Polyol composition, composition for polyurethane foam, and foam

Abstract

To provide a composition for a polyurethane foam which gives a foam having excellent adhesiveness to an adherend and suppressing shrinkage in a low-temperature environment and has excellent storage stability, and to provide a polyol composition used for preparing the composition for a polyurethane foam.SOLUTION: The polyol composition of the present invention is used by being combined with a foaming agent and a polyisocyanate to prepare the composition for a polyurethane foam to be used for producing a polyurethane foam and contains a polyol and a catalyst. The polyol contains an aromatic polyester polyol. The foaming agent contains a halogenated olefin. The catalyst contains at least one selected from an aromatic primary amine and an aromatic secondary amine.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition for polyurethane foam which provides a foam (polyurethane foam) that has excellent adhesion to an adherend and is inhibited from shrinking in a low-temperature environment, and a polyol composition used in the preparation of the composition. [Background technology]

[0002] Conventionally, known resin foams include polyurethane foam, phenol foam, etc. For example, polyurethane foam is widely used due to its excellent heat insulation properties, adhesion to objects, soundproofing properties, etc. When forming a heat insulating layer (heat insulating material) made of polyurethane foam, a method is generally used in which a polyol composition (premix liquid) containing a polyol, a foaming agent, and, as necessary, various auxiliaries such as a catalyst and a foam stabilizer, and a polyisocyanate composition containing a polyisocyanate are mixed, and then the resulting mixed liquid, i.e., a composition for polyurethane foam, is applied to the surface of an adherend, and the polyol and polyisocyanate are reacted in the formed coating film to foam and cure.

[0003] The following techniques are known for producing polyurethane foams or compositions used therein. Patent Document 1 discloses a method for producing a rigid polyurethane foam, which is characterized by reacting a polyol with a polyisocyanate in the presence of at least one type of cyclic primary amine compound selected from a carbocyclic compound containing at least one primary amino group and a heterocyclic compound containing at least one primary amino group, a catalyst, and a hydrocarbon having 4 to 6 carbon atoms as a blowing agent and water. Patent Document 2 discloses a two-component reaction type urethane resin composition prepared from a polyisocyanate component (X) and a polyol-containing component (Y), the polyol-containing component (Y) containing a polyol component (a), a catalyst (b), a foam stabilizer (c), an amine compound (d) having a primary amino group or a secondary amino group, and carbon dioxide (e), the two-component reaction type urethane resin composition being an open-cell flexible polyurethane foam when cured, the polyurethane foam having an average sound absorption coefficient of 30% or more from 63 Hz to 5000 Hz as measured according to JIS A 1405-2:2007, and a dripping length of 300 mm or less as measured by a specified method. Furthermore, Patent Document 3 discloses a method for producing a polyurethane foam by reacting and foaming a polyol composition containing a polyol, a blowing agent, and a catalyst with a polyisocyanate, the method being characterized in that the blowing agent contains a hydrofluoroolefin having a boiling point of 30°C or less, and the temperature of the polyol composition is set to 30°C or less before the reaction. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2001-172359 A [Patent Document 2] JP 2019-178207 A [Patent Document 3] JP 2022-30314 A Summary of the Invention [Problem to be solved by the invention]

[0005] When polyurethane foam is used for, for example, thermal insulation, it is common to integrate it with an adherend such as a wall, a ceiling, etc. When such an integrated product is used in a low-temperature environment, for example, below freezing, it is necessary that the polyurethane foam layer does not shrink. In addition, for example, a method may be adopted in which a polyurethane foam composition comprising a polyol composition and a polyisocyanate composition is supplied to a wall, ceiling, etc. by spray coating, foaming and curing the composition to form a polyurethane foam, and then the polyurethane foam is adhered to the wall, ceiling, etc., to obtain an integrated product having a heat insulating layer made of polyurethane foam. In this case, the polyurethane foam layer needs to have good adhesion to the adherend. Furthermore, in such a two-component polyurethane foam composition, a reaction between the polyol and the polyisocyanate begins when the polyol composition and the polyisocyanate composition are mixed, and therefore, in order to produce a foam (polyurethane foam) having uniform foam cells, the time from the start of mixing the polyol composition and the polyisocyanate composition to the start of foaming (hereinafter referred to as the "cream time"), the time from the start of mixing the polyol composition and the polyisocyanate composition to the start of thickening and the start of gel strength (resinization time, hereinafter referred to as the "gel time"), and the time from the start of mixing the polyol composition and the polyisocyanate composition to the end of foaming (hereinafter referred to as the "rise time") are measured. If the time difference between the cream time and the gel time, and the time difference between the gel time and the rise time are all 0 to 2 seconds, the polyurethane foam composition has been deemed to have particularly excellent storage stability.

[0006] The present invention aims to provide a composition for polyurethane foam that provides a foam (polyurethane foam) that has excellent adhesion to an adherend and is suppressed from shrinking in a low-temperature environment, and further has excellent storage stability. Another object of the present invention is to provide a polyol composition used in the preparation of such a composition for polyurethane foam. [Means for solving the problem]

[0007] The present invention is presented below. [1] A polyol composition used in preparing a polyurethane foam composition for use in producing a polyurethane foam, comprising a polyol composition, a blowing agent, and a polyisocyanate in combination, The polyol composition contains a polyol and a catalyst, The polyol includes an aromatic polyester polyol, The blowing agent comprises a halogenated olefin, The catalyst is a polyol composition containing at least one selected from an aromatic primary amine and an aromatic secondary amine. [2] The polyol composition according to [1] above, wherein the content of the aromatic polyester polyol is 30 mass % or more relative to the polyol. [3] The polyol composition according to [1] above, wherein the polyol comprises an amine-based polyol. [4] The polyol composition according to the above [1], wherein the polyol composition contains the above blowing agent. [5] The polyol composition according to [4] above, wherein the blowing agent further contains water. [6] The polyol composition according to the above [5], wherein the content of the water is 3 to 7 parts by mass per 100 parts by mass of the content of the polyol. [7] The polyol composition according to the above [1], wherein the halogenated olefin comprises at least one selected from HCFO1233zd, HFO1336mzz and HFO1224yd. [8] The polyol composition according to [1] above, wherein the catalyst further comprises a trimerization catalyst. [9] The polyol composition according to the above [1], wherein the catalyst further contains a tertiary amine.

[10] A composition for polyurethane foam, comprising a combination of the polyol composition described in [1] above and a polyisocyanate composition containing a polyisocyanate.

[11] A foam obtained by foaming the polyurethane foam composition described in

[10] above. Effect of the Invention

[0008] By using the polyurethane foam composition of the present invention, a foam (polyurethane foam) having excellent adhesion to an adherend and suppressed shrinkage in a low temperature environment can be obtained. In addition, since the composition has excellent storage stability, the foam exhibits adhesion to an adherend through foaming and curing after coating the polyurethane foam composition of the present invention on the adherend, and is suitable for forming members used for insulation in interior and exterior wall materials and panels of buildings, insulation in metal siding, refrigerators, insulation or dew prevention in the walls, ceilings, roofs, etc. of buildings, condominiums, and refrigerated warehouses, insulation in infusion pipes, etc., by rapid work using, for example, spray coating. The polyol composition of the present invention is suitable as a raw material for producing a polyurethane foam composition that gives such a foam (polyurethane foam). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention will be described below. The matters described herein are for illustrative purposes and for illustrative purposes of the embodiments of the present invention, and are described for the purpose of providing what is believed to be the most effective and easy-to-understand explanation of the principles and conceptual features of the present invention. In this respect, it is not intended to show the structural details of the present invention beyond a certain degree that are necessary for a fundamental understanding of the present invention, and the present description will make it clear to those skilled in the art how some aspects of the present invention can be actually embodied.

[0010] The polyol composition of the present invention is a composition used for preparing a polyurethane foam composition, which is a combination of the polyol composition, a blowing agent containing a halogenated olefin, and a polyisocyanate, and is applied to an adherend to form a foam made of a urethane resin having excellent adhesion to the adherend. The polyol composition of the present invention contains a polyol containing an aromatic polyester polyol (hereinafter referred to as a "polyol component") and at least one catalyst selected from aromatic primary amines and aromatic secondary amines. The polyol composition of the present invention can contain other components in addition to the polyol component and the catalyst, as described below.

[0011] The polyol component constituting the polyol composition of the present invention contains an aromatic polyester polyol, and may contain other polyols (described later) as necessary.

[0012] The aromatic polyester polyol is preferably a polyester polyol consisting of a condensation reaction product obtained by using phthalic acid or its anhydride and a diol. The phthalic acid may be either o-phthalic acid or terephthalic acid. The diol may be any of an aliphatic diol, an alicyclic diol, and an aromatic diol, but is preferably an aliphatic diol.

[0013] The aliphatic diol may be either 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.

[0014] The aromatic polyester polyol contained in the polyol composition of the present invention may be one type or two or more types. The aromatic polyester polyol according to the present invention preferably contains at least one type selected from a polyester polyol formed from o-phthalic acid or its anhydride and a diol (hereinafter referred to as "first polyester polyol"), and a polyester polyol formed from terephthalic acid and a diol (hereinafter referred to as "second polyester polyol").

[0015] The content of aromatic moieties in the first polyester polyol (hereinafter also referred to as "aromatic concentration"), i.e., the mass ratio of aromatic rings constituting the first polyester polyol, is preferably 5 mass% or more, more preferably 10 to 35 mass%, and even more preferably 15 to 25 mass%. The content of the aromatic moiety (aromatic concentration) in the second polyester polyol is preferably 5% by mass or more, more preferably 10 to 35% by mass, and even more preferably 15 to 25% by mass.

[0016] In the polyol composition of the present invention, the first polyester polyol and the second polyester polyol can be used in combination. The content ratios of the first polyester polyol and the second polyester polyol are P1 and P2, respectively, and the total of P1 and P2 is 100% by mass. The content ratios P1 and P2 are preferably 100-0% by mass and 0-100% by mass, more preferably 95-30% by mass and 5-70% by mass, and even more preferably 90-50% by mass and 10-50% by mass, respectively. This makes the storage stability of the polyurethane foam composition containing the polyol composition of the present invention excellent.

[0017] When the total of all polyol components constituting the polyol composition of the present invention is taken as 100% by mass, the lower limit of the content of aromatic polyester polyol is preferably 30% by mass, more preferably 40% by mass, and even more preferably 50% by mass, because a foam having excellent adhesion to an adherend and suppressed shrinkage in a low-temperature environment can be obtained when a polyurethane foam composition containing the polyol composition is used. The upper limit is usually 100% by mass, preferably 90% by mass, and more preferably 80% by mass.

[0018] Examples of other polyols that the polyol component may contain, as necessary, include amine-based polyols, aliphatic polyhydric alcohols (derivatives of aliphatic hydrocarbons), aromatic polyhydric alcohols (derivatives of aromatic hydrocarbons), natural fat-and-oil-based polyols (castor oil, etc.), polyether polyols (glycerin-based polyether polyols, aromatic polyether polyols, Mannich-based polyether polyols, sucrose-based polyether polyols, sorbitol-based polyether polyols, etc.), polyether ester polyols, aliphatic polyester polyols, polydiene polyols, etc. Among these, it is preferable to contain an amine-based polyol.

[0019] The amine polyol has any one of a primary amine, secondary amine and tertiary amine structures, and more preferably has a tertiary amine structure. In the present invention, since it has urethane reactivity and can act as a catalyst for promoting the formation of urethane bonds, ethylenediamine polyether polyol, Mannich polyether polyol, toluenediamine polyether polyol and the like are preferred, and among these, ethylenediamine polyether polyol is particularly preferred.

[0020] The ethylenediamine-based polyether polyol is preferably an alkylene oxide adduct of ethylenediamine, and examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, etc. The alkylene oxide may be one or more of these. From the viewpoint of the physical properties of the rigid foam and the price of the raw material, it is preferable that the alkylene oxide contains propylene oxide. In this case, the proportion of the amount 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, based on the total amount of the alkylene oxide. The hydroxyl value of the ethylenediamine-based polyether polyol is preferably 400 mgKOH / g or more from the viewpoint of the mechanical strength of the resulting foam.

[0021] The catalyst constituting the polyol composition of the present invention contains at least one selected from aromatic primary amines and aromatic secondary amines, and may contain other catalysts (described later) as necessary.

[0022] The aromatic primary amine is not particularly limited, and the number of amino groups contained therein is also not limited. In the present invention, a compound having a plurality of amino groups (-NH2) is preferred, and examples thereof include 1,4-diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,6-diamino-3,5-diethyltoluene, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 1-methyl-3,5-biphenylmethane, 1,2-diamino-3,5-biphenylmethane, 1,3-diamino-3,5-biphenylmethane, 1,4-diamino-3,5-biphenylmethane, 1,5-diamino-3,5-biphenylmethane, 1,6-diamino-3,5-biphenylmethane, 1,7-diamino-3,5-biphenylmethane, 1,8-diamino-3,5-biphenylmethane, 1,9-diamino-3,5-biphenylmethane, 1,9-diamino-3,5-biphenylmethane, 1,1-diamino-3,5-biphenylmethane, 1,2-diamino-3,5-biphenylmethane, 1,3-diamino-3,5-biphenylmethane, 1,4-diamino-3,5-biphenylmethane, 1,5 ... bis(methylthio)-2,4-diaminobenzene, 1-methyl-3,5-bis(methylthio)-2,6-diaminobenzene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1-methyl-3,5-diethyl-2,4-toluenediamine, 1-methyl-3,5-diethyl-2,6-toluenediamine, 3,5-dithiomethyl-2,4-diaminotoluene ene, 4,6-dimethyl-2-ethyl-1,3-diaminobenzene, 3,5,3',5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,5,3',5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3',5'-diisopropyl-4,4'-diaminodiphenylmethane, 2,4,6-triethyl-m-phenylenediamine, 3,5-diisopropyl-2,4-diaminotoluene, 3,5-di-sec-butyl-2,6-diaminotoluene, 3-ethyl-5-isopropyl-2,4-di Aminotoluene, 4,6-diisopropyl-m-phenylenediamine, 4,6-di-tert-butyl-m-phenylenediamine, 4,6-diethyl-m-phenylenediamine, 3-isopropyl-2,6-diaminotoluene, 5-isopropyl-2,4-diaminotoluene, 4-isopropyl-6-methyl-m-phenylenediamine, 4-isopropyl-6-tert-butyl-m-phenylenediamine, 4-ethyl-6-isopropyl-m-phenylenediamine, 4-methyl-6-tert-butyl-m-phenylenediamine, 4,6-di-sec-butyl-m-phenylenediamine, 4-ethyl-6-tert-butyl-m-phenylenediamine, 4-ethyl-6-sec-butyl-m-phenylenediamine, 4-ethyl-6-isobutyl-m-phenylenediamine, 4-isopropyl-6-isobutyl-m-phenylenediamine, 4-isopropyl-6-sec-butyl-m-phenylenediamine, 4-tert-butyl-6-isobutyl-m-phenylenediamine, 4-cyclopentyl-6-ethyl-m-phenylenediamine, 4-cyclohexyl-6-isopropyl-m-phenylenediamine amine, 4,6-dicyclopentyl-m-phenylenediamine, 2,2',6,6'-tetraethyl-4,4'-methylenebisaniline, 2,2',6,6'-tetraisopropyl-4,4'-methylenebisaniline, 2,2',6,6'-tetra-sec-butyl-4,4'-methylenebisaniline, 2,2'-dimethyl-6,6'-di-tert-butyl-4,4'-methylenebisaniline, 2,2'-di-tert-butyl-4,4'-methylenebisaniline, 2-isopropyl-2',6'-diethyl-4,4'-methylenebisaniline, etc.

[0023] The aromatic secondary amine is not particularly limited, and the number of -NHR groups (R is an organic group) contained is also not limited. In the present invention, a compound having a plurality of -NHR groups is preferred, and examples thereof include 4,4'-methylenebis(N-methylaniline), 4,4'-methylenebis[N-(1-methylpropyl)aniline], N,N'-di-iso-propyl-4,4'-diaminodiphenylmethane, N,N'-di-sec-butyl-4,4'-diaminodiphenylmethane, N,N'-di-iso-propyl-2,4-diaminotoluene, and N,N'-di-sec-butyl-2,4-diaminotoluene.

[0024] In the present invention, the polyol composition may contain only one of an aromatic primary amine and an aromatic secondary amine, or may contain both. Among these aromatic primary amines and aromatic secondary amines, those having a structure in which at least one of the carbons adjacent to the carbon having an amino group is substituted are preferred. In addition, from the viewpoint of odor and storage stability of the polyurethane foam composition containing the polyol composition of the present invention, it is preferred to use an aromatic primary amine.

[0025] In the polyol composition of the present invention, the total content of the aromatic primary amine and / or aromatic secondary amine is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1 to 6 parts by mass, relative to 100 parts by mass of the total of all polyol components constituting the polyol composition, from the viewpoints of odor and storage stability of a polyurethane foam composition containing the polyol composition of the present invention. By containing an aromatic primary amine and / or an aromatic secondary amine, when a polyurethane foam composition containing the polyol composition of the present invention is subjected to a storage stability test and the changes in cream time, gel time, and rise time before and after the test are observed, all of these can be made to be 0 to 5 seconds, so that a polyurethane foam composition with excellent storage stability can be obtained.

[0026] The catalyst according to the present invention may further contain, as other catalysts, a urethanization catalyst (resinification catalyst) that promotes the formation of a urethane bond, an isocyanurate catalyst (trimerization catalyst) that promotes the production of an isocyanurate ring, and the like.

[0027] Examples of the urethanization catalyst (resinization catalyst) include imidazole compounds, metal carboxylates, tertiary amines, etc. The urethanization catalyst used may be one type alone or two or more types.

[0028] Examples of the imidazole compound include imidazole, 1-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.

[0029] As the metal carboxylate, a compound in which a hydrogen atom constituting a carboxy group of a carboxylic acid is substituted with Sn, Pb, Zn, Fe, Cu, Ni, Co, Mn, Zr or Bi is preferably used.Specific examples of metal carboxylates include tin carboxylates such as tin acetate, tin butyrate, tin octylate, tin naphthenate, tin oleate, tin laurate, tin octanoate, tin dilaurate, tin dipalmitate, tin distearate, tin dioleate, tin bis(neodecanoate), tin stearate, and tin benzoate; lead carboxylates such as lead acetate, lead butyrate, lead octylate, lead naphthenate, lead oleate, lead octanoate, lead neodecanoate, lead laurate, lead stearate, and lead benzoate; zinc acetate, zinc butyrate, zinc octylate, zinc naphthenate, zinc oleate, and octanoate. zinc, zinc neodecanoate, zinc laurate, zinc stearate, zinc benzoate and other zinc carboxylates; iron acetate, iron butyrate, iron octylate, iron naphthenate, iron oleate, iron octanoate, iron neodecanoate, iron laurate, iron stearate, iron benzoate and other iron carboxylates; copper acetate, copper butyrate, copper octylate, copper naphthenate, copper oleate, copper octanoate, copper neodecanoate, copper laurate, copper stearate, copper benzoate and other copper carboxylates; nickel acetate, nickel butyrate, nickel octylate, nickel naphthenate, nickel oleate, nickel octanoate, neodecanoate, nickel carboxylates such as nickel acetate, nickel laurate, nickel stearate, and nickel benzoate; cobalt carboxylates such as cobalt acetate, cobalt butyrate, cobalt octylate, cobalt naphthenate, cobalt oleate, cobalt octanoate, cobalt neodecanoate, cobalt laurate, cobalt stearate, and cobalt benzoate; manganese acetate, manganese butyrate, manganese octylate, manganese naphthenate, manganese oleate, manganese octanoate, manganese neodecanoate, manganese laurate, manganese stearate, and manganese benzoate; Examples of the bismuth carboxylate include manganese carboxylate; zirconium carboxylates such as zirconium acetate, zirconium butyrate, zirconium octylate, zirconium naphthenate, zirconium oleate, zirconium octanoate, zirconium neodecanoate, zirconium laurate, zirconium stearate, and zirconium benzoate; and bismuth carboxylates such as bismuth acetate, bismuth butyrate, bismuth octylate, bismuth naphthenate, bismuth oleate, bismuth octanoate, bismuth neodecanoate, bismuth laurate, bismuth stearate, and bismuth benzoate.

[0030] Examples of tertiary amines 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; N,N-dicyclohexylmethylamine, (dimethylamino)acetonitrile, and N,N,N'-trimethylamine. Examples of the amines include methylethylenediamine, trimethylamine, N,N-dimethylcyclohexylamine, 1-(dimethylamino)pyrrole, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 4-dimethylaminotoluene, dimethylaniline, 4-dimethylaminoaniline, 2-(dimethylamino)pyridine, 4-(dimethylamino)pyridine, 4-(dimethylamino)benzonitrile, N,N-dimethylbenzylamine, 4-methylmorpholine, and bis(2-morpholinoethyl)ether.

[0031] In the present invention, the urethanization catalyst (resinification catalyst) preferably contains a tertiary amine, and particularly preferably comprises a combination of an imidazole compound, a metal carboxylate, and a tertiary amine.

[0032] When a urethane-forming catalyst (resin-forming catalyst) is used, polyurethane is efficiently formed, and therefore the amount used (total) is preferably 0.1 to 13 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 7 parts by mass, relative to 100 parts by mass of the total of all polyol components constituting the polyol composition.

[0033] Examples of the isocyanurate catalyst (trimerization catalyst) include quaternary ammonium salts, fatty acid alkali metal salts, nitrogen-containing aromatic compounds, tertiary ammonium salts, etc. The isocyanurate catalyst used may be one type alone or two or more types.

[0034] Examples of the quaternary ammonium group, which is the cation portion of the quaternary ammonium salt, 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; hydroxylammonium 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.

[0035] The anion portion of quaternary ammonium salts includes formate ion, acetate ion, octanoate ion, oxalate ion, malonate ion, succinate ion, glutarate ion, adipate ion, benzoate ion, toluate ion, ethylbenzoate ion, methylcarbonate ion, phenol ion, alkylbenzenesulfonate ion, toluenesulfonate ion, benzenesulfonate ion, phosphate ester ion, halide ion, OH - , CO3 2- , HCO3 - etc.

[0036] Examples of the fatty acid alkali metal salts include potassium octylate, potassium 2-ethylhexanoate, and sodium acetate. Examples of the nitrogen-containing aromatic compound include tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and tris(dimethylaminopropyl)hexahydrotriazine. Examples of the tertiary ammonium salt include trimethylammonium salt, triethylammonium salt, and triphenylammonium salt.

[0037] In the present invention, the isocyanurate catalyst (trimerization catalyst) preferably contains a quaternary ammonium salt.

[0038] When an isocyanurate catalyst (trimerization catalyst) is used, the production of an isocyanurate ring is promoted by the reaction between a hydroxy group of a polyol component and an isocyanate group of a polyisocyanate. Therefore, the amount (total) of the isocyanurate catalyst used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total of all the polyol components constituting the polyol composition.

[0039] The polyol composition of the present invention may contain other components in addition to the polyol component and catalyst as described above, such as a foaming agent, a foam stabilizer, a compatibilizer, a flame retardant, a formaldehyde scavenger, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, an antibacterial agent, a corrosion inhibitor, a colorant, etc.

[0040] In the present invention, a blowing agent containing a halogenated olefin is used as a raw material for a polyurethane foam composition used to produce a foam that has excellent adhesion to an adherend and is suppressed from shrinking in a low-temperature environment. This blowing agent can contain other blowing agents such as hydrocarbons, hydrofluorocarbons, water, etc. in addition to the halogenated olefin. The polyol composition of the present invention may be a composition containing the entire amount of the blowing agent contained in the polyurethane foam composition, or a composition that does not contain a part or all of the blowing agent.

[0041] The halogenated olefin is preferably an unsaturated hydrocarbon derivative having about 2 to 6 carbon atoms containing a chlorine atom, a fluorine atom or the like as a halogen atom, and examples thereof include hydrofluoroolefin and hydrochlorofluoroolefin.

[0042] Examples of hydrofluoroolefins 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); trifluoropropenes such as 3,3,3-trifluoropropene (HFO-1243zf); Examples of such fluoroisopropyl ethers include trifluorobutenes (HFO-1345); pentafluorobutene isomers (HFO-1354); 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); and nonafluoropentene isomers (HFO-1429).

[0043] In addition, examples of hydrochlorofluoroolefins 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), 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc), 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), and the like.

[0044] In a polyurethane foam composition containing the polyol composition of the present invention, the content of the halogenated olefin is preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass, and even more preferably 20 to 40 parts by mass, relative to 100 parts by mass of the total of all polyol components constituting the polyol composition.

[0045] Other examples of hydrocarbons and hydrofluorocarbons that can be used as blowing agents are given below.

[0046] Examples of the hydrocarbon include propane, butane, isobutane, pentane, isopentane, hexane, isohexane, neohexane, heptane, isoheptane, and cyclopentane.

[0047] Hydrofluorocarbons 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), 1,1,1,2,3,3,3-heptafluoropropane (H FC227ea), 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.

[0048] The other blowing agents are as described above, but the blowing agent according to the present invention is preferably composed of a halogenated olefin and water. In the polyurethane foam composition containing the polyol composition of the present invention, the content of water is preferably 3 to 7 parts by mass, more preferably 3.5 to 6.5 parts by mass, and even more preferably 4 to 6 parts by mass, based on 100 parts by mass of the total of all polyol components constituting the polyol composition.

[0049] The foam stabilizer may be any of nonionic, anionic and cationic compounds, but preferably contains a nonionic foam stabilizer. The foam stabilizer used may be one type only or two or more types. Specific examples of the foam stabilizer include silicone compounds such as organopolysiloxane, polyoxyalkylene-modified dimethylpolysiloxane, and polysiloxane oxyalkylene copolymers, as well as polyoxyethylene sorbitan fatty acid esters, polyoxyethylene castor oil fatty acid esters, and lauryl fatty acid ethylene oxide adducts.

[0050] In the present invention, the foam stabilizer preferably contains a silicone-based compound. When the polyol composition of the present invention contains a foam stabilizer, the content thereof is preferably 0.1 to 10 parts by mass, more preferably 1 to 7 parts by mass, and even more preferably 2 to 5 parts by mass, relative to 100 parts by mass of the total of all polyol components constituting the polyol composition.

[0051] Examples of the compatibilizer include a nonionic surfactant, propylene carbonate, etc. Examples of the nonionic surfactant include a polyoxyalkylene alkyl ether, a polyoxyalkyl ether, etc.

[0052] Examples of the flame retardant include organic phosphate esters, phosphates, stannates, halogen compounds (excluding organic phosphate esters), boron compounds, metal hydroxides, red phosphorus, phosphoric acid ester amides, phosphonitrile compounds, organic phosphonic acid compounds, organic phosphinic acid compounds, phosphine oxides, triazole compounds, tetrazole compounds, triazine compounds, cyclic monoureides, cyclic diureides, amidine compounds, etc. Only one type of flame retardant may be used, or two or more types may be used.

[0053] The method for producing the polyol composition of the present invention is not particularly limited and may be a method for mixing predetermined raw materials.

[0054] The polyurethane foam composition of the present invention is a composition comprising a combination of the polyol composition of the present invention, a blowing agent containing a halogenated olefin, and a polyisocyanate composition containing a polyisocyanate.

[0055] The polyisocyanate composition according to the present invention is a composition that contains a polyisocyanate and may contain a component that does not react with the isocyanate group of the polyisocyanate. The polyisocyanate composition may consist of only the polyisocyanate.

[0056] Polyisocyanate is a compound having two or more isocyanate groups in the molecule, which reacts with the polyol component in the polyol composition to produce polyurethane (resin).

[0057] Examples of the polyisocyanate include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, urethane prepolymers having an isocyanate group at the molecular end, isocyanurate-modified or carbodiimide-modified polyisocyanates, etc. The polyisocyanate composition may contain only one type of polyisocyanate or two or more types of polyisocyanates.

[0058] Examples of the aromatic polyisocyanate include diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, tolylene triisocyanate, polytolylene triisocyanate, xylylene diisocyanate, and naphthalene diisocyanate. Examples of the aliphatic polyisocyanate 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. Examples of alicyclic polyisocyanates include isophorone diisocyanate (3-isocyanatemethyl-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(isocyanatemethyl)cyclohexane, and 1,4-bis(isocyanatemethyl)cyclohexane.

[0059] In the present invention, the polyisocyanate preferably includes an aromatic polyisocyanate. The lower limit of the content of the aromatic polyisocyanate relative to the total polyisocyanate constituting the polyisocyanate composition is preferably 80 mass %, more preferably 90 mass %.

[0060] The polyisocyanate composition can contain, in addition to the polyisocyanate, a component that does not react with the polyisocyanate, such as a foaming agent, among the other components that may be contained in the polyol composition of the present invention.

[0061] The polyisocyanate contained in the polyisocyanate composition according to the present invention is a component that reacts with the polyol component contained in the polyol composition to give a foam having excellent adhesion to an adherend, and there is a preferred content ratio between the polyol and the polyisocyanate in the polyurethane foam composition according to the present invention. In the present invention, the polyol composition and the polyisocyanate composition are configured so that the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyol component is preferably 70 to 400, more preferably 100 to 250, and further preferably 120 to 200.

[0062] The method for producing the polyurethane foam composition of the present invention is not particularly limited as long as it is a method for mixing raw materials so that at least the polyol component, the blowing agent containing a halogenated olefin, and the polyisocyanate are contained. When mixing the raw materials, for example, a high-speed stirrer, an impingement mixer, etc. can be used.

[0063] In the present invention, for example, when a polyol composition containing a polyol component, a catalyst, and a blowing agent, all of which are kept at a constant temperature between 5°C and 15°C, is mixed with a polyisocyanate composition to prepare a polyurethane foam composition, the cream time, which is the time from the start of mixing to the start of foaming, can be preferably 7 seconds or less, more preferably 3 to 6 seconds. In addition, the gel time, which is the time from the start of mixing the polyol composition and the polyisocyanate composition to the start of thickening and gel strength, can be preferably 4 to 15 seconds, more preferably 5 to 13 seconds. Furthermore, the rise time, which is the time from the start of mixing the polyol composition and the polyisocyanate composition to the end of foaming, can be preferably 6 to 20 seconds, more preferably 8 to 17 seconds.

[0064] When the polyurethane foam composition of the present invention is applied to an adherend and foamed and cured on the surface of the adherend, a foam having excellent adhesion to the adherend can be obtained. The foam of the present invention is a rigid foam (rigid polyurethane foam) having a high closed cell ratio, and can be suitably used, for example, as a heat insulating material.

[0065] The method for producing the foam of the present invention is not particularly limited, and a conventionally known method can be applied depending on the application. For example, the laminate continuous foaming method in which the polyurethane foam composition is applied to an adherend and foamed and cured into a plate-like shape; the injection foaming method in which the polyurethane foam composition is injected into a predetermined space in an adherend and foamed and cured; and the spray foaming method in which the polyurethane foam composition is sprayed onto an adherend using a spray gun and foamed and cured, etc. can be mentioned. In addition, when the foaming agent is not contained in either the polyol composition or the polyisocyanate composition and the spray foaming method is adopted, the polyurethane foam composition is prepared on-site by mixing all the raw materials in advance using a foaming machine or the like. In addition, the constituent material of the adherend surface that the formed foam contacts is not particularly limited, and can be an inorganic material (metal, inorganic compound, etc.), an organic material (polymer, etc.), or a composite material containing these. When forming a thick polyurethane foam layer on the surface of an adherend, the spray foaming method is preferably used, which allows easy recoating. EXAMPLES

[0066] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" are by weight unless otherwise specified.

[0067] 1. Raw materials for the composition The raw materials for the polyurethane foam compositions used in the examples and comparative examples are shown below.

[0068] 1-1.Polyol 1-1-1. Aromatic polyester polyol (1) Phthalic anhydride polyester polyol (O-aromatic ester) The product used was "Maximol RDK-133" (trade name) manufactured by Air Water Performance Chemicals Inc. The aromatic concentration was 23%. (2) Terephthalic acid-based polyester polyol (P-aromatic ester) The product used was "Maximol RFK-505" (trade name) manufactured by Air Water Performance Chemicals Inc. The aromatic concentration was 22%.

[0069] 1-1-2. Aliphatic polyester polyol The succinic acid-based polyester polyol "Maximol SDK-145" (product name) manufactured by Air Water Performance Chemicals was used. The aromatic concentration was 0%.

[0070] 1-1-3. Amine-based polyol (1) Ethylenediamine-based polyether polyol 1 The initiator used was "EXCENOL 750ED" (product name) manufactured by AGC Co., Ltd. 100 mass % of the alkylene oxide added to the initiator was propylene oxide. (2) Ethylenediamine-based polyether polyol 2 "EXCENOL 500ED" (product name) manufactured by AGC was used. 100 mass % of the alkylene oxide added to the initiator was propylene oxide.

[0071] 1-2.Catalyst 1-2-1. Aromatic primary amines 2,6-Diamino-3,5-diethyltoluene (DETDA) or 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane was used. 1-2-2. Aromatic secondary amines 4,4'-methylenebis[N-(1-methylpropyl)aniline] was used. 1-2-3. Aliphatic primary amines Tetraethylenepentamine was used. 1-2-4. Trimerization catalyst A quaternary ammonium salt "Kao Raiser No. 420" (product name) manufactured by Kao Corporation was used.

[0072] 1-2-5. Resinification catalyst (1) Imidazole catalyst "Kao Raiser No. 350" (product name) manufactured by Kao Corporation was used. (2) Tertiary amines N,N-dicyclohexylmethylamine "Polycat 12" (product name) manufactured by Evonik Japan was used. (3) Metal carboxylates Bismuth octylate "Pucat 25" (trade name) manufactured by Nippon Chemical Industries Co., Ltd. was used.

[0073] 1-3.Foam stabilizer Silicone foam stabilizer "Niax" manufactured by Momentive Performance Materials Japan LLC TM "Silicone L-6100" (product name) was used.

[0074] 1-4.Flame retardant (TCPP) The organic phosphate ester "Tris(1-chloro-2-propyl)phosphate" (trade name) manufactured by Wanxiang Co., Ltd. was used.

[0075] 1-5. Foaming agents (1) Halogenated olefin 1 1-Chloro-3,3,3-trifluoropropene "HCFO-1233zd" (trade name) manufactured by Honeywell was used. (2) Halogenated olefin 2 1,1,1,4,4,4-Hexafluoro-2-butene "HFO-1336mzz" (trade name) manufactured by Chemours was used. (3)Water

[0076] 1-6.Polyisocyanate A polymeric MDI "Wannate PM-130" (product name) manufactured by Wanka Chemical Japan Co., Ltd. was used.

[0077] 2. Production and evaluation of polyurethane foam compositions The above-mentioned raw materials were used to produce a polyurethane foam composition. The composition was then used to produce a foam and various evaluations were performed.

[0078] Example 1 100 parts of O-aromatic ester, 1 part of aromatic primary amine "DETDA", 2 parts of trimerization catalyst, 1.5 parts of imidazole catalyst, 1.5 parts of tertiary amine, 2.5 parts of bismuth octylate, 3 parts of foam stabilizer, 30 parts of flame retardant, 25 parts of non-fluorocarbon blowing agent 1, and 4 parts of water were stirred and mixed to obtain a polyol composition (see Table 1). Thereafter, the resulting polyol composition (total 170.5 parts) and 170.5 parts of polyisocyanate were stirred and mixed to obtain a polyurethane foam composition.

[0079] Next, a foam (polyurethane foam) was produced using the obtained polyurethane foam composition according to a method conforming to JIS A 9526 (2022), that is, by spraying the polyurethane foam composition onto a concrete plate and curing it. Then, the adhesion of the foam to the concrete plate was evaluated. In addition, test pieces of a predetermined size were prepared from the formed foam, and the dimensional stability was evaluated. Furthermore, the storage stability of the polyurethane foam composition was also evaluated. These results are shown in Table 1.

[0080] (1) Adhesiveness The polyurethane foam composition was sprayed onto a concrete plate in an atmosphere at temperatures of 0°C and 10°C. After 3 minutes, the ends of the foam protruding from the concrete plate were cut along the concrete plate with a cutter, and the state of peeling near the adhesive surface between the concrete plate and the foam was visually observed, and the adhesion was evaluated according to the following criteria. ⊚: No peeling of the foam from the concrete plate was observed at either temperature. ○: No peeling of the foam from the concrete plate was observed at 10°C, but peeling of the foam was observed in less than 30% of the adhesive area at 0°C. △: No peeling of the foam from the concrete plate was observed at 10°C, but peeling of the foam was observed over 30% or more of the adhesive area at 0°C. ×: At 10°C, peeling of the foam from the concrete plate was observed over 30% or more of the adhesive area, and at 0°C, peeling of the foam was observed over 30% or more of the adhesive area.

[0081] (2) Dimensional stability Test pieces measuring 100 mm (length) x 100 mm (width) x 25 mm (thickness) were left to stand in an environment of -30°C for 48 hours, after which the length, width and thickness dimensions of the test pieces at -30°C were measured with vernier calipers, and the average dimensional change rate (shrinkage rate) was calculated using these measurements according to the following formula, and the dimensional stability was evaluated according to the following criteria. Dimensional change rate (%) = [((dimension after test)-(dimension before test)) / (dimension before test)] ×100 ◎: The dimensional change rate was -3% to +3%. ◯: The dimensional change rate was −5% or more and less than −3%, or more than +3% and less than +5%. Δ: The dimensional change rate was −10% or more but less than −5%, or more than +5% but not more than +10%. ×: The dimensional change rate was less than −10% or more than +10%.

[0082] (3) Storage stability A total of 170.5 parts of the polyol composition (hereinafter referred to as "liquid A") and 170.5 parts of the polyisocyanate (hereinafter referred to as "liquid B") in Example 1 shown in Table 1 were placed in a pressure-resistant container and left to stand for 120 hours in a thermostatic chamber maintained at 60°C. Thereafter, a storage stability test was performed in which the liquids A and B were uniformly mixed, and the reaction times (cream time, gel time, and rise time) at each stage from the start of mixing to the end of foaming were measured. The measured cream time (gel time, rise time) was compared with the cream time (gel time, rise time) measured after mixing without being left to stand in a thermostatic chamber. ⊚: The amount of change in cream time, gel time and rise time was all within 3 seconds. ◯: At least one of the changes in cream time, gel time, and rise time exceeded 3 seconds, and all were within 5 seconds. Δ: At least one of the changes in cream time, gel time, and rise time exceeded 5 seconds, and all were within 7 seconds. ×: At least one of the cream time, gel time and rise time exceeded 7 seconds.

[0083] Examples 2 to 14 and Comparative Examples 1 to 5 Compositions for polyurethane foams and polyurethane foams were produced in the same manner as in Example 1, except that the types and amounts of raw materials used were as shown in Tables 1, 2, and 3. Thereafter, various evaluations were carried out (see Tables 1 to 3).

[0084] [Table 1]

[0085] [Table 2]

[0086] [Table 3]

[0087] The following can be seen from Tables 1 to 3. Examples 1 to 14 are examples of polyurethane foam compositions containing a polyol composition having the configuration of the present invention, and foams having excellent adhesion to concrete, suppressed shrinkage in an environment of -30°C, and excellent dimensional stability could be obtained. The storage stability of the composition was also excellent. On the other hand, Comparative Example 1 is an example of using a polyurethane foam composition containing a polyol composition that does not contain an aromatic primary amine or an aromatic secondary amine, and the adhesion and dimensional stability of the obtained foam were insufficient. Comparative Example 2 is an example of using a polyurethane foam composition containing a polyol composition containing an aliphatic primary amine instead of an aromatic primary amine or an aromatic secondary amine, and the storage stability was insufficient, and the dimensional stability of the obtained foam was also insufficient. Comparative Examples 3 and 4 are examples of using a polyurethane foam composition containing a polyol composition containing an aliphatic polyester polyol instead of an aromatic polyester polyol, and the obtained foam had insufficient adhesion to concrete and dimensional stability. Comparative Example 5 is an example of using a polyurethane foam composition containing a polyol composition that does not contain a halogenated olefin as a foaming agent, and the obtained foam had insufficient adhesion to concrete and dimensional stability. [Industrial Applicability]

[0088] The composition for polyurethane foam of the present invention is suitable for forming foams used for insulation in interior and exterior wall materials and panels of buildings, insulation in metal siding, refrigerators, etc., insulation or prevention of condensation in the walls, ceilings, roofs, etc. of the framework of buildings, condominiums, cold storage warehouses, etc., and insulation in infusion pipes, etc. The composition for polyurethane foam of the present invention is particularly useful in applications requiring high adhesion to adherends made of concrete, etc.

Claims

1. A polyol composition used in preparing a polyurethane foam composition for use in producing a polyurethane foam, comprising a polyol composition, a blowing agent, and a polyisocyanate in combination, the polyol composition comprising: The polyol composition contains a polyol and a catalyst, The polyol comprises an aromatic polyester polyol, The blowing agent comprises a halogenated olefin, The catalyst is a polyol composition containing at least one selected from an aromatic primary amine and an aromatic secondary amine.

2. The polyol composition according to claim 1 , wherein the content of the aromatic polyester polyol is 30% by mass or more based on the polyol.

3. The polyol composition of claim 1 , wherein the polyol comprises an amine-based polyol.

4. The polyol composition of claim 1 , wherein the polyol composition contains the blowing agent.

5. The polyol composition of claim 4, wherein the blowing agent further comprises water.

6. The polyol composition according to claim 5, wherein the content of the water is 3 to 7 parts by mass per 100 parts by mass of the polyol.

7. 2. The polyol composition according to claim 1, wherein the halogenated olefin comprises at least one selected from HCFO1233zd, HFO1336mzz, and HFO1224yd.

8. The polyol composition of claim 1 , wherein the catalyst further comprises a trimerization catalyst.

9. The polyol composition of claim 1 , wherein the catalyst further comprises a tertiary amine.

10. A polyurethane foam composition comprising the polyol composition according to claim 1 in combination with a polyisocyanate composition containing a polyisocyanate.

11. A foam obtained by foaming the polyurethane foam composition according to claim 10.

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