1. A flame-retardant urethane resin composition comprising a polyol composition and a polyisocyanate composition, and used for producing a heat insulating material by mixing the polyol composition and the polyisocyanate composition, wherein the polyol composition contains a polyol compound, a liquid flame retardant, a catalyst, and a foaming agent, the polyisocyanate composition contains a polyisocyanate compound, the flame-retardant urethane resin composition does not contain a foam stabilizer, the liquid flame retardant is a phosphate ester-based flame retardant, and the water content of the polyol composition is 1.8% by mass or less (however, excluding those containing an acrylic-based surface conditioner).

2. The flame-retardant urethane resin composition according to Claim 1, wherein the catalyst contains a metal-based urethanization catalyst.

3. The flame-retardant urethane resin composition according to any one of Claims 1 and 2, wherein the catalyst contains a trimerization catalyst.

4. The flame-retardant urethane resin composition according to any one of Claims 1 to 3, wherein the polyol composition contains a filler.

5. The flame-retardant urethane resin composition according to any one of Claims 1 to 4, wherein the cream time of the flame-retardant urethane resin composition is 10 seconds or less.

6. The flame-retardant urethane resin composition according to any one of Claims 1 to 5, wherein the isocyanate index of the flame-retardant urethane resin composition is 150 to 700.

7. The flame-retardant urethane resin composition according to any one of Claims 1 to 6, which is for spraying application.

8. A polyurethane foam formed by foaming the flame-retardant urethane resin composition according to any one of Claims 1 to 7.

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