JP2024146097A - Polyol composition, polyurethane foam composition and foam - Google Patents

Abstract

To provide a composition for polyurethane foam, which affords foam having excellent adhesiveness to an adherend, has excellent workability with lateral elongation suppressed and, further, has excellent storage stability; and a polyol composition used for preparing the same.SOLUTION: A polyol composition of the present invention is used in combination with a phosphoric acid ester, a blowing agent containing a halogenated olefin, a catalyst containing an imidazole compound, and a polyisocyanate to prepare a polyurethane foam composition for use in the production of polyurethane foam and contains an aromatic polyester polyol and an autocatalytic polyol. The polyol composition may contain water, and in that case, the content is less than 0.5 pt.mass relative to the total of 100 pts.mass of the polyols. The content of the phosphoric acid ester in the polyurethane foam composition is 1 to 15 pts.mass when the total of the polyols is taken as 100 pts.mass.SELECTED DRAWING: None

Description

The present invention relates to a composition for polyurethane foam that provides a foam (polyurethane foam) with excellent adhesion to an adherend and has excellent storage stability and workability.

Conventionally, polyurethane foam, phenol foam, etc. are known as resin foams. Among these, polyurethane foam is widely used because it has excellent heat insulation, soundproofing, etc. when filled in a gap or recess in a building, an electric product, furniture, a vehicle, etc.
For example, when forming an insulating layer (insulating material) made of polyurethane foam for insulating interior and exterior building wall materials and panels, insulating metal siding and electric refrigerators, insulating the walls, ceilings, roofs, etc. of buildings, condominiums, and refrigerated warehouses, a two-liquid composition, i.e., a mixture of a polyol composition (premix liquid) containing a polyol, a foaming agent, and, if necessary, various auxiliaries such as a catalyst and a foam stabilizer, and a polyisocyanate composition (polyurethane foam composition) containing a polyisocyanate, is generally applied to an adherend (object to be foamed), and the polyol and polyisocyanate are reacted, and the polyurethane foam layer formed while foaming and curing is adhered to the adherend. At this time, in order to obtain a thick polyurethane foam layer, spray coating or the like is applied, which allows easy recoating.

The following techniques are known for producing polyurethane foams or compositions used to form the polyurethane foams.
Patent Document 1 discloses a rigid polyurethane foam obtained by reacting a polyisocyanate with a polyol in the presence of a blowing agent, a catalyst, and the like, characterized in that the polyol contains a polyester polyol having an aromatic concentration of 17 to 35 wt %, a non-amine-based polyether polyol, and/or an aromatic amine-based polyether polyol, and the blowing agent contains a halogenated olefin.
Patent Document 2 discloses a foamable composition for polyurethane foam, which is composed of a polyol composition mainly containing a polyol and a polyisocyanate, and which forms a polyurethane foam by reacting the polyol with the polyisocyanate and foaming with a foaming agent, and which is characterized in that the polyol composition contains at least a halogenated hydroolefin as the foaming agent and further contains a cell opener.
Patent Document 3 discloses a foamable composition for polyurethane foam, which is composed of a polyol composition mainly composed of a polyol and a polyisocyanate, and which is prepared by reacting the polyol and the polyisocyanate using at least a metal carboxylate catalyst as a catalyst and foaming with a blowing agent to form a polyurethane foam, wherein the polyol composition contains a polyester polyol (A) and a polyether polyol (B) in a mass ratio of A:B=70:30 to 40:60, and 70 mass% or more of the polyether polyol is composed of an ethylenediamine-based polyether polyol, and further contains polymer fine particles.

JP 2016-155905 A JP 2022-15801 A JP 2022-32435 A

For example, a method may be adopted in which a polyurethane foam composition consisting of a polyol composition and a polyisocyanate composition is supplied to a wall, ceiling, etc. by spray coating, while foaming and curing the composition to form a polyurethane foam, and then the composition is adhered to obtain an integrated product having a heat insulating layer consisting of polyurethane foam. In this case, the polyurethane foam layer needs to be adhesive to the substrate. In addition, in such two-liquid polyurethane foam compositions, the reaction between the polyol and the polyisocyanate begins when the polyol composition and the polyisocyanate composition are mixed, so that in order to produce a foam (polyurethane foam) having uniform foam cells, it has been required that 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") be 0 to 8 seconds. It was also required that the time from the start of mixing the polyol composition and the polyisocyanate composition until thickening occurs and gel strength begins to appear (resinization time, hereinafter referred to as "gel time") be 4 to 15 seconds, and that the time from the start of mixing the polyol composition and the polyisocyanate composition until foaming ends (hereinafter referred to as "rise time") be 10 to 30 seconds. It was also required that the storage stability of the polyurethane foam composition be excellent if the cream time, gel time, and rise time are within the above ranges and 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.

Furthermore, in the spray application of polyurethane foam compositions, in order to form a thick polyurethane foam layer, the composition is usually sprayed in mist form onto a specific portion of the adherend, forming a coating film over a large area, while the reaction, foaming, and growth are repeated. When sprayed, any composition that unintentionally exceeds the specific portion spreads around the specific portion along the surface of the adherend without coming into contact with the adherend, forming an unnecessary polyurethane foam portion. The polyurethane foam portion in this unintentional foam formation phenomenon (hereinafter, this phenomenon is referred to as "lateral stretching") has poorer adhesion to the adherend than a polyurethane foam layer formed by spraying onto a specific portion of the adherend, resulting in reduced application (workability).

The present invention aims to provide a polyurethane foam composition that gives a foam with excellent adhesion to an adherend, has excellent workability due to suppressed lateral stretching, and has excellent storage stability. Another object of the present invention is to provide a polyol composition that can be used in the preparation of such a polyurethane foam composition.

The present invention is described below: By "autocatalytic polyol" is meant a polyol that has urethane reactivity and also acts as a catalyst to promote the formation of urethane bonds.
[1] A polyol composition used in preparing a polyurethane foam composition for use in producing a polyurethane foam, comprising a polyol composition, a phosphoric acid ester, a blowing agent, a catalyst, and a polyisocyanate in combination, the polyol composition comprising:
The blowing agent comprises a halogenated olefin,
The catalyst comprises an imidazole compound,
the content of the phosphoric acid ester in the composition for polyurethane foam is 1 to 15 parts by mass relative to 100 parts by mass of the total amount of all polyols constituting the composition for polyurethane foam;
The polyol composition contains an aromatic polyester polyol that does not have autocatalytic properties and an autocatalytic polyol,
The polyol composition may contain water, and when it contains water, the content of the water is less than 0.5 parts by mass when the total amount of all polyols constituting the polyol composition is 100 parts by mass.
[2] The polyol composition according to [1], wherein the total amount of the aromatic polyester polyol and the autocatalytic polyol is 70% by mass or more when the total amount of all polyols constituting the polyol composition is 100% by mass.
[3] The polyol composition according to [1], wherein the content of the aromatic polyester polyol is 60 to 90 mass% when the total of all polyols constituting the polyol composition is 100 mass%.
[4] The polyol composition according to [1] above, wherein the autocatalytic polyol comprises an alkylene oxide adduct of ethylenediamine.
[5] The polyol composition according to [1] above, which contains the phosphoric acid ester.
[6] The polyol composition according to the above [1], which contains the above blowing agent.
[7] The polyol composition according to [1] above, which contains the catalyst.
[8] The polyol composition according to the above [1], which does not contain water.
[9] A composition for polyurethane foam comprising the polyol composition according to [1] above, a blowing agent containing a halogenated olefin, a catalyst containing a phosphoric acid ester and an imidazole compound, and a polyisocyanate composition containing a polyisocyanate, wherein the content of the phosphoric acid ester is 1 to 15 parts by mass, relative to 100 parts by mass of the total amount of all polyols contained in the composition for polyurethane foam.
[10] The composition for polyurethane foam according to [9] above, wherein the polyol composition contains the blowing agent, the phosphate ester and the catalyst.
[11] The composition for polyurethane foam according to [9] above, wherein when the composition for polyurethane foam contains water, the content of the water is less than 0.5 parts by mass per 100 parts by mass of the total of all polyols contained in the composition for polyurethane foam.
[12] A foam obtained by foaming the polyurethane foam composition described in [9] above.

By using the polyurethane foam composition of the present invention, a foam (polyurethane foam) having excellent workability due to suppressed lateral expansion and excellent adhesion to an adherend 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 spray coating, etc.
The polyol composition of the present invention is suitable as a raw material for producing a polyurethane foam composition that provides such a foam (polyurethane foam).

The present invention will be described below. The matters set forth herein are illustrative and are intended to exemplify embodiments of the present invention, and are described for the purpose of providing what is believed to be the most effective and easily understandable explanation of the principles and conceptual features of the present invention. In this regard, it is not intended to show structural details of the present invention beyond the extent necessary for a fundamental understanding of the present invention, but rather to clarify to those skilled in the art how some aspects of the present invention are actually embodied through this description.

The polyol composition of the present invention is a composition used in the preparation of a polyurethane foam composition used in the production of polyurethane foam, which is a combination of the polyol composition, a blowing agent containing a phosphoric acid ester and a halogenated olefin, a catalyst containing an imidazole compound, and a polyisocyanate. In the present invention, a polyurethane foam composition having a phosphoric acid ester content of 1 to 15 parts by mass when the total of all polyols constituting the polyurethane foam composition is taken as 100 parts by mass can be applied to an adherend or supplied to a gap formed in the adherend to form a foam made of a urethane resin having excellent workability and excellent adhesion to the adherend due to suppressed lateral stretching, and the polyol composition of the present invention is a suitable composition for the preparation of such a polyurethane foam composition. The polyol composition of the present invention contains a polyol (hereinafter referred to as a "polyol component") containing an aromatic polyester polyol that does not have autocatalytic properties and a polyol that has autocatalytic properties, and may contain water, and when water is contained, the content of water is less than 0.5 parts by mass when the total of all polyol components is taken as 100 parts by mass. The polyol composition of the present invention may contain other components in addition to the polyol components, as described below. Examples of other components include a blowing agent, and water is known to act as a blowing agent. However, in the polyol composition of the present invention, the water content is less than 0.5 parts by mass when the total of all polyol components is 100 parts by mass, as described above, regardless of the origin of the water.

The polyol components constituting the polyol composition include an aromatic polyester polyol that does not have autocatalytic properties and an autocatalytic polyol, and may contain other polyols (described below) as necessary.

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.

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.

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 of 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 the "first polyester polyol"), and a polyester polyol formed from terephthalic acid and a diol (hereinafter referred to as the "second polyester polyol").

The content ratio 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.

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 60% by mass, more preferably 65% by mass, and even more preferably 70% by mass, from the viewpoint of adhesion to an adherend of a foam obtained using a polyurethane foam composition containing the polyol composition. The upper limit is preferably 90% by mass, more preferably 88% by mass, and even more preferably 85% by mass.

The polyol contained in the polyol composition of the present invention specifically has a nitrogen atom, preferably has a structure of any of primary amine, secondary amine and tertiary amine, more preferably has a tertiary amine structure. Examples of the self-catalytic polyol include ethylenediamine-based polyether polyol, Mannich-based polyether polyol, and toluenediamine-based polyether polyol. Of these, ethylenediamine-based polyether polyol is preferred. Furthermore, the aromatic polyester polyol that does not have self-catalytic properties specifically does not have a nitrogen atom.

The ethylenediamine-based polyether polyol is preferably an alkylene oxide adduct of ethylenediamine, and the alkylene oxide may be 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, the alkylene oxide preferably 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.

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 the autocatalytic polyol is preferably 5% by mass, more preferably 8% by mass, and even more preferably 10% by mass, from the viewpoints of the storage stability of the polyurethane foam composition containing the polyol composition and the adhesion of the foam obtained using this polyurethane foam composition to an adherend. The upper limit is preferably 30% by mass, more preferably 25% by mass, and even more preferably 20% by mass.

When the total of all polyol components constituting the polyol composition of the present invention is taken as 100% by mass, the ratio of the total amount of aromatic polyester polyol and autocatalytic polyol is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, from the viewpoints of the storage stability of a polyurethane foam composition containing the polyol composition and the adhesion of a foam obtained using this polyurethane foam composition to an adherend.

The polyol composition according to the present invention may further contain other polyols as necessary. Examples of other polyols include polyhydric alcohols, polyhydric phenols, natural fat-and-oil 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, toluene diamine-based polyether polyols, tolylene diamine-based polyether polyols, etc.

The polyol composition according to the present invention may contain other components (additives) in addition to polyol, such as a catalyst, a foaming agent, a foam stabilizer for uniformizing the cell structure of the foam, a phosphate ester, a flame retardant, a formaldehyde scavenger, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, an antibacterial agent, a corrosion inhibitor, a colorant, and water. Water may be used as a foaming agent, but is not limited to this.

Examples of catalysts include urethane-forming catalysts (resin-forming catalysts) that promote the formation of urethane bonds, and isocyanurate-forming catalysts (trimerization catalysts) that promote the production of isocyanurate rings. In the present invention, it is preferable to use a urethane-forming catalyst (resin-forming catalyst) and an isocyanurate-forming catalyst (trimerization catalyst) in combination.

Examples of urethane-forming catalysts (resin-forming catalysts) include imidazole compounds, tertiary amines, and metal salts of carboxylates containing K, Sn, Pb, Zn, Fe, Cu, Ni, Co, Mn, Zr, or Bi. The urethane-forming catalysts used may be one type or two or more types.

Imidazole compounds 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.

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 such compounds include ethylethylenediamine, 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.

As the metal carboxylate, a compound in which the hydrogen atom constituting the carboxy group of the carboxylic acid is replaced by K, Sn, Pb, Zn, Fe, Cu, Ni, Co, Mn, Zr, or Bi is preferably used. Specific metal carboxylates include potassium carboxylates such as potassium acetate, potassium butyrate, potassium octylate, potassium naphthenate, potassium oleate, potassium octanoate, potassium neodecanoate, potassium laurate, potassium stearate, and potassium benzoate; tin carboxylates such as tin acetate, tin butyrate, tin octylate, tin naphthenate, tin oleate, tin laurate, stannous octanoate, stannous dilaurate, stannous dipalmitate, stannous distearate, stannous dioleate, tin bis(neodecanoate), tin stearate, and tin benzoate; lead acetate, lead butyrate, lead octylate, lead naphthenate, lead oleate, octadecanoate, tin stearate, and tin benzoate; lead carboxylates such as lead phosphate, lead neodecanoate, lead laurate, lead stearate, and lead benzoate; zinc carboxylates such as zinc acetate, zinc butyrate, zinc octylate, zinc naphthenate, zinc oleate, zinc octanoate, zinc neodecanoate, zinc laurate, zinc stearate, and zinc benzoate; iron carboxylates such as iron acetate, iron butyrate, iron octylate, iron naphthenate, iron oleate, iron octanoate, iron neodecanoate, iron laurate, iron stearate, and iron benzoate; copper carboxylates such as copper acetate, copper butyrate, copper octylate, copper naphthenate, copper oleate, copper octanoate, copper neodecanoate, copper laurate, copper stearate, and copper benzoate; nickel acetate nickel carboxylates such as nickel butyrate, nickel octylate, nickel naphthenate, nickel oleate, nickel octanoate, nickel neodecanoate, 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, and manganese laurate manganese carboxylates such as manganese, manganese stearate, and manganese benzoate; 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; 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.

When the polyol composition of the present invention contains a catalyst, it is preferable that the polyol composition contains an imidazole compound as a urethane-forming catalyst (resin-forming catalyst), and it is particularly preferable that the imidazole compound is a combination of a tertiary amine and a metal salt of a carboxylate.

When a urethane catalyst (resin catalyst) is used, polyurethane is efficiently formed, so the amount used (total) is preferably 0.5 to 10 parts by mass, more preferably 1 to 7 parts by mass, and even more preferably 2 to 5 parts by mass, assuming that the total of all polyol components constituting the polyol composition is 100 parts by mass.

Examples of isocyanuration catalysts (trimerization catalysts) include fatty acid alkali metal salts, quaternary ammonium salts, nitrogen-containing aromatic compounds, tertiary ammonium salts, etc. Only one type of isocyanuration catalyst may be used, or two or more types may be used.

Examples of fatty acid alkali metal salts include potassium octylate, potassium 2-ethylhexanoate, and sodium acetate.

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.

Examples of the anion portion of the quaternary ammonium salt include 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- ^, _CO32- , _HCO3- ^, and the like.

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.

In the present invention, the isocyanurate catalyst (trimerization catalyst) preferably contains a fatty acid alkali metal salt or a quaternary ammonium salt.

When an isocyanurate catalyst (trimerization catalyst) is used, the reaction between the hydroxyl group of the polyol and the isocyanate group of the polyisocyanate promotes the formation of isocyanurate rings. Therefore, the amount of the catalyst used is preferably 0.3 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 1 to 4 parts by mass, assuming that the total amount of all the polyol components constituting the polyol composition is 100 parts by mass.

In the present invention, a catalyst is usually included as a raw material of the polyurethane foam composition used to produce a foam having excellent adhesion to an adherend. The polyol composition of the present invention may be a composition containing the entire amount of catalyst contained in the polyurethane foam composition, or a composition containing no part or all of the catalyst.

Examples of blowing agents include halogenated olefins, hydrocarbons, hydrofluorocarbons, water, and the like. The blowing agent contained in the polyol composition of the present invention may be one type or two or more types. In the present invention, since the polyurethane foam composition contains a halogenated olefin, when the polyol composition of the present invention contains a blowing agent, it is preferable that the blowing agent contains a halogenated olefin.

When the polyol composition of the present invention contains a blowing agent other than water (hereinafter referred to as "blowing agent (S)"), the content thereof 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.
The blowing agent (S) may consist solely of a halogenated olefin, or may consist of a halogenated olefin and at least one member selected from the group consisting of a hydrocarbon and a hydrofluorocarbon.

The halogenated olefin is preferably an unsaturated hydrocarbon derivative having about 2 to 6 carbon atoms and containing a halogen atom such as a chlorine atom or a fluorine atom, and examples of such an unsaturated hydrocarbon include hydrofluoroolefin and hydrochlorofluoroolefin.

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); tetrafluoropropenes such as tetrafluoropropene (HFO-1243zf); These 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).

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), and 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc).

Examples of hydrocarbons include propane, butane, isobutane, pentane, isopentane, hexane, isohexane, neohexane, heptane, isoheptane, and cyclopentane.

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, etc.

In the present invention, the blowing agent is included as a raw material of a polyurethane foam composition used to produce a foam having excellent adhesion to an adherend. 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 may be a composition containing no part or all of the blowing agent.

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 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.

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 5 parts by mass, more preferably 0.5 to 4 parts by mass, and even more preferably 1 to 3 parts by mass, relative to 100 parts by mass of the total of all polyol components constituting the polyol composition.

Examples of phosphate esters include monophosphate esters and condensed phosphate esters. Only one type of phosphate ester may be used, or two or more types may be used.

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, monoisodecyl phosphate, 2-acryloyl Examples include oxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resylcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), phosphaphenanthrene, and tris(β-chloropropyl)phosphate.

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

In the present invention, the phosphate ester is included as a raw material of a polyurethane foam composition used for producing a foam having excellent storage stability, workability, and adhesion to an adherend. The polyol composition of the present invention may be a composition containing the entire amount of the phosphate ester contained in the polyurethane foam composition, or a composition not containing a part or all of the phosphate ester.
When the polyol composition of the present invention contains a phosphoric acid ester, the content thereof is preferably 1 to 15 parts by mass, more preferably 1.5 to 14 parts by mass, and even more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the total of all polyol components constituting the polyol composition of the present invention.

Examples of flame retardants include phosphates, stannates, halogen compounds (excluding phosphate esters), boron compounds, metal hydroxides, red phosphorus, phosphonitrile compounds, organic phosphonic acid compounds, organic phosphinic acid compounds, phosphine oxides, triazole compounds, tetrazole compounds, triazine compounds, cyclic monoureides, cyclic diureides, amidine compounds, and the like. Only one type of flame retardant may be used, or two or more types may be used. It is preferable that the flame retardant be liquid in order to improve the heat insulating properties of the foam obtained by using the polyurethane foam composition.

In the polyurethane foam composition of the present invention described later, when the total of all polyol components contained is taken as 100 parts by mass, if the water content is less than 0.5 parts by mass (may be 0 parts by mass), a foam having excellent workability and excellent adhesion to an adherend can be efficiently produced. Therefore, it is useful to use a polyol composition having a water content of less than 0.5 parts by mass when the total of all polyol components is taken as 100 parts by mass as a raw material for producing such a polyurethane foam composition. When the polyol composition of the present invention contains water, the content is preferably less than 0.5 parts by mass, more preferably 0.4 parts by mass or less, and even more preferably 0.3 parts by mass or less when the total of all polyol components is taken as 100 parts by mass.
In the present invention, the water-free polyol composition also provides a polyurethane foam composition suitable for producing a foam having excellent workability and excellent adhesion to an adherend.

The method for producing the polyol composition of the present invention is not particularly limited. When producing a polyol composition containing water, it is preferable to mix the raw materials while taking into consideration the water content after production.

The polyurethane foam composition of the present invention is a composition obtained by combining the polyol composition of the present invention, a blowing agent containing a phosphoric acid ester and a halogenated olefin, a catalyst containing an imidazole compound, and a polyisocyanate composition containing a polyisocyanate.

The polyisocyanate composition according to the present invention is a composition that contains a polyisocyanate, but may also contain a component that does not react with the isocyanate group of the polyisocyanate. The polyisocyanate composition may consist of only polyisocyanate.

Polyisocyanate is a compound that has two or more isocyanate groups in its molecule and reacts with the polyol component in the polyol composition to produce polyurethane (resin).

Examples of polyisocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, urethane prepolymers having isocyanate groups at the molecular terminals, and isocyanurate- or carbodiimide-modified polyisocyanates. The polyisocyanate composition may contain one or more types of polyisocyanates.

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 the alicyclic polyisocyanate 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.

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 %.

The polyisocyanate composition may contain other components in addition to the polyisocyanate. As the other components, among the other components (additives) that may be contained in the polyol composition, components that do not react with the polyisocyanate, such as phosphate esters, blowing agents (S), catalysts, etc., can be used.

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 that has excellent adhesion to an adherend, and there is a preferred content ratio between the polyol and the polyisocyanate in the polyurethane foam composition of 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 0.9 to 4.5, more preferably 1 to 3, and even more preferably 1.1 to 2.

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 a polyol component, a phosphate ester, a blowing agent containing a halogenated olefin, a catalyst containing an imidazole compound, and a polyisocyanate are contained. When mixing the raw materials, for example, a high-speed stirrer, an impingement mixer, etc. can be used.

In the present invention, the polyol composition used in the production of the polyurethane foam composition may be a composition that does not contain any or all of the phosphoric acid ester. In this case, the method for producing the polyurethane foam composition may include (1) a method using a polyol composition that does not contain a phosphoric acid ester, a phosphoric acid ester, and a polyisocyanate composition as production raw materials, (2) a method using a polyol composition that does not contain a phosphoric acid ester and a polyisocyanate composition that contains a phosphoric acid ester as production raw materials, and (3) a method using a polyol composition that contains a portion of the phosphoric acid ester and a polyisocyanate composition that contains the remainder of the phosphoric acid ester as production raw materials. In this way, when the polyol composition of the present invention does not contain a phosphoric acid ester, the phosphoric acid ester is used alone or in the form contained in the polyisocyanate composition, and the amount used at that time is a preferred amount relative to the total amount of all the polyol components contained in the polyol composition as described above. In each of the above methods, the method for using the blowing agent (S) and the catalyst is not particularly limited.

Furthermore, in the present invention, the polyol composition used in the production of the polyurethane foam composition may be a composition that does not contain a part or all of the blowing agent. In this case, the following methods are applicable: (1) a method of using a polyol composition that may contain water but does not contain a blowing agent (S) such as a halogenated olefin, a blowing agent (S), and a polyisocyanate composition as raw materials for production; (2) a method of using a polyol composition that may contain water but does not contain a blowing agent (S) and a polyisocyanate composition containing a blowing agent (S) as raw materials for production; (3) a method of using a polyol composition that does not contain a blowing agent, water if necessary, a blowing agent (S), and a polyisocyanate composition as raw materials for production; (4) a method of using a polyol composition that does not contain a blowing agent, water if necessary, and a polyisocyanate composition containing a blowing agent (S) as raw materials for production; (5) a method of using a polyol composition that contains a part of the blowing agent (S) and a polyisocyanate composition containing the remainder of the blowing agent (S) as raw materials for production. In particular, when the polyol composition of the present invention does not contain a blowing agent (S), the blowing agent (S) is used alone or in the form of being contained in the polyisocyanate composition when producing a polyurethane foam composition, and the amount used at that time is a preferred amount relative to the total of all the polyol components contained in the polyol composition as described above. In addition, in each of the above methods, the method of using the phosphoric acid ester and the catalyst is not particularly limited.

In the present invention, when a polyurethane foam composition is produced without using a water-containing blowing agent or without using water alone, a polyurethane foam composition that does not contain water at all is produced, and such a composition is also a preferred embodiment for obtaining a foam that has excellent adhesion to an adherend.

In the present invention, for example, when a polyol composition containing a polyol component, a phosphate ester, a blowing agent containing a halogenated olefin, and a catalyst containing an imidazole compound, 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 8 seconds or less, more preferably 1 to 5 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 12 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 10 to 30 seconds, more preferably 10 to 25 seconds. And when the cream time, gel time, and rise time are in the above ranges, the time difference between the cream time and the gel time, and the time difference between the gel time and the rise time can all be 0 to 2 seconds, so that the polyurethane foam composition of the present invention has excellent storage stability.

When a foam is produced using the polyurethane foam composition of the present invention, a conventional method can be applied. For example, the laminate continuous foaming method includes coating the polyurethane foam composition on an adherend and foaming and curing it into a plate-like shape; the injection foaming method includes injecting the polyurethane foam composition into a predetermined space in an adherend and foaming and curing it; and the spray foaming method includes spraying the polyurethane foam composition on an adherend using a spray gun or the like to foam and cure it. In addition, when the catalyst, phosphate ester, water, and blowing agent (S) are 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 the individual 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.
In the case where a thick polyurethane foam layer is formed on the surface of an adherend, a spray foaming method is preferably used.

Here, when a polyurethane foam composition is sprayed onto an adherend to form a thick polyurethane foam layer, it is common to spray the composition in a mist onto the adherend to form a continuous coating film, and then repeat the reaction, foaming, and growth. However, during repeated spraying, the mist composition may unintentionally exceed a predetermined portion. At this time, the composition overflows the growing (accumulating) polyurethane foam layer and spreads around it along the adherend surface, resulting in "lateral stretching" in which unnecessary polyurethane foam portions are formed. As described above, the polyurethane foam composition of the present invention has a specific configuration, and thus the occurrence of lateral stretching is suppressed. This allows the polyurethane foam layer to be efficiently formed on the desired portion of the adherend, improving workability (workability).

The foam (polyurethane foam) of the present invention is a rigid foam (rigid polyurethane foam) with a high closed cell ratio, which is produced by foaming and curing the polyurethane foam composition of the present invention. As described above, the polyurethane foam composition of the present invention, which has a specific structure, is used, and when the composition is applied to an adherend and foamed and cured on the surface, it has particularly excellent adhesion to the adherend.

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.

1. Raw materials for producing the composition Raw materials for the polyurethane foam composition used in the examples and comparative examples are shown below.

1-1. Polyol 1-1-1. Aromatic polyester polyol (1) Phthalic anhydride polyester polyol (O-aromatic ester 1)
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 1)
The product used was "Maximol RFK-505" (trade name) manufactured by Air Water Performance Chemicals Inc. The aromatic concentration was 22%.

1-1-2. Autocatalytic polyol (1) Ethylenediamine-based polyether polyol 1
"EXCENOL 750ED" (product name) manufactured by AGC was used. 100% by 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% by mass of the alkylene oxide added to the initiator was propylene oxide.

Aliphatic polyester polyol: "Maximol SDK-145" (product name), a succinic acid-based polyester polyol manufactured by Air Water Performance Chemical Co., Ltd., was used. The aromatic concentration was 0%.

1-2. Catalyst 1-2-1. Trimerization catalyst Potassium octylate "Pucat 15G" (product name) manufactured by Nippon Chemical Industries Co., Ltd. was used.

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

1-3. Foam stabilizer A silicone foam stabilizer "Niax ^™ Silicone L-6100" (product name) manufactured by Momentive Performance Materials Japan, LLC was used.

1-4. Phosphate ester "Tris(1-chloro-2-propyl)phosphate" (trade name) manufactured by Wanxiang Co., Ltd. was used.

1-5. Blowing agents (1) Non-fluorocarbon blowing agents 1
1-chloro-3,3,3-trifluoropropene "HCFO-1233zd" (trade name) manufactured by Honeywell was used.
(2) Non-fluorocarbon blowing agent 2
1,1,1,4,4,4-hexafluoro-2-butene "HFO-1336mzz" (product name) manufactured by Chemours was used.
(3) Water

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

2. Production and Evaluation of Compositions for Polyurethane Foams Compositions for polyurethane foams were produced using the above-mentioned raw materials, and then various evaluations were carried out.

Example 1
80 parts of O-aromatic ester 1, 20 parts of ethylenediamine-based polyether 1, 1.5 parts of potassium octylate, 2 parts of imidazole-based catalyst, 1.5 parts of tertiary amine, 1 part of bismuth octylate, 2 parts of foam stabilizer, 8 parts of phosphoric acid ester, 30 parts of non-fluorocarbon-based blowing agent 1, and 0.3 parts of water were stirred and mixed to obtain a polyol composition (see Table 1).
Thereafter, the resulting polyol composition (total 151.3 parts) and 151.3 parts of polyisocyanate were stirred and mixed to obtain a polyurethane foam composition.

Next, 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. At this time, the adhesion to the concrete plate was evaluated. In addition, the polyurethane foam composition was sprayed onto a plywood sample board and cured to produce a polyurethane foam, and the workability (lateral elongation and edge adhesion) at this time was evaluated. Furthermore, the storage stability of the polyurethane foam composition was also evaluated. These results are also shown in Table 1.

(1) Adhesion to Concrete Plate A polyurethane foam composition was sprayed onto a concrete plate under ambient temperatures of 0°C and 10°C. After 3 minutes, the ends of the foam protruding from the concrete plate were cut off along the concrete plate with a cutter, and the vicinity of the adhesive surface between the concrete plate and the foam was visually observed to confirm whether or not the foam had peeled off.
◯: No peeling of the foam from the concrete plate was observed at either temperature.
Δ: No peeling of the foam from the concrete plate was observed at 10°C, but peeling of the foam was observed at 0°C.
×: Peeling of the foam from the concrete plate was observed.

(2) Workability (lateral expansion)
The polyurethane foam composition was sprayed onto a plywood sample board at 20° C. to form a polyurethane foam layer with a thickness of 70 mm. After curing was completed, the foam was cut horizontally relative to the plywood sample board, and the distance (mm) from the end of the applied part of the polyurethane foam composition to the tip of the foam part formed by foaming in the lateral direction was measured. The measurement was performed at 10 points, and the average value was calculated.
Good: The distance from the edge of the coated area to the tip of the foam was 10 mm or less.
Δ: The distance from the edge of the coated area to the tip of the foam was more than 10 mm and 30 mm or less.
x: The distance from the edge of the coated area to the tip of the foam exceeded 30 mm.

(3) Workability (edge adhesion)
The polyurethane foam composition was sprayed onto the entire surface of a plywood sample board (size: 900 mm x 900 mm) at 20°C to form a polyurethane foam layer having a thickness of 70 mm. Five test pieces (size: 25 mm x 25 mm) each made of an integrated body including a 50 mm thick polyurethane foam layer were taken out from each end at a position 50 mm from each end, for a total of 10 test pieces. The adhesive strength of the polyurethane foam layer to the plywood sample board was measured by a method conforming to A 9526. The measuring device was a universal testing machine manufactured by Minebea Co., Ltd.
A: The adhesive strength was 120 kPa or more.
×: The adhesive strength was less than 120 kPa.

(4) Storage stability 151.3 parts of a polyol composition (hereinafter referred to as "liquid A") and 151.3 parts of a polyisocyanate (hereinafter referred to as "liquid B") were placed in a pressure-resistant container and allowed to stand for 120 hours in a thermostatic chamber maintained at 60°C. Thereafter, a storage stability test was conducted in which liquid A and liquid 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 standing in a thermostatic chamber.
A: The amount of change in cream time, gel time and rise time was within 2 seconds.
x: At least one of the cream time, gel time and rise time exceeded 2 seconds.

Examples 2 to 13 and Comparative Examples 1 to 7
Compositions for 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).

The following can be seen from Tables 1 to 3.
Examples 1 to 13 are examples of polyurethane foam compositions containing a polyol composition having the configuration of the present invention, and the obtained foams had excellent storage stability and workability, and were excellent in adhesion to the adherend. On the other hand, Comparative Examples 1 to 3 are examples using polyurethane foam compositions containing a polyol composition with too much water content, and in particular, the adhesion to the adherend and workability were insufficient. Comparative Example 4 is an example using a polyurethane foam composition that does not contain an imidazole compound, and the storage stability, workability, and adhesion to the adherend were insufficient. Comparative Example 5 is an example using a polyurethane foam composition containing a polyol composition containing an aliphatic polyester polyol instead of an aromatic polyester polyol, and the storage stability, workability, and adhesion to the adherend were insufficient. Comparative Example 6 is an example using a polyurethane foam composition containing a polyol composition that does not contain an autocatalytic polyol, and the storage stability, workability, and adhesion to the adherend were insufficient. In addition, Comparative Example 7 is an example using a polyurethane foam composition containing a polyol composition with too much phosphoric acid ester content, and the adhesion to the adherend and workability were insufficient.

The polyurethane foam composition 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 and refrigerators, insulation or condensation prevention in the walls, ceilings, roofs, etc. of buildings, condominiums, refrigerated warehouses, etc., and insulation in infusion pipes, etc.

Claims (12)

A polyol composition for use in preparing a polyurethane foam composition for use in producing a polyurethane foam, comprising a polyol composition, a phosphate ester, a blowing agent, a catalyst, and a polyisocyanate in combination, the polyol composition comprising:
The blowing agent comprises a halogenated olefin;
The catalyst comprises an imidazole compound,
the content of the phosphate ester in the composition for polyurethane foam is 1 to 15 parts by mass relative to 100 parts by mass of the total amount of all polyols constituting the composition for polyurethane foam;
The polyol composition contains an aromatic polyester polyol that does not have autocatalytic properties and an autocatalytic polyol,
The polyol composition may contain water, and when it contains water, the content of the water is less than 0.5 parts by mass when the total amount of all polyols constituting the polyol composition is 100 parts by mass. The polyol composition according to claim 1, wherein the total amount of the aromatic polyester polyol and the autocatalytic polyol is 70% by mass or more when the total amount of all polyols constituting the polyol composition is 100% by mass. The polyol composition according to claim 1, wherein the content of the aromatic polyester polyol is 60 to 90% by mass, assuming that the total of all polyols constituting the polyol composition is 100% by mass. The polyol composition according to claim 1, wherein the autocatalytic polyol comprises an alkylene oxide adduct of ethylenediamine. The polyol composition according to claim 1, which contains the phosphate ester. The polyol composition according to claim 1, which contains the blowing agent. The polyol composition according to claim 1, which contains the catalyst. The polyol composition according to claim 1, which does not contain water. A polyurethane foam composition comprising the polyol composition according to claim 1, a blowing agent containing a halogenated olefin, a catalyst containing a phosphoric acid ester and an imidazole compound, and a polyisocyanate composition containing a polyisocyanate, the content of the phosphoric acid ester being 1 to 15 parts by mass when the total of all polyols contained in the polyurethane foam composition is 100 parts by mass. The polyurethane foam composition according to claim 9, wherein the polyol composition contains the blowing agent, the phosphate ester, and the catalyst. The polyurethane foam composition according to claim 9, wherein when the polyurethane foam composition contains water, the content of the water is less than 0.5 parts by mass when the total of all polyols contained in the polyurethane foam composition is taken as 100 parts by mass. A foam obtained by foaming the polyurethane foam composition according to claim 9.