Composite thermal insulation structure, method for manufacturing the same, and composition for forming a polyurethane foam layer

Abstract

The present invention provides a composition that allows for the formation of a polyurethane foam layer on the surface of a substrate, which exhibits excellent dimensional stability due to suppressed shrinkage in sub-zero low-temperature environments, and also has excellent flame retardancy, and provides a polyurethane foam layer with excellent adhesion to an inorganic coating layer formed on its surface, as well as a composite thermal insulation structure with excellent heat insulation properties for fire resistance and a method for manufacturing the same. [Solution] When manufacturing a composite thermal insulation structure 1 by forming a polyurethane foam layer 3 and an inorganic coating layer 4 on the surface of a substrate 2, the composition used to form the polyurethane foam layer 3 contains a polyol, polymer fine particles, a catalyst, a blowing agent, and a polyisocyanate, wherein the catalyst consists of a resinification catalyst and a trimerization catalyst, and the resinification catalyst contains a tertiary amine and a resinification metal catalyst. Preferably, the polyol contains a polyester polyol and a polyether polyol.

Description

[Technical Field]

[0001] The present invention relates to a composite thermal insulation structure comprising a polyurethane foam layer and an inorganic coating layer, which has excellent thermal insulation properties and can be used in low-temperature environments, as well as a method for manufacturing the same and a composition for forming a polyurethane foam layer. [Background technology]

[0002] Conventionally, polyurethane foam, phenolic foam, and the like have been known as resin foams, and these have been used to form insulating layers on substrates such as walls and ceilings. When forming an insulating layer (insulating material) made of polyurethane foam, a general method is applied in which a polyol composition (premix liquid) containing polyol, a blowing agent, and various auxiliary agents such as catalysts and foam stabilizers as needed, and a polyisocyanate composition containing polyisocyanate are mixed, the resulting mixture, i.e., the polyurethane foam composition, is applied to the surface of the adherend, and the polyol and polyisocyanate react in the formed coating film to foam and harden.

[0003] Because insulation layers (insulating materials) made solely of polyurethane foam have poor heat resistance, a technology has recently been proposed to create composite insulation materials by applying an inorganic coating layer to the surface of the polyurethane foam layer. Patent Document 1 discloses a composite thermal insulation material comprising a polyurethane foam and an inorganic coating laminated on its surface, wherein the polyurethane foam is a sprayed polyurethane foam and the polyurethane foam contains a polyisocyanurate structure. It is stated that the polyurethane foam is preferably formed from a urethane resin composition containing a polyol composition comprising a polyol, a trimerizing catalyst, a blowing agent, and a flame retardant, and a polyisocyanate. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-129045 [Overview of the project] [Problems that the invention aims to solve]

[0005] When a polyurethane foam insulation layer is bonded to a substrate, it is necessary that the polyurethane foam layer does not shrink or shrinks only when used in a specific environment. The present invention aims to provide a polyurethane foam layer forming composition that can form a polyurethane foam layer with excellent dimensional stability due to suppressed shrinkage in sub-zero low-temperature environments, as well as excellent flame retardancy, and that provides a polyurethane foam layer with excellent adhesion to an inorganic coating layer formed on its surface for manufacturing a composite insulation structure. The present invention also aims to provide a method for manufacturing a fire-resistant composite insulation structure with excellent heat insulation properties using such a polyurethane foam layer forming composition. [Means for solving the problem]

[0006] The present inventors have found that the above problem can be solved by using a specific configuration for the catalyst in a polyurethane foam layer forming composition containing a polyol, polymer fine particles, a catalyst, a blowing agent, and a polyisocyanate.

[0007] The present invention is described below. [1] A composition used for forming a polyurethane foam layer when manufacturing a composite thermal insulation structure by forming a polyurethane foam layer and an inorganic coating layer on the surface of a substrate, It contains polyols, polymer microparticles, catalysts, blowing agents, and polyisocyanates. The above catalyst consists of a resin catalyst and a trimerization catalyst. The above resin-forming catalyst is characterized by comprising a tertiary amine and a resin-forming metal catalyst, and is a composition for forming a polyurethane foam layer of a composite thermal insulation structure. [2] The polyurethane foam layer forming composition according to [1] above, wherein the polyol comprises polyester polyol and polyether polyol. [3] The polyurethane foam layer forming composition according to [2] above, wherein the polyester polyol comprises an aromatic polyester polyol. [4] The polyurethane foam layer forming composition according to [2] above, wherein the polyether polyol comprises an alkylene oxide adduct of ethylenediamine. [5] The polyurethane foam layer forming composition according to [1], wherein the trimerizing catalyst is at least one selected from quaternary ammonium salts and alkali metal carboxylates. [6] The polyurethane foam layer forming composition according to [1], wherein the tertiary amine is at least one selected from alicyclic amines and heterocyclic compounds. [7] The polyurethane foam layer forming composition according to [1], wherein the resinified metal catalyst is at least one selected from Sn salt, Pb salt, Zn salt, Fe salt, Cu salt, Ni salt, Co salt, Mn salt, Zr salt, and Bi salt of a carboxylic acid. [8] A method for manufacturing a composite thermal insulation structure, characterized by coating a substrate with the polyurethane foam layer forming composition described in [1] above, then forming a polyurethane foam layer by a reaction of polyol and polyisocyanate contained in the polyurethane foam layer forming composition, and then forming an inorganic coating layer on the polyurethane foam layer. [9] The method for manufacturing a composite thermal insulation structure according to [8] above, wherein the inorganic coating layer is formed by coating the surface of the polyurethane foam layer with a composition comprising at least one selected from perlite, vermiculite, aluminum hydroxide, potassium silicate, potassium oxide, shirasu balloon, glass balloon, vermiculite, perlite, obsidian, volcanic rock, and natural pumice.

[10] A composite thermal insulation structure characterized by being obtained by the method described in [8] above. [Effects of the Invention]

[0008] When the polyurethane foam layer-forming composition of the present invention is applied to the surface of a substrate, it is possible to form a polyurethane foam layer that exhibits excellent dimensional stability due to suppressed shrinkage in sub-zero low-temperature environments, as well as excellent flame retardancy. Furthermore, it is possible to obtain a polyurethane foam layer with excellent adhesion to the inorganic coating layer formed on its surface for manufacturing composite insulation structures. As a result, composite insulation structures with excellent fire resistance and thermal insulation properties can be efficiently manufactured. Such composite insulation structures are suitable, for example, for insulation in interior and exterior wall materials of buildings, ceilings, roofs, floors, etc. of buildings, vehicles, ships, etc. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic cross-sectional view showing a composite thermal insulation structure manufactured according to the present invention. [Modes for carrying out the invention]

[0010] The present invention will now be described. The matters described herein are illustrative and illustrative to illustrate embodiments of the present invention, and are intended to provide what is considered to be the most effective and readily understandable explanation of the principles and conceptual features of the present invention. In this regard, it is not intended to describe the constituent details of the present invention beyond what is necessary for a fundamental understanding of the invention, and this description will make it clear to those skilled in the art how some forms of the present invention are actually embodied.

[0011] The present invention provides a composition for forming a polyurethane foam layer in a composite thermal insulation structure, which is used to form the polyurethane foam layer when manufacturing a composite thermal insulation structure 1 shown in Figure 1 by sequentially forming a polyurethane foam layer 3 and an inorganic coating layer 4 on a substrate 2 such as gypsum board, slate board, metal plate, calcium silicate board, or concrete. The composition comprises a polyol, polymer fine particles, a specific catalyst, a blowing agent, and a polyisocyanate.

[0012] The polyol constituting the polyurethane foam layer-forming composition of the present invention is not particularly limited as long as it is a conventionally known polyol used for forming polyurethane foams. At least one selected from polyester polyols, polyether polyols, polyether ester polyols, polyurethane polyols, polycarbonate polyols, polyolefin polyols and the like can be used. In the present invention, it is particularly preferable to use a polyester polyol and a polyether polyol.

[0013] The polyester polyol may be at least one selected from aliphatic polyester polyols, alicyclic polyester polyols and aromatic polyester polyols. Among these, aromatic polyester polyols are preferable.

[0014] The aromatic polyester polyol is preferably at least one of a polycondensate formed from o-phthalic acid or an anhydride thereof and a diol (hereinafter referred to as "first polyester polyol") and a polycondensate formed from terephthalic acid and a diol (hereinafter referred to as "second polyester polyol"). The first polyester polyol contained in the polyurethane foam layer-forming composition of the present invention may be only one type, or may be two or more types. Further, the second polyester polyol contained in the polyurethane foam layer-forming composition of the present invention may be only one type, or may be two or more types.

[0015] The diol used for forming the first polyester polyol and the second polyester polyol may be any of an aliphatic diol, an alicyclic diol and an aromatic diol, but is preferably an aliphatic diol. The diol used for forming the first polyester polyol and the diol used for forming the second polyester polyol may be the same or different.

[0016] This aliphatic diol may be linear or branched. Examples of linear diols include ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,8-octanediol. Examples of branched diols include propylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 2,2-diethyl-1,3-propanediol.

[0017] In the present invention, it is preferable to use a combination of a first polyester polyol and a second polyester polyol as the aromatic polyester polyol. When the total amount of both is 100% by mass, the content ratios of the first polyester polyol and the second polyester polyol are preferably 40-90% by mass and 10-60% by mass, more preferably 50-80% by mass and 20-50% by mass, and even more preferably 55-75% by mass and 25-45% by mass, respectively. By using a polyol containing the first polyester polyol and the second polyester polyol in such content ratios, a polyurethane foam layer can be suitably formed on the surface of the substrate, which has a high closed-cell ratio, excellent dimensional stability and flame retardancy in high-humidity environments, and even more suitable compressive strength.

[0018] In the present invention, the ratio of polyester polyol to the total amount of polyols (100% by mass) contained in the polyurethane foam layer forming composition is preferably 30 to 70% by mass, more preferably 35 to 65% by mass, and even more preferably 40 to 50% by mass, in order to obtain a polyurethane foam layer on the surface of the substrate that has a high closed-cell ratio, excellent dimensional stability and flame retardancy in high humidity environments, and even more suitable compressive strength.

[0019] Polyether polyols are preferably compounds obtained by adding alkylene oxide to an organic compound containing two or more active hydrogens. Specifically, examples include alkylene oxide adducts of hydrocarbon compounds having two or more hydroxyl groups (diol-based polyether polyols; triol-based polyether polyols; sucrose-based polyether polyols; sorbitol-based polyether polyols, etc.) and alkylene oxide adducts of hydrocarbon compounds having amino groups (ethylenediamine-based polyether polyols; tolylenediamine-based polyether polyols; Mannich condensates obtained by reacting phenols, aldehydes and alkanolamines; Mannich-based polyether polyols obtained by adding alkylene oxide to Mannich condensates, etc.). Of these, alkylene oxide adducts of hydrocarbon compounds having amino groups are preferred, ethylenediamine-based polyether polyols and Mannich-based polyether polyols are more preferred, and ethylenediamine-based polyether polyols are particularly preferred. The polyether polyol contained in the polyurethane foam layer forming composition of the present invention may be one type or two or more types.

[0020] The ethylenediamine-based polyether polyol is preferably an alkylene oxide adduct of ethylenediamine, and examples of this alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. One or more of these alkylene oxides may be used. From the viewpoint of the moisture permeability resistance of the resulting polyurethane foam layer, it is preferable that the alkylene oxide includes propylene oxide. In this case, the proportion of propylene oxide used is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, relative to the total amount of alkylene oxide.

[0021] Mannich polyether polyols are compounds obtained by adding alkylene oxide to Mannich condensates, which are reaction products of phenols, aldehydes, and alkanolamines, as described above.

[0022] As phenols, at least one selected from phenol and its derivatives (phenol derivatives) can be used. Preferably, alkylphenols are used as phenol derivatives, in which at least one hydrogen atom is located at the ortho position relative to the hydroxyl group of phenol, and at least one of the other hydrogen atoms bonded to the aromatic ring is substituted with an aliphatic hydrocarbon group.

[0023] It is preferable to use at least one aldehyde selected from formaldehyde and acetaldehyde as the aldehyde.

[0024] As the alkanolamine, it is preferable to use at least one selected from monoethanolamine, diethanolamine, 1-amino-2-propanol, etc.

[0025] The method for synthesizing Mannich condensates using phenols, aldehydes, and alkanolamines (Mannich condensation reaction) is not particularly limited, and conventionally known methods can be applied.

[0026] Mannich-type polyether polyols are preferably alkylene oxide adducts (ring-opening adducts) of Mannich condensates, and examples of alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide. One or more of these alkylene oxides may be used.

[0027] In the present invention, the polyether polyol may include alkylene oxide adducts of hydrocarbon compounds having two or more hydroxyl groups, as described above. Examples of hydrocarbon compounds having two or more hydroxyl groups include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decamethylene glycol, 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, polyoxyethylene glycol, and dip Aliphatic compounds such as propyl glycol, tripropylene glycol, polyoxypropylene glycol, ditetramethylene glycol, polytetramethylene ether glycol, glycerin, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, and dipentaerythritol; cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, cycloheptanediol, cyclooctanediol, 1,1-cyclohexanediethanol, hydroxypropylcyclohexanol, tricyclo[5,2,1,02,6]decane-dimethanol, bicyclo[4.Alicyclic compounds such as 3,0]-nonanediol, dicyclohexanediol, tricyclo[5,3,1,1]dodecanediol, bicyclo[4,3,0]nonanedimethanol, tricyclo[5,3,1,1]dodecane-diethanol, hydroxypropyltricyclo[5,3,1,1]dodecanol, spiro[3,4]octanediol, butylcyclohexanediol, 1,1′-bicyclohexylidenediol, 2,2-bis-(4-hydroxycyclohexyl)propane, 1,3-adamantanediol; hydroquinone, resorcinol Examples of aromatic compounds include dihydroxyphenyl, naphthalenediol, dihydroxydiphenyl ether, bisphenol A, diethoxylated bisphenol A, p-xylylene glycol, m-xylylene glycol, o-xylylene glycol, 4,4′-bishydroxymethylbiphenyl, 4,2′-bishydroxymethylbiphenyl, 2,2′-bishydroxymethylbiphenyl, 4,3′-bishydroxymethylbiphenyl, 3,3′-bishydroxymethylbiphenyl, and 3,2′-bishydroxymethylbiphenyl.

[0028] In the present invention, the content ratio of polyether polyol to the total amount of polyol (100% by mass) contained in the polyurethane foam layer forming composition is preferably 20 to 50% by mass, more preferably 25 to 45% by mass, and even more preferably 30 to 40% by mass, in order to obtain a polyurethane foam layer on the surface of the substrate that has a high closed-cell ratio, excellent dimensional stability and flame retardancy in high humidity environments, and even more suitable compressive strength. Furthermore, the content ratio of ethylenediamine-based polyether polyols to the total amount of polyether polyols (100% by mass) is preferably 15 to 50% by mass, more preferably 20 to 40% by mass, and even more preferably 25 to 35% by mass.

[0029] The polymer fine particles constituting the polyurethane foam layer forming composition of the present invention are well dispersed within the polyurethane resin formed from a polyol and a polyisocyanate, thereby providing a polyurethane foam layer on the surface of the substrate that exhibits suppressed shrinkage in sub-zero low-temperature environments and has excellent dimensional stability.

[0030] The polymer constituting the polymer nanoparticles is not particularly limited as long as it does not cause deformation, alteration, etc. during the reaction between the polyol and polyisocyanate, and may include vinyl resins (acrylic resins, aromatic vinyl resins, etc.), polyester resins, polycarbonate resins, polyamide resins, polyimide resins, urethane resins, epoxy resins, phenolic resins, melamine resins, aniline resins, ionomer resins, etc.

[0031] In the present invention, polymer fine particles made of vinyl resin are preferred, and their structural units can be derived from cyano group-containing monomers such as acrylonitrile, methacrylonitrile, and 2,4-diciabutene-1; styrene monomers such as styrene, α-methylstyrene, and halogenated styrene; acrylic monomers such as acrylic acid, methacrylic acid or their alkyl esters, fluorine-containing acrylate, and fluorine-containing methacrylate; acrylamide and methacrylamide; vinyl ester monomers such as vinyl acetate and vinyl propionate; diene monomers such as isoprene and butadiene; unsaturated fatty acid esters such as maleic acid diester and itaconic acid diester; halogenated vinyls such as vinyl chloride, vinyl bromide, and vinyl fluoride; halogenated vinylides such as vinylidene chloride, vinylidene bromide, and vinylidene fluoride; and vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, and isopropyl vinyl ether. Furthermore, polymer microparticles made of vinyl resin may also contain structural units derived from divinylbenzene, ethylene di(meth)acrylate, polyalkylene oxide glycol di(meth)acrylate, pentaerythritol trialyl ether, and trimethylolpropane tri(meth)acrylate.

[0032] The shape and particle size of the polymer microparticles are not particularly limited. The particle size of the polymer microparticles is preferably about 0.01 to 10 μm, as determined by laser diffraction / scattering.

[0033] The polymer fine particles according to the present invention can be derived from a polymer polyol (described later) which is preferably used as a raw material component.

[0034] The polymer fine particles contained in the polyurethane foam layer forming composition of the present invention are preferably 1 to 20% by mass, more preferably 2 to 10% by mass, and even more preferably 3 to 5% by mass, in order to obtain a polyurethane foam layer with excellent dimensional stability due to suppressed shrinkage in sub-zero low temperature environments.

[0035] The catalyst comprising the polyurethane foam layer forming composition of the present invention consists of a resinification catalyst that promotes the formation of urethane bonds and a trimerization catalyst that promotes the formation of isocyanurate rings.

[0036] The resin catalyst according to the present invention requires a tertiary amine and a resin metal catalyst, and may optionally contain other resin catalysts.

[0037] A tertiary amine can be at least one selected from aliphatic amines, alicyclic amines, and heterocyclic compounds. Specifically, these include N,N-dimethylalkylamines such as N,N-dimethylbutylamine, N,N-dimethylhexylamine, N,N-dimethyloctylamine, N,N-dimethyldecylamine, N,N-dimethyldodecylamine, and N,N-dimethylhexadecylamine; (dimethylamino)alkylamines such as 2-(dimethylamino)ethylamine and 3-(dimethylamino)propylamine; alicyclic amines such as N,N-dicyclohexylmethylamine, (dimethylamino)acetonitrile, and N,N-dimethylcyclohexylamine; N,N,N'-trimethylethylenediamine and trimethylamine; and imidazole. Examples include imidazole compounds such as -methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 1-isobutyl-2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole; and 1-(dimethylamino)pyrrole, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 2-(dimethylamino)pyridine, 4-(dimethylamino)pyridine, 4-methylmorpholine, and bis(2-morpholinoethyl) ether.

[0038] The tertiary amines according to the present invention are preferably alicyclic amines and heterocyclic compounds, and it is particularly preferable to use them in combination.

[0039] In the present invention, the content of the tertiary amine is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, and even more preferably 1.5 to 3 parts by mass, based on the total amount of polyols contained in the polyurethane foam layer forming composition being 100 parts by mass.

[0040] The resinified metal catalyst is preferably an organometallic compound, and can be at least one selected from the Sn, Pb, Zn, Fe, Cu, Ni, Co, Mn, Zr, and Bi salts of a carboxylic acid. The carboxylic acid may be an aliphatic carboxylic acid, an alicyclic carboxylic acid, or an aromatic carboxylic acid.

[0041] Examples of sn salts of carboxylic acids include tin acetate, tin butyrate, tin octoate, tin naphthenate, tin oleate, tin laurate, stannous octanoate, stannous dilaurate, stannous dipalmitate, stannous distearate, stannous dioleate, tin bis(neodecanate), tin stearate, tin benzoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate, and dioctyltin dilaurate.

[0042] Examples of Pb salts of carboxylic acids include lead acetate, lead butyrate, lead octoate, lead naphthenate, lead oleate, lead octanoate, lead neodecanoate, lead laurate, lead stearate, lead benzoate, dibutyllead diacetate, dibutyllead dilaurate, and dioctyllead dilaurate.

[0043] Examples of zinc salts of carboxylic acids include zinc acetate, zinc butyrate, zinc octoate, zinc naphthenate, zinc oleate, zinc octanoate, zinc neodecanoate, zinc laurate, zinc stearate, and zinc benzoate.

[0044] Examples of carboxylic acid iron salts include iron acetate, iron butyrate, iron octoate, iron naphthenate, iron oleate, iron octanoate, iron neodecanoate, iron laurate, iron stearate, and iron benzoate.

[0045] Examples of copper salts of carboxylic acids include copper acetate, copper butyrate, copper octoate, copper naphthenate, copper oleate, copper octanoate, copper neodecanoate, copper laurate, copper stearate, and copper benzoate.

[0046] Examples of nickel salts of carboxylic acids include nickel acetate, nickel butyrate, nickel octoate, nickel naphthenate, nickel oleate, nickel octanoate, nickel neodecanoate, nickel laurate, nickel stearate, and nickel benzoate.

[0047] Examples of Co salts of carboxylic acids include cobalt acetate, cobalt butyrate, cobalt octoate, cobalt naphthenate, cobalt oleate, cobalt octanoate, cobalt neodecanoate, cobalt laurate, cobalt stearate, and cobalt benzoate.

[0048] Examples of manganese salts of carboxylic acids include manganese acetate, manganese butyrate, manganese octylate, manganese naphthenate, manganese oleate, manganese octanoate, manganese neodecanoate, manganese laurate, manganese stearate, and manganese benzoate.

[0049] Examples of Zr salts of carboxylic acids include zirconium acetate, zirconium butyrate, zirconium octoate, zirconium naphthenate, zirconium oleate, zirconium octanoate, zirconium neodecanoate, zirconium laurate, zirconium stearate, and zirconium benzoate.

[0050] Examples of Bi salts of carboxylic acids include bismuth acetate, bismuth butyrate, bismuth octoate, bismuth naphthenate, bismuth oleate, bismuth octanoate, bismuth neodecanoate, bismuth laurate, bismuth stearate, bismuth benzoate, dibutylbismuth diacetate, dibutylbismuth dilaurate, and dioctylbismuth dilaurate.

[0051] As the resinified metal catalyst according to the present invention, Pb salts and Bi salts of carboxylic acids are preferred.

[0052] In the present invention, the content ratio of the resinified metal catalyst is preferably 0.1 to 3 parts by mass, more preferably 0.2 to 2.5 parts by mass, and even more preferably 0.3 to 2 parts by mass, based on the total amount of polyols contained in the polyurethane foam layer forming composition being 100 parts by mass.

[0053] The trimerizing catalyst according to the present invention is not particularly limited, as long as it is a catalyst that is conventionally known for the production of polyurethane resins. Examples of trimerizing catalysts include quaternary ammonium salts, alkali metal carboxylic acid salts, nitrogen-containing aromatic compounds, and tertiary ammonium salts. The trimerizing catalyst contained in the polyurethane foam layer forming composition of the present invention may be one type or two or more types.

[0054] Quaternary ammonium salts are (NR 1 R 2 R 3 R 4 ) + The cation portion (quaternary ammonium group) represented by and the counterion A - It is a compound having an anion part represented by . Examples of the cationic moiety include: aliphatic ammonium groups such as tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, heptyltrimethylammonium, octyltrimethylammonium, nonyltrimethylammonium, decyltrimethylammonium, undecyltrimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, tetradecyltrimethylammonium, heptadecyltrimethylammonium, hexadecyltrimethylammonium, heptadecyltrimethylammonium and octadecyltrimethylammonium; hydroxyammonium groups such as (2-hydroxypropyl)trimethylammonium, hydroxyethyltrimethylammonium and hydroxyethyl-2-hydroxypropyldimethylammonium; and alicyclic ammonium groups such as 1-methyl-1-azania-4-azabicyclo[2.2.2]octanium, 1,1-dimethyl-4-methylpiperidinium, 1-methylmorpholinium and 1-methylpiperidinium.

[0055] Examples of the anionic moiety include formate ions, acetate ions, octanoate ions, oxalate ions, malonate ions, succinate ions, glutarate ions, adipate ions, benzoate ions, toluylate ions, ethylbenzoate ions, methyl carbonate ions, phenoxide ions, alkylbenzenesulfonate ions, toluenesulfonate ions, benzenesulfonate ions, phosphate ester ions, halide ions, OH - , CO3 2- , HCO3 - , and the like.

[0056] As fatty acid alkali metal salts, sodium carboxylates such as sodium acetate; potassium carboxylates such as potassium acetate, potassium butyrate, potassium octoate, potassium 2-ethylhexanoate, potassium naphthenate, potassium oleate, potassium octanoate, potassium neodecanoate, potassium laurate, potassium stearate, and potassium benzoate can be used.

[0057] Examples of nitrogen-containing aromatic compounds include 4-dimethylaminotoluene, dimethylaniline, 4-dimethylaminoaniline, 4-(dimethylamino)benzonitrile, N,N-dimethylbenzylamine, tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and tris(dimethylaminopropyl)hexahydrotriazine.

[0058] Examples of tertiary ammonium salts include trimethylammonium salt, triethylammonium salt, and triphenylammonium salt.

[0059] The trimerizing catalyst according to the present invention is preferably a quaternary ammonium salt and an alkali metal carboxylate, and it is particularly preferable to use them in combination.

[0060] In the present invention, the content ratio of the trimerizing catalyst is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and even more preferably 1 to 2 parts by mass, based on the total amount of polyols contained in the polyurethane foam layer forming composition being 100 parts by mass.

[0061] Examples of foaming agents constituting the polyurethane foam layer-forming composition of the present invention include hydrocarbons, halogen-containing compounds, and water. The composition may contain only one type of foaming agent or two or more types.

[0062] Examples of hydrocarbons (HC) include propane, butane, isobutane, n-pentane, isopentane, hexane, isohexane, neohexane, heptane, isoheptane, and cyclopentane.

[0063] Examples of halogen-containing compounds include hydrofluorocarbons (HFCs) and halogenated olefins (halogenated alkenes).

[0064] Examples of hydrofluorocarbons (HFCs) include difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,1-trifluoroethane (HFC143a), 1,1,2,2-tetrafluoroethane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), and 1,1,1,2,3,3,3-heptafluoropropane. Examples include HFC227ea, 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluorobutane (HFC365mfc), and 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC4310mee), dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, and the like.

[0065] Halogenated olefins (halogenated alkenes) are preferably unsaturated hydrocarbon derivatives with approximately 2 to 6 carbon atoms, containing chlorine atoms, fluorine atoms, etc., as halogen atoms, and also include halogenated hydroolefins called hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs).

[0066] Examples of hydrofluoroolefins (HFOs) include pentafluoropropenes such as 1,2,3,3,3-pentafluoropropene (HFO-1225ye); tetrafluoropropenes such as 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2,3,3,3-tetrafluoropropene (HFO-1234yf), and 1,2,3,3-tetrafluoropropene (HFO-1234ye); and trifluoropropenes such as 3,3,3-trifluoropropene (HFO-1243zf). Examples include tetrafluorobutene (HFO-1345) isomers; pentafluorobutene isomers (HFO-1354) isomers; hexafluorobutene isomers (HFO-1336) such as 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz); heptafluorobutene isomers (HFO-1327); heptafluoropentene isomers (HFO-1447); octafluoropentene isomers (HFO-1438); nonafluoropentene isomers (HFO-1429), etc. Examples of hydrochlorofluoroolefins (HCFOs) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), dichlorotrifluoropropene (HCFO-1223), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), 1-chloro-1,3,3-trifluoropropene (HCFO-1233zb), 2-chloro-1,3,3-trifluoropropene (HCFO-1233xe), 2-chloro-2,2,3-trifluoropropene (HCFO-1233xc), 3-chloro-1,2,3-trifluoropropene (HCFO-1233ye), and 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc).

[0067] In the present invention, it is preferable to use water, which is a blowing agent source that reacts with polyisocyanate to produce carbon dioxide as a blowing agent, and a halogen-containing compound as the blowing agent. In this embodiment, it is particularly preferable to use a halogenated olefin as the halogen-containing compound. By using a halogenated olefin, the moisture resistance of the polyurethane foam layer can be increased. In such a polyurethane foam layer forming composition, when the total amount of polyol is 100 parts by mass, the water content is preferably 0.1 to 5 parts by mass, more preferably 1 to 4 parts by mass, and the halogenated olefin content is preferably 36 parts by mass or more, more preferably 10 to 50 parts by mass, and even more preferably 25 to 40 parts by mass.

[0068] The polyisocyanate constituting the polyurethane foam layer forming composition of the present invention is not particularly limited, as long as it has two or more isocyanate groups in its molecule and reacts with a polyol to produce polyurethane (resin).

[0069] Examples of polyisocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, urethane prepolymers having isocyanate groups at the molecular ends, isocyanurate-modified polyisocyanates, or carbodiimide-modified polyisocyanates. The polyisocyanate contained in the polyurethane foam layer-forming composition of the present invention may be one type or two or more types.

[0070] Examples of aromatic polyisocyanates include diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, polytollylene diisocyanate, xylylene diisocyanate, and naphthalene diisocyanate.

[0071] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

[0072] Examples of alicyclic polyisocyanates include isophorone diisocyanate (3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanate methyl)cyclohexane, and 1,4-bis(isocyanate methyl)cyclohexane.

[0073] The polyisocyanate according to the present invention preferably contains an aromatic polyisocyanate, as shrinkage is suppressed in sub-zero low-temperature environments, resulting in the formation of a polyurethane foam with excellent dimensional stability and flame retardancy.

[0074] Assuming that the total amount of all polyisocyanates contained in the polyurethane foam layer-forming composition of the present invention is 100% by mass, the lower limit of the aromatic polyisocyanate content is preferably 80% by mass, more preferably 90% by mass, and even more preferably 95% by mass, from the viewpoint of the mechanical strength of the polyurethane foam layer. The upper limit is usually 100% by mass.

[0075] In the polyurethane foam layer forming composition of the present invention, there is a preferred ratio between the polyol and the polyisocyanate. In the present invention, the polyol and polyisocyanate are configured such that the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyol is preferably 0.9 to 4.5, more preferably 1 to 3, and even more preferably 1.1 to 2.

[0076] In addition to the polyol, polymer fine particles, catalyst, foaming agent, and polyisocyanate mentioned above, the polyurethane foam layer forming composition of the present invention may further contain other components (additives) such as foam stabilizers, flame retardants, formaldehyde scavenging agents, compatibilizers, antioxidants, antistatic agents, antibacterial agents, corrosion inhibitors, and colorants to homogenize the cell structure of the foam.

[0077] The foam stabilizer may be a nonionic, anionic, or cationic compound, but it is preferable to include a nonionic foam stabilizer. The foam stabilizer may be one type or two or more types. Specific examples of foam stabilizers include silicone compounds such as organopolysiloxanes, polyoxyalkylene-modified dimethylpolysiloxanes, and polysiloxane-oxyalkylene copolymers, as well as polyoxyethylene sorbitan fatty acid esters, polyoxyethylene castor oil fatty acid esters, lauryl fatty acid ethylene oxide adducts, and polyoxyalkylene alkyl ethers.

[0078] If the polyurethane foam layer forming composition of the present invention contains a foam stabilizer, the proportion of the foam stabilizer is preferably 0.1 to 5 parts by mass, more preferably 1 to 3 parts by mass, based on 100 parts by mass of the total amount of polyols.

[0079] Examples of flame retardants include organophosphate esters, organophosphonic acid compounds, organophosphinic acid compounds, phosphine oxide compounds, phosphonitrile compounds, triazole compounds, tetrazole compounds, triazine compounds, cyclic monoureides, cyclic diureides, amidine compounds, phosphates, stanates, halogen compounds (excluding organophosphate esters), boron compounds, metal hydroxides, and red phosphorus. The flame retardant may be one type or two or more types.

[0080] Examples of organic phosphate esters include monophosphate esters and condensed phosphate esters.

[0081] Examples of monophosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, tris(phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl(2-ethylhexyl) phosphate, di(isopropylphenyl)phenyl phosphate, and monoisodecyl phosphate.

[0082] Examples of condensed phosphate esters include trialkyl polyphosphates, resorcinol polyphenyl phosphates, resorcinol poly(di-2,6-xylyl) phosphates, hydroquinone poly(2,6-xylyl) phosphates, resorcinol polyphenyl phosphates, and bisphenol A polycresyl phosphates.

[0083] Examples of organic phosphonic acid compounds include hydroxyethylidene diphosphonic acid, nitrilotris (methylenephosphonic acid), phosphonovutanetricarboxylic acid, ethylenediaminetetra (methylenephosphonic acid), and diethylenetriaminepenta (methylenephosphonic acid).

[0084] Examples of organophosphinic acid compounds include metal salts of phosphinic acids such as aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, aluminum triphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, zinc triphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, titanium tetrakisdiphenylphosphinate, and titanyl tetraphosphinate; and phosphinic acid esters such as phenyl diphenylphosphinate and methyl diphenylphosphinate.

[0085] Examples of phosphine oxide compounds include diphenylvinylphosphine oxide, triphenylphosphine oxide, tricresylphosphine oxide, trialkylphosphine oxide, and tris(hydroxyalkyl)phosphine oxide.

[0086] The flame retardant preferably contains an organic phosphate ester. If the polyurethane foam layer forming composition of the present invention contains a flame retardant, the proportion of the flame retardant is preferably 5 to 30 parts by mass, more preferably 10 to 15 parts by mass, based on a total amount of polyols of 100 parts by mass.

[0087] The method for producing the polyurethane foam layer-forming composition of the present invention is not particularly limited. A preferred production method involves using raw material components excluding polyisocyanate in predetermined proportions, mixing them, and then mixing the resulting mixture with polyisocyanate. The polyurethane foam layer-forming composition of the present invention contains a polyol and polymer fine particles, but it is preferable to use a so-called polymer polyol as one of the raw material components relating to the polymer fine particles, in which polymer fine particles are dispersed in at least one selected from polyester polyol and polyether polyol. A suitable polymer polyol as a raw material component is usually a mixture obtained by a polymerization reaction using monomers that generate polymer fine particles, polymerization initiators, etc., in a polyol component of a dispersion medium, and the polyurethane foam layer-forming composition can be produced using such a mixture as is. The content of polymer fine particles in the polymer polyol is not particularly limited, but is preferably 1 to 50 parts by mass when the polymer polyol is 100 parts by mass. For the manufacture of a composition for forming a polyurethane foam layer, equipment such as a high-speed agitator or an impact mixer can be used to mix the raw material components.

[0088] The foam (polyurethane foam) obtained using the polyurethane foam layer-forming composition of the present invention preferably has a high closed-cell ratio, thereby possessing high compressive strength. Therefore, a composite thermal insulation structure comprising a polyurethane foam layer, formed by applying the polyurethane foam layer-forming composition of the present invention to the surface of a substrate and allowing it to foam, exhibits excellent structural stability for fire resistance.

[0089] The polyurethane foam layer forming composition of the present invention is suitable for forming a polyurethane foam layer made of a rigid foam (rigid polyurethane foam) with a high closed-cell ratio by coating it onto a substrate such as gypsum board, slate board, metal plate, calcium silicate board, or concrete, and then foaming and curing it. Furthermore, by forming an inorganic coating layer on the surface of this polyurethane foam layer to create a composite insulation structure, it is possible to improve the flame retardancy and heat resistance in addition to the insulation properties of the polyurethane foam.

[0090] The present invention provides a method for manufacturing a composite thermal insulation structure, which involves coating a substrate with the polyurethane foam layer forming composition described above, then forming a polyurethane foam layer by a reaction between the polyol and polyisocyanate contained in the polyurethane foam layer forming composition, and finally forming an inorganic coating layer on the polyurethane foam layer.

[0091] Methods for forming a polyurethane foam layer on the surface of the substrate using a polyurethane foam layer forming composition include: a spray foaming method in which the polyurethane foam composition is sprayed onto the substrate using a spray gun and then foamed and cured; a laminate continuous foaming method in which the polyurethane foam composition is coated onto the substrate and then foamed and cured; and an injection method in which the composition is filled into molds and cavities and then foamed and cured. When forming a thick polyurethane foam layer on the surface of the substrate, for example, the spray foaming method, which allows for easy recoating, is preferably applied.

[0092] Since the polyurethane foam layer forming composition contains a polyol, polyisocyanate, and a catalyst, it is preferable that this composition be prepared immediately before coating the substrate. When coated onto the substrate, polyurethane is instantly generated by the reaction of the polyol and polyisocyanate, and foaming and curing proceed, forming a polyurethane foam layer on the surface of the substrate.

[0093] The thickness of the polyurethane foam layer is set appropriately depending on the application of the composite insulation structure, but is preferably 400 mm or less, more preferably 300 mm or less, and even more preferably 100 mm or less.

[0094] Subsequently, an inorganic coating layer is formed on the surface of the polyurethane foam layer, and a composite insulation structure is manufactured. The inorganic coating layer is a non-combustible film mainly composed of inorganic materials with low thermal conductivity. Examples of such inorganic materials include perlite, vermiculite, aluminum hydroxide, potassium silicate, potassium oxide, shirasu balloon, glass balloon, vermiculite, perlite, obsidian, volcanic rock, and natural pumice. These inorganic materials may be solid or porous, and their particle size is not particularly limited.

[0095] When forming an inorganic coating layer, it is preferable to use a liquid composition containing at least one of the above-mentioned inorganic materials. This composition preferably further contains adhesive components such as cement (Portland cement, alumina cement, lime-mixed cement, blast furnace cement, silica cement, fly ash cement, high-sulfate slag cement, etc.), and may further contain additives that improve coating properties (polymer aqueous solution, synthetic resin emulsion, surfactant, etc.). The viscosity of such a liquid composition is not particularly limited. Commercially available liquid compositions that have been conventionally used in fire-retardant construction methods can be used as the liquid composition for forming the inorganic coating layer. Some of these commercial products combine a liquid composition for primer treatment with a liquid composition that provides a substantially fire-retardant inorganic coating layer.

[0096] Liquid compositions for primer treatment can include film-forming resins (such as acrylic resins, urethane resins, vinyl chloride resins, vinyl acetate resins, polyester resins, and styrene resins), fillers, dispersants, thickeners, defoamers, coloring pigments, and the like.

[0097] The thickness of the inorganic coating layer is set appropriately depending on the application of the composite insulation structure, but is preferably 12 mm or more, and the upper limit is usually 40 mm.

[0098] The method for applying the liquid composition to the polyurethane foam layer is not particularly limited, and methods such as coating using a brush, roller, spatula, etc., or spray coating can be applied.

[0099] A composite thermal insulation structure manufactured according to the present invention is shown in Figure 1, for example. Figure 1 is a schematic cross-sectional view of the composite thermal insulation structure, and the composite thermal insulation structure 1 is a laminated structure comprising a polyurethane foam layer 3 and an inorganic coating layer 4 sequentially on the surface of a substrate 2. In the present invention, since the polyurethane foam layer 3 is obtained using a polyurethane foam layer-forming composition containing a specific polyol, this polyurethane foam layer 3 has excellent adhesion to the inorganic coating layer 4, and the thermal insulation properties of both are further enhanced. [Examples]

[0100] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" refer to mass unless otherwise specified.

[0101] 1. Raw materials for manufacturing the composition The raw materials for the polyurethane foam compositions used in the examples and comparative examples are shown below.

[0102] 1-1. Polyols 1-1-1. Polyester Polyol (1) Phthalic anhydride-based polyester polyol (O-aromatic polyester polyol) We used "Maximol RDK-133" (product name) manufactured by Air Water Performance Chemicals. (2) Terephthalic acid-based polyester polyol (P-aromatic polyester polyol) We used "Maximol RFK-505" (product name) manufactured by Air Water Performance Chemicals.

[0103] 1-1-2. Polyether polyols (1) Ethylenediamine-based polyether polyol AGC's "EXCENOL 750ED" (product name) was used. 100% by mass of the alkylene oxide added to the initiator was propylene oxide. (2) Mannich-type polyether polyol We used "DK Polyol 3776" (product name) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0104] 1-1-3. Polymer microparticle dispersion polyol (1) AGC Corporation's "FB512" (product name) This product consists of acrylic resin particles dispersed in a polyether polyol, with the acrylic resin particle content ranging from 1% to 50% by mass. (2) Sanyo Chemical Industries, Ltd. "Sannix FA728R" (product name) This product consists of acrylic resin particles dispersed in a polyether polyol, with the acrylic resin particles accounting for 20% by mass.

[0105] 1-2. Catalyst 1-2-1. Resin-based catalyst (1) Tertiary amines (alicyclic amines) We used N,N-dicyclohexylmethylamine "Polycat 12" (trade name) manufactured by Evonik Japan. (2) Tertiary amines (heterocyclic compounds) We used 1,2-dimethylimidazole "Kaorizer No. 350" (product name) manufactured by Kao Corporation. (3) Resin-based metal catalyst (metal carboxylic acid salt) We used "Hexoate Lead 20%" (product name), a hexoate lead manufactured by Toei Chemical Co., Ltd. (4) Resin-based metal catalyst (metal carboxylate salt) We used bismuth octoate "Pukat 25" (product name), manufactured by Nippon Chemical Industries, Ltd. 1-2-2. Trimerization catalyst (1) Quaternary ammonium salts We used Kao Corporation's quaternary ammonium salt, "Kaorizer No. 420" (product name). (2) Alkali metal salts of carboxylic acids Potassium octoate "Pucat 15G" (product name), manufactured by Nippon Chemical Industries, Ltd., was used.

[0106] 1-3. Foam stabilizers Niax, a silicone-based foam stabilizer manufactured by Momentive Performance Materials Japan LLC. TM The product used was "Silicone L-6100" (product name).

[0107] 1-4. Flame retardants We used the organophosphate ester "Tris(1-chloro-2-propyl)phosphate" (trade name) manufactured by Wanshan.

[0108] 1-5. Foaming agent (1)Water (2) Non-fluorocarbon blowing agent 1 We used 1-chloro-3,3,3-trifluoropropene "HCFO-1233zd" (trade name) manufactured by Honeywell. (3) Non-fluorocarbon blowing agent 2 We used 1,1,1,4,4,4-hexafluoro-2-butene "HFO-1336mzz" (trade name) manufactured by Chemours.

[0109] 1-6. Polyisocyanates We used polymeric MDI "Wannate PM-130" (product name) manufactured by Manka Chemical Japan Co., Ltd.

[0110] 2. Manufacturing and evaluation of polyurethane foam layer formation compositions and composite thermal insulation structures. Using the above raw materials, a composition for forming a polyurethane foam layer on the surface of a substrate (polyurethane foam layer forming composition, hereinafter also referred to as "polyurethane foam composition") was manufactured, and then a composite thermal insulation structure was manufactured using this polyurethane foam composition.

[0111] Example 1 A polyol composition was obtained by stirring and mixing 50 parts O-aromatic polyester polyol, 20 parts P-aromatic polyester polyol, 30 parts ethylenediamine-based polyether polyol, 3 parts polymer fine particle dispersion polyol "FB512", 2 parts N,N-dicyclohexylmethylamine, 1 part 1,2-dimethylimidazole, 0.6 parts hexoate lead, 1 part quaternary ammonium salt, 3 parts foam stabilizer, 20 parts organic phosphate ester, 3 parts water, and 30 parts non-fluorocarbon foaming agent 1. Subsequently, the obtained polyol composition and 163.6 parts of polyisocyanate were stirred and mixed to prepare a polyurethane foam composition (polyurethane foam layer forming composition) (see Table 1). In the obtained polyurethane foam composition, the content of polymer fine particles was 0.9 parts when the total amount of polyol was 100 parts.

[0112] Next, the obtained polyurethane foam composition was sprayed onto the surface of an inorganic flexible board a predetermined number of times, and then foamed and cured to bond a rigid foam to it. Subsequently, the density, foam processability, dimensional change rate, flame retardancy, and thermal insulation properties of this foam were measured or evaluated, and these results are shown in Table 1.

[0113] (1) Density The mass of a test specimen (size: 100mm × 100mm × 30mm) that had been prepared 72 hours or more after foaming and left to stand at 23℃±2℃ for 16 hours or more before density measurement was measured, and the density ρ was calculated using the following formula. ρ(kg / m 3 )=[M(g) / V(mm 3 )] × 10 6 (ρ: density, M: mass of the specimen, V: volume of the specimen)

[0114] (2) Formability In a foam with a skin layer formed on the surface of an inorganic flexible board, the edges of the foam that protruded from the flexible board were cut along the periphery of the flexible board with a utility knife, and the processability of the polyurethane foam was evaluated based on the feel at that time according to the following criteria. ◎: Requires almost no force to cut, and produces a good cut surface. ○: Some force is required when cutting, but the cut surface is good. △: Requires considerable force to cut, resulting in some roughness on the cut surface. ×: Cutting with a utility knife is difficult, but cutting with a saw is possible, although the cut surface will be rough.

[0115] (3) Dimensional stability Test specimens (size: 100mm x 100mm x 25mm) were prepared by cutting out a foam layer formed on an inorganic flexible board, including the internal skin layer (the skin layer formed by the first top-blowing). After being left to stand for 48 hours at a temperature of -30°C, the dimensions were measured with calipers, and the dimensional change rate was calculated using the following formula. Dimensional change rate (%) = [([Dimensions of the test specimen after testing] - [Dimensions of the test specimen before testing]) / [Dimensions of the test specimen before testing]] × 100 Subsequently, dimensional stability was evaluated based on the rate of dimensional change, according to the following criteria. ◎: The dimensional change rate is less than 1%. ○: The dimensional change rate is 1% or more but less than 2%. △: The dimensional change rate is 2% or more but less than 3%. ×: The dimensional change rate is 3% or more.

[0116] (4) Flame retardant In accordance with JIS A 9526:2015, a test specimen (size: 50mm x 150mm x 13mm) was prepared by cutting it from a foamed layer formed on an inorganic flexible board. One end of the specimen was burned for 60 seconds using a Bunsen burner equipped with a fishtail lamp, and the time until flame extinction and the burning distance were measured. The flame retardancy of these measurement results was determined according to the following criteria. ○: The burning distance was less than 60 mm and the burning time was less than 120 seconds. ×: The burning distance was 60 mm or more, or the burning time was 120 seconds or more.

[0117] (5) Thermal insulation The thermal conductivity of test specimens (size: 200mm x 200mm x 25mm) prepared by cutting from a foamed layer formed on an inorganic flexible board according to the method conforming to JIS A 1412 was measured using the "AUTO-A-HC-074 / 200" thermal conductivity measuring device (model name) manufactured by Eiko Seiki Co., Ltd. The thermal insulation performance was then determined according to the following criteria. ○: It was 0.023 W / m·K or less. △: The value was greater than 0.023 W / m·K and less than or equal to 0.026 W / m·K.

[0118] (6) Detachment of the non-combustible coating (adhesion test) A polyurethane foam composition was sprayed onto the surface of a gypsum board (size: 50mm x 50mm x 12.5mm) to form a foam layer approximately 38mm thick. Then, a solution of "Kikusui Noncombustible Coat" (product name, manufactured by Kikusui Chemical Industry Co., Ltd.), an inorganic coating composition containing perlite, white cement (binder), etc., diluted 1.5 times with water, was sprayed onto this surface using an Anest Iwata spraying device "Ricin Gun MG-2D" (product name). The mixture was dried at 20°C for 7 days to produce a composite insulation structure with a 12mm thick inorganic coating layer. The adhesive strength between the inorganic coating layer and the foam layer was then measured using a Minebea universal testing machine "TG-50kN" (model name) in accordance with JIS A 9526. The results are shown in Table 1. ○: 80kPa or higher ×: Less than 80kPa

[0119] Examples 2-16 and Comparative Examples 1-9 A polyol composition was obtained by mixing a polyol, catalyst, foam stabilizer, flame retardant, and blowing agent according to the formulation described in Table 1, Table 2, or Table 3. This polyol composition was then stirred and mixed with a predetermined amount of polyisocyanate to prepare a polyurethane foam composition. In the polyurethane foam composition obtained in Example 7 using "FA728" as the polymer microparticle-dispersed polyol, the content of polymer microparticles was 1.8 parts when the total amount of polyol was 100 parts. Next, the same evaluation as in Example 1 was performed, and the results are shown together in Tables 1, 2, and 3.

[0120] [Table 1]

[0121] [Table 2]

[0122] [Table 3]

[0123] From Tables 1, 2, and 3, the following can be seen. Examples 1 to 16 are examples using polyurethane foam compositions containing a polyol, polymer fine particles, a catalyst, a blowing agent, and a polyisocyanate, wherein the catalyst consists of a resin-forming catalyst containing a tertiary amine and a resin-forming metal catalyst, and a trimerizing catalyst. These compositions successfully formed polyurethane foam layers with excellent dimensional stability and flame retardancy. Furthermore, a composite thermal insulation structure with excellent thermal insulation properties was obtained by laminating an inorganic coating layer. On the other hand, Comparative Examples 1 to 9 are examples using polyurethane foam layer-forming compositions that do not have the configuration of the present invention, and the effects of the present invention could not be fully obtained. [Industrial applicability]

[0124] The composite thermal insulation structure obtained using the polyurethane foam layer-forming composition of the present invention is suitable for use in interior and exterior wall materials of buildings, and for thermal insulation of ceilings, roofs, floors, etc. of buildings, vehicles, ships, etc. [Explanation of symbols]

[0125] 1: Composite insulation structure 2: Base 3: Polyurethane foam layer 4: Inorganic coating layer

Claims

1. A composition used for forming a polyurethane foam layer when manufacturing a composite thermal insulation structure by forming a polyurethane foam layer and an inorganic coating layer on the surface of a substrate, It contains polyols, polymer microparticles, catalysts, blowing agents, and polyisocyanates. The catalyst consists of a resin catalyst and a trimerization catalyst. The resin catalyst is characterized by comprising a tertiary amine and a resin metal catalyst, and is a composition for forming a polyurethane foam layer of a composite thermal insulation structure.

2. The polyurethane foam layer forming composition according to claim 1, wherein the polyol comprises polyester polyol and polyether polyol.

3. The polyurethane foam layer forming composition according to claim 2, wherein the polyester polyol comprises an aromatic polyester polyol.

4. The polyurethane foam layer forming composition according to claim 2, wherein the polyether polyol comprises an alkylene oxide adduct of ethylenediamine.

5. The polyurethane foam layer forming composition according to claim 1, wherein the trimerizing catalyst is at least one selected from quaternary ammonium salts and alkali metal carboxylic acid salts.

6. The polyurethane foam layer forming composition according to claim 1, wherein the tertiary amine is at least one selected from alicyclic amines and heterocyclic compounds.

7. The polyurethane foam layer forming composition according to claim 1, wherein the resinified metal catalyst is at least one selected from Sn salt, Pb salt, Zn salt, Fe salt, Cu salt, Ni salt, Co salt, Mn salt, Zr salt, and Bi salt of a carboxylic acid.

8. A method for manufacturing a composite thermal insulation structure, characterized by coating a substrate with the polyurethane foam layer forming composition described in claim 1, then forming a polyurethane foam layer by a reaction between the polyol and polyisocyanate contained in the polyurethane foam layer forming composition, and subsequently forming an inorganic coating layer on the polyurethane foam layer.

9. The method for manufacturing a composite thermal insulation structure according to claim 8, wherein the inorganic coating layer is formed by coating the polyurethane foam layer with a composition comprising at least one selected from perlite, vermiculite, aluminum hydroxide, potassium silicate, potassium oxide, shirasu balloon, glass balloon, vermiculite, perlite, obsidian, volcanic rock, and natural pumice.

10. A composite thermal insulation structure characterized by being obtained by the method described in claim 8.

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