Polyurethane foam-forming composition, polyurethane foam, and polyisocyanate composition

Abstract

To provide a polyurethane foam-forming composition exhibiting excellent storage stability of a polyol composition and contributing to formation of a polyurethane foam with superior flame retardancy.SOLUTION: A polyurethane foam-forming composition comprises a polyol composition and a polyisocyanate composition, wherein the polyisocyanate composition includes a polyisocyanate compound and at least one solid flame retardant selected from the group consisting of an organic salt-based flame retardant and an inorganic salt-based flame retardant.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to polyurethane foam-forming compositions, polyurethane foams, and polyisocyanate compositions. [Background technology]

[0002] Taking advantage of their excellent thermal insulation properties, polyurethane foams are used in practical applications for insulating and preventing condensation on ceilings, roofs, walls, and other surfaces of buildings such as apartment complexes, detached houses, and commercial buildings. Although polyurethane foams are lightweight, they are flammable because they are organic. To address this issue, polyurethane foams containing flame retardants or other additives to enhance their flame retardancy are being used.

[0003] For example, Japanese Patent Application Laid-Open No. 2019-031651 (Patent Document 1) describes a foam-forming curable composition containing a polyol compound, a blowing agent, a catalyst, a foam stabilizer, a phosphorus compound, and a polyisocyanate compound, and the phosphorus compound includes a phosphinate compound.

[0004] Furthermore, International Publication No. 2020 / 110332 (Patent Document 2) describes a foamable composition for non-flammable polyurethane foam, which is composed of composition A containing a polyol and composition B containing a polyisocyanate, and in which a polyurethane foam is formed by the reaction between the polyol and the polyisocyanate and foaming with a blowing agent, wherein composition A contains at least a trimerization catalyst as a catalyst, and an organic phosphinic acid metal salt is contained in at least one of composition A and composition B in a ratio of 30 parts by mass or more per 50 parts by mass of the polyol. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2019-031651 [Patent Document 2] International Publication No. 2020 / 110332 Summary of the Invention [Problem to be solved by the invention]

[0006] However, conventional foamable compositions for forming polyurethane foams do not necessarily have sufficient storage stability.

[0007] Accordingly, an object of one aspect of the present disclosure is to provide a polyurethane foam-forming composition that contributes to the production of polyurethane foams having excellent flame retardancy and excellent storage stability of a polyol composition. Another object of the present disclosure is to provide a polyisocyanate composition for use in the polyurethane foam-forming composition. Still another object of the present disclosure is to provide a polyurethane foam that is a foam of the polyurethane foam-forming composition and has excellent flame retardancy. [Means for solving the problem]

[0008] The present disclosure provides the following aspects.

[0009] [1] A polyurethane foam-forming composition comprising a polyol composition and a polyisocyanate composition, The polyisocyanate composition is a polyurethane foam-forming composition comprising a polyisocyanate compound and at least one solid flame retardant selected from the group consisting of organic salt-based flame retardants and inorganic salt-based flame retardants. [2] The polyurethane foam-forming composition according to [1], wherein the content of the solid flame retardant is 1 to 20 mass %, based on the mass of polyurethane foam solids in the polyurethane foam-forming composition. [3] The polyurethane foam-forming composition according to [1] or [2], wherein the solid flame retardant is at least one selected from the group consisting of a phosphinate-containing flame retardant, a phosphate-containing flame retardant, a borate-containing flame retardant, and an antimonate-containing flame retardant. [4] The polyurethane foam-forming composition according to any one of [1] to [3], wherein the polyurethane foam-forming composition contains a liquid flame retardant. [5] The polyurethane foam-forming composition according to [4], wherein the content of the liquid flame retardant is 1 to 30 mass %, based on the mass of polyurethane foam solids in the polyurethane foam-forming composition. [6] The polyurethane foam-forming composition may optionally contain a solid flame retardant other than the solid flame retardant, The polyurethane foam-forming composition according to [4] or [5], wherein the total amount of the solid flame retardant, the liquid flame retardant, and the other solid flame retardant is 5 to 50 mass %, based on the mass of polyurethane foam solids in the polyurethane foam-forming composition. [7] The polyurethane foam-forming composition according to any one of [4] to [6], wherein the liquid flame retardant is a phosphate ester-based flame retardant. [8] The polyurethane foam-forming composition according to any one of [1] to [7], having an isocyanate index in the range of 200 to 700. [9] The polyurethane foam-forming composition comprises a blowing agent; the blowing agent comprises water; The polyurethane foam-forming composition according to any one of [1] to [8], wherein the water content in the polyurethane foam-forming composition is 0.01 to 1.0 mass %, based on the mass of polyurethane foam solids in the polyurethane foam-forming composition.

[10] A polyurethane foam, which is a foam of the polyurethane foam-forming composition according to any one of [1] to [9].

[11] Radiant heat intensity of 50 kW / m2, based on the test method described in ISO-5660 2 When heated for 10 minutes under the conditions, the total heat generation is 11MJ / m 2 The polyurethane foam according to

[10] , which is:

[12] A polyisocyanate composition for use in a polyurethane foam-forming composition, comprising a polyol composition and a polyisocyanate composition, The polyisocyanate composition comprises a polyisocyanate compound and at least one solid flame retardant selected from the group consisting of organic salt-based flame retardants and inorganic salt-based flame retardants.

[13] The polyisocyanate composition according to

[12] , wherein the solid flame retardant is at least one selected from the group consisting of phosphinate-containing flame retardants, phosphate-containing flame retardants, borate-containing flame retardants, and antimonate-containing flame retardants.

[14] The polyisocyanate composition according to

[12] or

[13] , wherein the content of the solid flame retardant is 1 to 30 mass % based on the total amount of the polyisocyanate composition. [Effects of the Invention]

[0010] One aspect of the present disclosure provides a polyurethane foam-forming composition that contributes to the production of polyurethane foams having excellent flame retardancy and excellent storage stability of a polyol composition. Another aspect of the present disclosure provides a polyisocyanate composition for use in the polyurethane foam-forming composition. Yet another aspect of the present disclosure provides a polyurethane foam that is a foam of the polyurethane foam-forming composition and has excellent flame retardancy. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present inventors have found that when a composition containing a polyol compound, water, and a catalyst is blended with a phosphinate or the like, the phosphinate or the like dissolves in water, making the composition acidic and deactivating the catalyst, resulting in a decrease in the storage stability of the composition. Based on this finding, the present inventors have discovered that adding at least one solid flame retardant selected from the group consisting of organic salt-based flame retardants and inorganic salt-based flame retardants to a polyisocyanate composition improves the storage stability of the polyurethane foam-forming composition and the flame retardancy of the resulting polyurethane foam, thereby achieving the various aspects of the present disclosure. Specifically, the decrease in storage stability refers to a decrease in the reaction rate between the polyol compound and the polyisocyanate compound.

[0012] Exemplary embodiments for carrying out each aspect of the present disclosure will be described in further detail below, although the present disclosure is not limited to the following embodiments.

[0013] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. Furthermore, the upper and lower limit values ​​described individually can be combined in any way.

[0014] [Polyurethane foam-forming composition, polyol composition, polyisocyanate composition] A polyurethane foam-forming composition according to one embodiment of the present disclosure is a polyurethane foam-forming composition comprising a polyol composition and a polyisocyanate composition, The polyisocyanate composition comprises a polyisocyanate compound and at least one solid flame retardant selected from the group consisting of organic salt-based flame retardants and inorganic salt-based flame retardants. The polyurethane foam-forming composition may be a two-component type or a multi-component type consisting of two or more components. The term "two-component type" refers to a configuration in which a first component containing a polyol composition and a second component containing a polyisocyanate composition are stored separately and mixed when foam is formed. The term "multi-component type" refers to a configuration in which a first component containing a polyol composition, a second component containing a polyisocyanate composition, and a third component (and a fourth or more components) containing components other than the polyol composition and the polyisocyanate composition are stored separately and mixed when foam is formed.

[0015] Polyurethane foam can be formed by mixing the polyol composition and the polyisocyanate composition.

[0016] Further, a polyisocyanate composition according to another embodiment of the present disclosure is a polyisocyanate composition for use in a polyurethane foam-forming composition, the polyisocyanate composition comprising a polyol composition and a polyisocyanate composition, The polyisocyanate composition contains a polyisocyanate compound and at least one solid flame retardant selected from the group consisting of organic salt-based flame retardants and inorganic salt-based flame retardants.

[0017] [Polyisocyanate composition] The polyisocyanate composition can be mixed with a polyol composition to form a polyurethane foam. The polyisocyanate composition is preferably used as the second component of a two-component or multi-component polyurethane foam-forming composition. Specifically, during distribution, the composition is prepared in a two-component or multi-component form, combining a first component containing a polyol composition, a second component containing a polyisocyanate composition, and, in the case of a multi-component composition, a third component (and / or fourth component) containing components other than the polyol composition and the polyisocyanate composition. During foam formation, the first component and the second component, or in the case of a multi-component composition, the third component (and / or fourth component) are mixed and used. The polyisocyanate composition contains, as essential components, a polyisocyanate compound and at least one solid flame retardant selected from the group consisting of organic salt-based flame retardants and inorganic salt-based flame retardants. The polyisocyanate composition preferably does not contain a catalyst.

[0018] <Polyisocyanate compounds> Examples of polyisocyanate compounds include various polyisocyanate compounds, such as aromatic, alicyclic, and aliphatic polyisocyanate compounds having two or more isocyanate groups. Liquid diphenylmethane diisocyanate (MDI) is preferred because of its ease of handling, rapid reaction, excellent physical properties of the resulting polyurethane foam, and low cost. Examples of liquid MDI include crude MDI (also known as polymeric MDI). Specific commercial liquid MDI products include "44V-10" and "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.) and "Millionate MR-200" (manufactured by Tosoh Corporation). Uretonimine-containing MDI (e.g., commercially available product "Millionate MTL" (manufactured by Tosoh Corporation)) may also be used. Liquid MDI may be used in combination with other polyisocyanate compounds, and any polyisocyanate compound known in the polyurethane technical field can be used without limitation.

[0019] <Solid flame retardant> The solid flame retardant is at least one selected from the group consisting of organic salt-based flame retardants and inorganic salt-based flame retardants. In the present disclosure, the solid flame retardant refers to one that is in a solid state at 23°C.

[0020] Examples of organic salt-based flame retardants include, but are not limited to, organic acid salt-based flame retardants such as organic phosphinate-containing flame retardants and organic phosphate-containing flame retardants. Examples of inorganic salt-based flame retardants include, but are not limited to, inorganic phosphate-containing flame retardants, inorganic polyphosphate-containing flame retardants, borate-containing flame retardants, antimonate-containing flame retardants, and other inorganic acid salt-based flame retardants. Among these solid flame retardants, at least one selected from the group consisting of phosphinate-containing flame retardants, phosphate-containing flame retardants, borate-containing flame retardants, and antimonate-containing flame retardants is preferred.

[0021] (Phosphinate-containing flame retardants) The phosphinate-containing flame retardant is preferably one containing a phosphinate represented by the following formula (A-1) or (A-2) and / or a polymer thereof.

[0022] [ka]

[0023] [ka]

[0024] (R 1 , R 2 are the same or different and are a hydrogen atom, a methyl group, an ethyl group, or a linear or branched alkyl group having 3 to 6 carbon atoms. 3 is a methyl group, an ethyl group, or a linear or branched alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group having 7 to 20 carbon atoms, or an arylalkylene group having 7 to 20 carbon atoms. M is Na, Li, K, Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base. m is 1 to 4, n is 1 to 4, and x is 1 to 4, provided that in the formula (A-2), 2×n=m×x.

[0025] Above R 1 , R 2 are preferably the same or different and are a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-pentyl group, or a phenyl group. 3 is preferably a methylene group, an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, a t-butylene group, an n-pentylene group, an n-octylene group, an n-dodecylene group, a phenylene group, a naphthylene group, a methylphenylene group, an ethylphenylene group, a t-butylphenylene group, a methylnaphthylene group, an ethylnaphthylene group, a t-butylnaphthylene group, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or a phenylbutylene group. The above M is preferably Mg, Ca, Al, Sn, Ti, Zn, Fe, or Zr.

[0026] Examples of such phosphinates include aluminum phosphinate, sodium phosphinate, calcium phosphinate, potassium phosphinate, aluminum tris(dimethylphosphinate), aluminum tris(diethylphosphinate), potassium tris(diethylphosphinate), calcium tris(diethylphosphinate), sodium tris(diethylphosphinate), aluminum tris(methylethylphosphinate), aluminum tris(butylethylphosphinate), aluminum tris(diphenylphosphinate), zinc bis(diethylphosphinate), zinc bis(methylethylphosphinate), zinc bis(diphenylphosphinate), titanyl bis(diethylphosphinate), titanium tetrakis(diethylphosphinate), titanyl bis(methylethylphosphinate), titanium tetrakis(methylethylphosphinate), titanyl bis(diphenylphosphinate), titanium tetrakis(diphenylphosphinate), and the like, as well as combinations of any two or more thereof. Among these, aluminum tris(phosphinate) selected from aluminum phosphinate, sodium phosphinate, aluminum tris(dimethylphosphinate), aluminum tris(diethylphosphinate), aluminum tris(methylethylphosphinate), aluminum tris(butylethylphosphinate), and aluminum tris(diphenylphosphinate) is particularly preferred. Such phosphinates may be commercially available products or synthesized products. For example, in the case of alkylphosphinate metal salts, they can be obtained by reacting phosphinic acid and / or its alkali metal salt with an olefin in the presence of a free radical initiator, and then, if necessary, reacting the resulting alkylphosphinic acid and / or its alkali metal salt with a metal compound.

[0027] (phosphate-containing flame retardants) Examples of phosphate-containing flame retardants include those containing a phosphate salt formed from phosphoric acid and at least one metal or amine compound selected from the group consisting of metals from Groups IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. Examples of metals from Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron(II), iron(III), and aluminum. Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, and combinations of any two or more of these. Examples of aromatic amines include pyridine, triazine, and melamine. The phosphate-containing flame retardants may be subjected to known water resistance-improving treatments, such as treatment with a silane coupling agent or coating with a melamine resin.

[0028] Specific examples of phosphate-containing flame retardants include monophosphates, pyrophosphates, and polyphosphates. The monophosphate salt is not particularly limited, but examples thereof include ammonium salts such as monoammonium phosphate and diammonium phosphate; sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, and sodium hypophosphite; potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, and potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, and lithium hypophosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, and barium hypophosphite; magnesium salts such as magnesium dihydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite; aluminum salts such as aluminum dihydrogen phosphate, aluminum phosphate, aluminum phosphite, and aluminum hypophosphite; and combinations of any two or more thereof. Among these, monoammonium phosphate, diammonium phosphate, trisodium phosphate, and aluminum phosphate are preferred.

[0029] Specific examples of polyphosphates include, but are not limited to, ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, aluminum polyphosphate, and combinations of any two or more of these. Among these, ammonium polyphosphate and melamine polyphosphate are preferred.

[0030] Among the phosphate-containing flame retardants, polyphosphates are preferred from the viewpoint of improving the flame retardancy of polyurethane foams and from the viewpoint of significantly improving storage stability.

[0031] (Borate-containing flame retardants) Specific examples of borate-containing flame retardants include alkali metal borates such as lithium borate, sodium borate, potassium borate, and cesium borate, alkaline earth metal borates such as magnesium borate, calcium borate, and barium borate, zirconium borate, zinc borate, aluminum borate, and ammonium borate, and combinations of any two or more of these. Of these, zinc borate is preferred.

[0032] (Antimonate-containing flame retardants) Examples of antimonate-containing flame retardants include metal antimonates such as sodium antimonate and potassium antimonate, metal pyroantimonates such as sodium pyroantimonate and potassium pyroantimonate, and combinations of any two or more of these.

[0033] The content of the solid flame retardant in the polyisocyanate composition may be 1 to 40% by mass, preferably 1 to 30% by mass, more preferably 2 to 30% by mass, even more preferably 3 to 25% by mass, particularly preferably 4 to 23% by mass, and most preferably 5 to 20% by mass, based on the total amount of the polyisocyanate composition. When the content of the solid flame retardant is within the above range, a polyurethane foam-forming composition that contributes to the production of polyurethane foams having excellent storage stability and good flame retardancy is more likely to be obtained. Furthermore, when the content of the solid flame retardant is 1% by mass or more, polyurethane foams with particularly excellent flame retardancy are more likely to be obtained. When the content of the solid flame retardant is equal to or less than the above upper limit, the formation rate of an isocyanurate structure is increased, and polyurethane foams with even better flame retardancy are more likely to be obtained.

[0034] The content of the solid flame retardant in the polyurethane foam-forming composition is preferably 1 to 20 mass%, more preferably 2 to 15 mass%, even more preferably 3 to 13 mass%, particularly preferably 4 to 11 mass%, and most preferably 5 to 10 mass%, based on the mass of the polyurethane foam solids in the polyurethane foam-forming composition. When the content of the solid flame retardant is within the above range, a polyol composition with good storage stability and a polyurethane foam with good flame retardancy tend to be more easily obtained. Furthermore, when the content of the solid flame retardant is 1 mass% or more, a polyurethane foam with particularly excellent flame retardancy tends to be more easily obtained. When the content of the solid flame retardant is equal to or less than the above upper limit, the formation rate of an isocyanurate structure increases, and a polyurethane foam with even more excellent flame retardancy tends to be more easily obtained.

[0035] In the present disclosure, the polyurethane foam solids content in a polyurethane foam-forming composition refers to the components, among the various components contained in the polyurethane foam-forming composition, that form foam as polyurethane resin components, excluding those that turn into gas and are released outside the polyurethane foam, and those that turn into gas and are contained in the cells of the polyurethane foam.

[0036] [Polyol composition] The polyol composition forms a polyurethane foam by mixing with a polyisocyanate composition. The polyol composition is preferably used as a first liquid of a polyurethane foam-forming composition. That is, during distribution, the polyol composition is preferably in a two-liquid form, combining a first liquid containing the polyol composition with a second liquid comprising the polyisocyanate composition according to one embodiment of the present disclosure, and these first and second liquids are mixed together during foam formation. The polyol composition contains a polyol compound as an essential component. The polyol composition may further contain a catalyst. The polyol composition may contain an organic salt-based flame retardant and an inorganic salt-based flame retardant to the extent that storage stability is not significantly impaired. However, it is preferable that the polyol composition be free of, or substantially free of, organic salt-based flame retardants and inorganic salt-based flame retardants.

[0037] <Polyol compounds> The polyol compound is not particularly limited, but preferably contains a polyether polyol or a polyester polyol. In particular, from the viewpoint of further improving the flame retardancy and the like of the resulting polyurethane foam, it is preferable to contain an aromatic polyol compound such as an aromatic polyether polyol or an aromatic polyester polyol, as described below.

[0038] <Polyether polyol> The polyether polyol is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of an alkylene oxide with an initiator having two or more active hydrogen atoms. Examples of the initiator include aliphatic polyhydric alcohols such as glycols (e.g., ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, cyclohexanedimethanol), triols (e.g., trimethylolpropane, glycerin), and tetrafunctional alcohols (e.g., pentaerythritol); aliphatic amines (e.g., alkylenediamines (e.g., ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine), and alkanolamines (e.g., monoethanolamine, diethanolamine); aromatic amines (e.g., aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, Mannich condensation products); and combinations of any two or more thereof. As the polyether polyol, from the viewpoint of further improving the flame retardancy of the polyurethane foam, an aromatic polyether polyol having an aromatic ring in the molecule is preferred, and among them, amine-based polyether polyols such as tolylenediamine-based polyether polyols and Mannich-based polyether polyols are preferred, with Mannich-based polyether polyols being more preferred. Note that the tolylenediamine-based polyether polyol refers to a polyether polyol obtained using tolylenediamine as an initiator. The Mannich-based polyether polyol refers to a polyether polyol produced by utilizing the Mannich reaction of phenols, primary or secondary amines, and aldehydes, such as a polyether polyol obtained using a Mannich condensation product as an initiator.

[0039] The hydroxyl value of the polyether polyol is preferably 200 to 1000 mgKOH / g, more preferably 300 to 600 mgKOH / g. The hydroxyl value is a value measured in accordance with JIS K1557-1:2007.

[0040] <Polyester polyol> Examples of polyester polyols include aromatic polyester polyols and aliphatic polyester polyols. However, considering the flame retardancy of the resulting polyurethane foam, it is preferable to use an aromatic polyester polyol. The aromatic polyester polyol is preferably a condensate of an aromatic dicarboxylic acid, such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), or naphthalenedicarboxylic acid, with a glycol. Among these, from the viewpoint of further improving the flame retardancy of the polyurethane foam, a phthalic acid-based polyester polyol, which is a condensate of at least one of o-phthalic acid, m-phthalic acid, and p-phthalic acid with a glycol, is preferred, and a p-phthalic acid-based polyester polyol, which is a condensate of p-phthalic acid with a glycol, is more preferred.

[0041] The glycol is not particularly limited, but it is preferable to use low molecular weight aliphatic glycols known as constituent components of polyester polyols, such as ethylene glycol, propylene glycol, and diethylene glycol.

[0042] The hydroxyl value of the polyester polyol is preferably from 100 to 400 mgKOH / g, and more preferably from 150 to 350 mgKOH / g.

[0043] Among the above-mentioned polyol compounds, from the viewpoint of further enhancing the flame retardancy of the polyurethane foam, aromatic polyol compounds are preferred, and it is more preferred that the aromatic polyol compound contains at least one of a phthalic acid-based polyester polyol and an aromatic amine-based polyether polyol.

[0044] The polyol compound preferably contains 50% by mass or more, more preferably 80% by mass or more, and even more preferably 100% by mass of an aromatic polyol compound. The aromatic polyol compound preferably contains 50% by mass or more, more preferably 80% by mass or more, and even more preferably 100% by mass of at least one of a phthalic acid-based polyester polyol and an aromatic amine-based polyether polyol. When the content of the aromatic polyol compound is equal to or greater than the lower limit, a polyurethane foam having excellent flame retardancy tends to be obtained more easily.

[0045] <Catalyst> The polyol composition may contain a catalyst. The catalyst may include, for example, one or more catalysts selected from the group consisting of a urethane / urea catalyst and a trimerization catalyst. Alternatively, the polyol composition may contain two catalysts: one urethane / urea catalyst having both urethane-forming activity and urea-forming activity, and one trimerization catalyst. Preferably, the polyol composition contains three catalysts: one urethane / urea catalyst having high urethane-forming activity, one urethane / urea catalyst having high urea-forming activity, and one trimerization catalyst. More preferably, the polyol composition contains four catalysts: one urethane / urea catalyst having high urethane-forming activity, one urethane / urea catalyst having high urea-forming activity, and two trimerization catalysts. Note that a urethane / urea catalyst having high urethane-forming activity is sometimes referred to as a urethane catalyst, and a urethane / urea catalyst having low urea-forming activity is sometimes referred to as a urea catalyst.

[0046] The urethane / urea catalyst is a catalyst that promotes the reaction between a polyol compound and a polyisocyanate compound. Specific examples include amino compounds, tin compounds, bismuth compounds, and acetylacetone metal salts. Examples of the amino compounds include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholine bis(2-dimethylaminoethyl) ether, bis(2-dimethylaminoethyl) ether, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl) ether, N-methyl-N',N'-dimethylaminoethylpiperazine, an imidazole compound in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group, N,N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylethylenediamine, tetramethylhexamethylenediamine, 1-methylimidazole, trimethylaminoethylpiperazine, and tripropylamine. Examples of tin compounds include stannous octoate, dibutyltin diacetate, and dibutyltin dilaurate. Examples of bismuth compounds include bismuth neodecanoate and bismuth octoate. Examples of acetylacetone metal salts include aluminum acetylacetone, iron acetylacetone, copper acetylacetone, zinc acetylacetone, beryllium acetylacetone, chromium acetylacetone, indium acetylacetone, manganese acetylacetone, molybdenum acetylacetone, titanium acetylacetone, cobalt acetylacetone, vanadium acetylacetone, and zirconium acetylacetone, as well as combinations of any two or more of these.

[0047] The amount of the urethane / urea catalyst added in the polyurethane foam-forming composition is not particularly limited, but is preferably 0.01 to 1 mass %, more preferably 0.03 to 0.9 mass %, even more preferably 0.05 to 0.8 mass %, particularly preferably 0.07 to 0.7 mass %, and most preferably 0.1 to 0.6 mass %, based on the mass of the polyurethane foam solids in the polyurethane foam-forming composition. By adjusting the amount within this range, the reaction between the polyol component and the polyisocyanate component can be further promoted at an appropriate reaction rate.

[0048] The trimerization catalyst promotes the trimerization that forms isocyanurate bonds. This promotion of trimerization further improves the flame retardancy of polyurethane foams. Examples of trimerization catalysts include aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; alkali metal salts such as potassium acetate, sodium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, potassium octoate, and sodium octoate; aziridines such as 2-ethylaziridine; lead compounds such as lead naphthenate and lead octoate; alcoholate compounds such as sodium methoxide; phenolate compounds such as potassium phenoxide; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt; quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, and tetraphenylammonium salt; and combinations of any two or more of these.

[0049] The amount of trimerization catalyst in the polyurethane foam-forming composition is not particularly limited, but from the viewpoint of further improving the curing rate of the polyurethane foam-forming composition and the flame retardancy of the polyurethane foam, the amount is preferably 0.5 to 6.0 mass%, more preferably 0.8 to 4.0 mass%, even more preferably 1.1 to 3.0 mass%, particularly preferably 1.3 to 2.5 mass%, and most preferably 1.5 to 2.0 mass%, relative to the mass of the polyurethane foam solids in the polyurethane foam-forming composition. By keeping the amount of trimerization catalyst within this range, an appropriate amount of isocyanurate bonds are formed, further improving flame retardancy.

[0050] <Foam stabilizer> The polyurethane foam-forming composition may contain a foam stabilizer. Either the polyisocyanate composition or the polyol composition may contain a foam stabilizer, or both may contain one. Preferably, only the polyol composition contains a foam stabilizer. Examples of foam stabilizers include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, surfactants such as silicone foam stabilizers such as organopolysiloxanes, and combinations of any two or more of these. Furthermore, the silicone foam stabilizer may contain a graft copolymer of polydimethylsiloxane and polyethylene glycol.

[0051] The content of the foam stabilizer in the polyurethane foam-forming composition is not particularly limited, but is preferably 0.05 to 1.5 mass %, more preferably 0.1 to 1.2 mass %, even more preferably 0.15 to 0.9 mass %, particularly preferably 0.2 to 0.6 mass %, and most preferably 0.25 to 0.4 mass %, relative to the mass of the polyurethane foam solids in the polyurethane foam-forming composition.

[0052] <Foaming agent> The polyurethane foam-forming composition may contain a blowing agent. Either the polyol composition or the polyisocyanate composition may contain the blowing agent, or both may contain the blowing agent. Preferably, only the polyol composition contains a foam stabilizer. Examples of the blowing agent include water and / or a physical blowing agent. Preferably, the blowing agent contains water.

[0053] Specific examples of physical blowing agents include low-boiling hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, and hydrofluoroolefins. Further examples of blowing agents include organic physical blowing agents such as mixtures of these compounds, and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Examples of low-boiling hydrocarbons include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane. Examples of chlorinated aliphatic hydrocarbon compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. Examples of fluorine compounds include CHF, CHF, and CHF. Examples of the hydrochlorofluorocarbon compounds include trichloromonofluoromethane, trichlorotrifluoroethane, and dichloromonofluoroethane (e.g., HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), and HCFC142b (1-chloro-1,1-difluoroethane)). Examples of the hydrofluorocarbons include HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane). Examples of the ether compounds include diisopropyl ether. Examples of the hydrofluoroolefins include HFO-1233zd(E) (trans-1-chloro-3,3,3-trifluoropropene), HFO-1234yf (2,3,3,3-tetrafluoro-1-propene), and combinations of any two or more of these. Among these, hydrofluoroolefins are preferred.

[0054] The content of the blowing agent in the polyurethane foam-forming composition is preferably 1 to 20 mass% based on the mass of the polyurethane foam solids in the polyurethane foam-forming composition, more preferably 2 to 18 mass%, even more preferably 3 to 16 mass%, particularly preferably 4 to 14 mass%, and most preferably 5 to 12 mass%. When the content of the blowing agent is equal to or less than the upper limit, a polyurethane foam having excellent mechanical properties such as compressive strength, dimensional stability, and adhesiveness tends to be more easily obtained. On the other hand, when the content of the blowing agent is equal to or more than the lower limit, a polyurethane foam having excellent heat insulating properties tends to be more easily obtained.

[0055] The water content in the polyurethane foam-forming composition is preferably 0.01 to 1.0 mass%, more preferably 0.03 to 0.5 mass%, even more preferably 0.05 to 0.3 mass%, particularly preferably 0.07 to 0.2 mass%, and most preferably 0.09 to 0.15 mass%, based on the mass of the polyurethane foam solids in the polyurethane foam-forming composition. When the water content is equal to or less than the upper limit, a polyurethane foam with excellent flame retardancy tends to be more easily obtained. On the other hand, when the water content is equal to or more than the lower limit, a polyurethane foam with excellent mechanical properties such as compressive strength tends to be more easily obtained.

[0056] The content of the physical blowing agent in the polyurethane foam-forming composition is preferably 1 to 20 mass%, more preferably 2 to 18 mass%, even more preferably 3 to 16 mass%, particularly preferably 4 to 14 mass%, and most preferably 5 to 12 mass%, based on the mass of the polyurethane foam solids in the polyurethane foam-forming composition. When the content of the physical blowing agent is equal to or less than the upper limit, polyurethane foams with excellent mechanical properties such as compressive strength, dimensional stability, and adhesiveness tend to be more easily obtained. On the other hand, when the content of the physical blowing agent is equal to or more than the lower limit, polyurethane foams with lower raw material costs tend to be more easily obtained.

[0057] When water and a physical blowing agent are used in combination as blowing agents, the content of the physical blowing agent in the polyurethane foam-forming composition is preferably 50 to 99 mol%, more preferably 60 to 98 mol%, even more preferably 70 to 97 mol%, particularly preferably 80 to 96 mol%, and most preferably 90 to 95 mol%, based on the total content of water and physical blowing agent. When the content of the physical blowing agent is at least the above lower limit, polyurethane foams with excellent flame retardancy tend to be more easily obtained. When the content of the physical blowing agent is at most the above upper limit, polyurethane foams with excellent mechanical properties such as compressive strength tend to be more easily obtained.

[0058] <Additives> The polyurethane foam-forming composition may further contain an additive. The additive is not particularly limited, and examples thereof include solid flame retardants other than organic salt-based flame retardants and inorganic salt-based flame retardants, liquid flame retardants, inorganic fillers, anti-settling agents, dispersants, etc.

[0059] That is, the polyurethane foam-forming composition may contain, as an optional component, a solid flame retardant other than the solid flame retardants described above.

[0060] (Other solid flame retardants) The polyurethane foam-forming composition may contain, as an additive, another solid flame retardant in addition to the organic salt-based flame retardant and the inorganic salt-based flame retardant. Either the polyol composition or the polyisocyanate composition may contain the other solid flame retardant, or both may contain the other solid flame retardant. It is preferred that only the polyol composition contains the other solid flame retardant. This further improves the handleability of the polyisocyanate composition.

[0061] Examples of other solid flame retardants include red phosphorus, bromine-containing flame retardants, antimony-containing flame retardants other than the above-mentioned antimonate-containing flame retardants, and metal hydroxide-based flame retardants. Among these, red phosphorus and bromine-containing flame retardants are preferred. Use of other solid flame retardants tends to make it easier to obtain polyurethane foams with even better flame retardancy.

[0062] (red phosphorus) There is no limitation on the red phosphorus, and commercially available products can be appropriately selected and used.

[0063] (Bromine-containing flame retardants) The bromine-containing flame retardant is not particularly limited as long as it contains a compound containing bromine in its molecular structure, and examples thereof include those containing aromatic brominated compounds, etc. Specific examples of the aromatic brominated compounds include hexabromobenzene, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (SR-245), pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenediamine, ethylenediamine, ethylenediamine ether ... Low molecular weight organic bromine compounds such as ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), tetrabromobisphenol A, 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazine-2,4,6-trione (SR-750), and tetrabromobisphenol A bis(dibromopropyl ether) (SR-720), and homopolymers derived from 2,6-(or 2,4-)dibromophenol (SR-460B) ), brominated polycarbonates such as polycarbonate oligomers produced using brominated bisphenol A as a raw material, and copolymers of the polycarbonate oligomers with bisphenol A (FG-8500, FG-7500, FG-7000), brominated epoxy compounds such as brominated diepoxy compounds produced by reacting brominated bisphenol A with epichlorohydrin, and brominated monoepoxy compounds obtained by reacting brominated phenols with epichlorohydrin, polymers of bromine compounds and brominated polymers such as poly(brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, condensates of cyanuric chloride and brominated phenol, brominated (polystyrene), poly(brominated styrene), brominated polystyrenes such as crosslinked brominated polystyrene, crosslinked or non-crosslinked brominated poly(α-methylstyrene), and combinations of any two or more of these.Among these, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (SR-245), ethylene bis(pentabromophenyl), tetrabromobisphenol A bis(dibromopropyl ether) (SR-720), homopolymer derived from 2,6-(or 2,4-)dibromophenol (SR-460B), polycarbonate oligomer produced from brominated bisphenol A as a raw material, and brominated polycarbonates such as copolymers of the above polycarbonate oligomers with bisphenol A (FG-8500, FG-7500, FG-7000), are preferred.

[0064] (Other antimony-containing flame retardants) Examples of other antimony-containing flame retardants include antimony oxide. Examples of antimony oxide include antimony trioxide and antimony pentoxide. The other antimony-containing flame retardant is preferably antimony trioxide. The other antimony-containing flame retardants may be used alone or in combination of two or more.

[0065] (Metal hydroxide flame retardant) Examples of metal hydroxide flame retardants include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, and combinations of any two or more of these.

[0066] In addition, phosphazene, silicone-based flame retardants, organic sulfonate-based flame retardants, etc. can also be used as other solid flame retardants.

[0067] The content of the other solid flame retardant in the polyurethane foam-forming composition is not particularly limited, but is preferably 1 to 20 mass% relative to the mass of the polyurethane foam solids in the polyurethane foam-forming composition, more preferably 2 to 15 mass%, even more preferably 3 to 13 mass%, particularly preferably 4 to 11 mass%, and most preferably 5 to 10 mass%. By setting the content of the other solid flame retardant to 1 mass% or more, the flame retardancy of the polyurethane foam can be further improved. Furthermore, by setting the content of the other solid flame retardant to 20 mass% or less, the formation rate of an isocyanurate structure increases, which tends to make it easier to obtain a polyurethane foam with better flame retardancy.

[0068] (liquid flame retardant) The polyurethane foam-forming composition may contain a liquid flame retardant as an additive. Preferably, at least one of the polyol composition and the polyisocyanate composition contains the liquid flame retardant. More preferably, only the polyol composition contains the liquid flame retardant. This improves the flame retardancy of the resulting polyurethane foam. In the present disclosure, the liquid flame retardant refers to a flame retardant that is in a liquid state at 23°C.

[0069] Preferred liquid flame retardants include phosphate ester-based flame retardants such as monophosphate esters and condensed phosphate esters. Examples of monophosphate esters include, but are not limited to, trimethyl phosphate, triethyl phosphate, tributoxyethyl phosphate, tributyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresyl phenyl phosphate, dimethyl methyl phosphonate, tris(chloroethyl)phosphate, tris(dichloropropyl)phosphate, tris(β-chloropropyl)phosphate, and combinations of any two or more of these. Examples of condensed phosphate esters include, but are not limited to, resorcinol polyphenyl phosphate (product name: CR-733S), bisphenol A polycresyl phosphate (product name: CR-741), and aromatic condensed phosphate ester (product name: CR747). Among these, tris(chloroethyl)phosphate, tris(dichloropropyl)phosphate, and tris(β-chloropropyl)phosphate are preferred.

[0070] The content of the liquid flame retardant in the polyurethane foam-forming composition is preferably 1 to 30 mass%, more preferably 5 to 25 mass%, even more preferably 8 to 23 mass%, particularly preferably 10 to 20 mass%, and most preferably 12 to 18 mass%, based on the mass of the polyurethane foam solids in the polyurethane foam-forming composition. When the content of the liquid flame retardant is at least as high as the lower limit, a polyurethane foam with excellent flame retardancy tends to be more easily obtained. On the other hand, when the content of the liquid flame retardant is at most as high as the upper limit, the formation rate of an isocyanurate structure increases, and a polyurethane foam with even better flame retardancy tends to be more easily obtained.

[0071] The total amount of organic salt-based flame retardants, inorganic salt-based flame retardants, other solid flame retardants, and liquid flame retardants in the polyurethane foam-forming composition (hereinafter simply referred to as the "total amount of flame retardants") is not particularly limited, but is preferably 5 to 50 mass% relative to the mass of polyurethane foam solids in the polyurethane foam-forming composition, more preferably 10 to 45 mass%, even more preferably 15 to 40 mass%, particularly preferably 20 to 35 mass%, and most preferably 25 to 30 mass%. When the total amount of flame retardants is equal to or less than the upper limit, the formation rate of isocyanurate structures increases, and polyurethane foams with even better flame retardancy tend to be obtained. When the total amount of flame retardants is equal to or greater than the lower limit, polyurethane foams with even better flame retardancy tend to be obtained.

[0072] (Inorganic filler) The polyurethane foam-forming composition may contain an inorganic filler as an additive, provided that the effect of one embodiment of the present disclosure is not impaired. At least one of the polyol composition and the polyisocyanate composition may contain an inorganic filler, or both may contain an inorganic filler. It is also possible for the inorganic filler to be contained in the polyol composition alone, and it is preferred that the inorganic filler be contained in the polyol composition alone. Examples of inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica palan, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon palan, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber, and the like, and combinations of any two or more thereof.

[0073] From the viewpoint of the foamability of the polyurethane foam-forming composition, the content of the inorganic filler in the polyurethane foam-forming composition is preferably 5 to 99 mass%, more preferably 10 to 90 mass%, even more preferably 20 to 80 mass%, and particularly preferably 30 to 70 mass%, relative to the mass of the polyurethane foam solids in the polyurethane foam-forming composition.

[0074] (Anti-settling agent) The polyurethane foam-forming composition may contain an anti-settling agent as an additive. At least one of the polyol composition and the polyisocyanate composition may contain an anti-settling agent, or both may contain an anti-settling agent. Examples of anti-settling agents include organic bentonite, aliphatic amide wax, hydrogenated castor oil wax, carbon black, silica powder, etc., and combinations of any two or more of these. The inclusion of an anti-settling agent can suppress the settling of solid flame retardants and inorganic fillers with high specific gravity.

[0075] The content of the anti-settling agent in the polyurethane foam-forming composition is preferably 0.1 to 3.0 mass%, more preferably 0.2 to 2.5 mass%, even more preferably 0.3 to 2.0 mass%, particularly preferably 0.4 to 1.5 mass%, and most preferably 0.5 to 1.0 mass%, based on the mass of the polyurethane foam solids in the polyurethane foam-forming composition. When the content of the anti-settling agent is at least as high as the aforementioned lower limit, a polyurethane foam-forming composition with good storage stability tends to be more easily obtained. On the other hand, when the content of the anti-settling agent is at most as high as the aforementioned upper limit, a polyurethane foam with excellent flame retardancy tends to be more easily obtained.

[0076] (dispersant) The polyurethane foam-forming composition may contain a dispersant as an additive. At least one of the polyol composition and the polyisocyanate composition may contain a dispersant, or both may contain a dispersant. The dispersant is a material that improves the dispersibility of the solid flame retardant and inorganic filler.

[0077] Examples of dispersants include alkylammonium salts, organic ammonium salts, phosphate esters, and phosphate ester salts of hydroxyl-containing acidic copolymers. Examples of organic ammonium salts include alkylammonium salts, alkylolammonium salts, and combinations of any two or more of these. The inclusion of a dispersant improves the wetting and dispersion rate of the solid flame retardant and inorganic filler during dispersion and reduces viscosity, thereby allowing for a higher blending amount of the solid flame retardant and inorganic filler. Furthermore, the dispersant significantly delays the time it takes for the solid flame retardant and inorganic filler to settle to the bottom of a container after stirring and mixing with a stirring blade or the like. These dispersants are suitable because, even when present in small amounts in the polyurethane foam-forming composition, they can effectively suppress aggregation of the solid flame retardant and inorganic filler when used in combination with an anti-settling agent.

[0078] The content of the dispersant in the polyurethane foam-forming composition is preferably 0.1 to 3.0 mass%, more preferably 0.2 to 2.5 mass%, even more preferably 0.3 to 2.0 mass%, particularly preferably 0.4 to 1.5 mass%, and most preferably 0.5 to 1.0 mass%, based on the mass of the polyurethane foam solids in the polyurethane foam-forming composition. When the content of the dispersant is at least as high as the aforementioned lower limit, a polyurethane foam-forming composition with good storage stability tends to be more easily obtained. On the other hand, when the content of the dispersant is at most as high as the aforementioned upper limit, a polyurethane foam with excellent flame retardancy tends to be more easily obtained.

[0079] (Other additives) The polyurethane foam-forming composition may further contain other additives in addition to the organic salt-based flame retardant, inorganic salt-based flame retardant, other solid flame retardant, liquid flame retardant, inorganic filler, anti-settling agent, and dispersant. It is preferred that only the polyol composition contains other additives.

[0080] Examples of other additives include phenol-based, amine-based, and sulfur-based antioxidants, heat stabilizers, metal inhibitors, antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, pigments, and additives such as tackifying resins, and tackifiers such as polybutene and petroleum resins.

[0081] (Isocyanate Index) The isocyanate index of the polyurethane foam-forming composition is not particularly limited, but from the viewpoint of improving flame retardancy, it is preferably 200 to 700, more preferably 250 to 600, even more preferably 300 to 500, particularly preferably 350 to 450, and most preferably 380 to 420. When the isocyanate index is equal to or greater than the lower limit, polyurethane foams with excellent flame retardancy tend to be more readily obtained. On the other hand, when the isocyanate index is equal to or less than the upper limit, the formation rate of isocyanurate structures increases, and polyurethane foams with even better flame retardancy tend to be more readily obtained. Here, the isocyanate index refers to the equivalent ratio (NCO groups / active hydrogen groups) of the isocyanate groups of the polyisocyanate compound to all active hydrogen groups contained in the polyol composition (water as a blowing agent is calculated as a bifunctional active hydrogen compound), expressed as a percentage (equivalent ratio of isocyanate groups to 100 equivalents of active hydrogen groups).

[0082] [Polyurethane foam] The polyurethane foam of another embodiment of the present disclosure is a foam of the polyurethane foam-forming composition of one embodiment of the present disclosure.

[0083] The method for producing a polyurethane foam is not particularly limited, and examples thereof include a method in which a polyol composition and a polyisocyanate composition are previously prepared by kneading them, and a method in which the components constituting the polyurethane foam are kneaded together. However, the polyurethane foam is usually produced by kneading a polyol composition and a polyisocyanate composition. The kneading can be carried out by a known method, and the polyurethane foam can be obtained by kneading using a known device such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a Raikai mixer, or a planetary mixer.

[0084] (Total heat generation) For polyurethane foam, the test was conducted in accordance with the ISO-5660 standard, with a radiant heat intensity of 50 kW / m 2 The total heat generated when heated for 10 minutes under the conditions above (total heat generated by heating for 10 minutes) is 11MJ / m 2 The total calorific value is preferably 11 MJ / m or less. 2 In order to further improve the flame retardancy of the polyurethane foam, the total calorific value is 10 MJ / m or less. 2 Preferably, it is 9MJ / m or less. 2 It is more preferable that the gross calorific value is equal to or less than 100%. The gross calorific value can be obtained by a cone calorimeter test, and specifically, can be measured by the method described in the Examples. In the cone calorimeter test, it is preferable that the polyurethane foam used in the test has shape stability to such an extent that it does not come into contact with the spark igniter of the cone calorimeter.

[0085] (Application) The uses of the polyurethane foam are not particularly limited, but it can be used to fill cavities in structures such as buildings, furniture, automobiles, trains, and ships, or to spray onto such structures. Among these, the use of the polyurethane foam for spraying onto structures, i.e., as a polyurethane foam for spraying, is preferred. Spraying can be carried out using a spraying device (e.g., A-25 manufactured by GRACO) and a spray gun (e.g., D-gun manufactured by Gasmar). Spraying can be carried out by adjusting the temperature of a polyol composition and a polyisocyanate composition contained in separate containers in the spraying device, causing them to collide and mix at the tip of the spray gun, and then atomizing the mixture using air pressure. Spraying devices and spray guns are well known, and commercially available products can be used.

[0086] The density of the polyurethane foam is not particularly limited, but is preferably 20 to 200 kg / m 3 The density is preferably in the range of 200 kg / m 3 By setting the weight of the polyurethane foam to 20 kg / m or less, the foam becomes lighter and the workability in structures is further improved. 3 By setting the density to 25 to 100 kg / m or more, the desired flame retardancy is more easily exhibited. 3 More preferably, it is in the range of 25 to 80 kg / m 3 It is more preferable that the density of the polyurethane foam is in the range of

[0045] The density of the polyurethane foam can be measured in accordance with JIS K7222.

[0087] <Calculation method for each composition> Mass (g) of polyurethane foam solids = Amount of polyisocyanate compound (g) + Amount of polyol compound (g) + Amount of solid flame retardant (organic salt-based flame retardant and / or inorganic salt-based flame retardant) (g) + Amount of various additives (g) + Amount of foam stabilizer (g) + Amount of catalyst (g) Content of solid flame retardant in polyisocyanate composition (mass%) = Content of solid flame retardant (mass%) / (Charged amount of polyisocyanate compound (g) + Content of solid flame retardant (g)) × 100 Solid flame retardant content (mass%) = solid flame retardant charge (g) / polyurethane foam solid content (g) x 100 Content of various additives (mass%) = Content of various additives (g) / Mass of polyurethane foam solids (g) × 100 Polyol compound content (mass%) = polyol compound charge (g) / polyurethane foam solid content (g) × 100 Catalyst content (mass%) = total catalyst charge (g) / mass of polyurethane foam solids (g) × 100 Foam stabilizer content (mass%) = foam stabilizer charge (g) / polyurethane foam solids mass (g) × 100 Foaming agent content (mass%) = total amount of foaming agent charged (g) / mass of polyurethane foam solids (g) × 100 Water content (mass%) = Water amount (g) / Polyurethane foam solids mass (g) × 100 Physical foaming agent content (mass%) = amount of physical foaming agent charged (g) / mass of polyurethane foam solids (g) × 100 Physical blowing agent content (mol%) = amount of physical blowing agent (mol) / (amount of water (mol) + amount of physical blowing agent (mol)) x 100 Content of other solid flame retardants (mass%) = Charge amount of other solid flame retardants (g) / Mass of polyurethane foam solids (g) × 100 Liquid flame retardant content (mass%) = liquid flame retardant charge (g) / polyurethane foam solids mass (g) × 100 Total amount of flame retardant (mass%) = total amount of flame retardant charged (g) / mass of polyurethane foam solids (g) × 100 Inorganic filler content (mass%) = inorganic filler charge (g) / polyurethane foam solids mass (g) × 100 Anti-settling agent content (mass%) = Anti-settling agent amount (g) / Polyurethane foam solids mass (g) × 100 Dispersant content (mass%) = Amount of dispersant charged (g) / Mass of polyurethane foam solids (g) × 100 Content of other additives (mass%) = Amount of other additives charged (g) / Mass of polyurethane foam solids (g) × 100 [Example]

[0088] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples.

[0089] Details of each component used in each example and comparative example are as follows. (1) Polyisocyanate compounds Polymeric MDI (Tosoh Corporation, product name: MR-200) (2) Solid flame retardants Aluminum diethylphosphinate (a phosphinate-containing flame retardant manufactured by Clariant Chemicals, product name: OP930) Ammonium polyphosphate (phosphate-containing flame retardant manufactured by Clariant Chemicals, product name: AP-462) Zinc borate (Kinseimatec Co., Ltd. borate-containing flame retardant) Melamine polyphosphate (a phosphate-containing flame retardant manufactured by Nissan Chemical Industries, Ltd., product name: PHOSMEL (R) -100) (3) Polyol compounds Phthalic acid-based polyester polyol (Kawasaki Chemical Industries, Ltd., product name: Maximol RFK-505, hydroxyl value = 250 mg KOH / g) (4) Liquid flame retardants Tris(β-chloropropyl)phosphate (phosphate ester flame retardant manufactured by Yoke Chemicals and New Materials (Shanghai) Co., Ltd., product name: TCPP) (5) Foam stabilizer Silicone foam stabilizer (Toray Dow Corning, product name: SH-193) (6) Catalyst (i) Urethane catalyst Tin compounds (manufactured by Evonik, product name: DABCO T-9) (ii) Urea catalyst Tertiary ammonium compound (manufactured by Tosoh Corporation, product name: TOYOCATDT) (iii) Trimerization catalyst Quaternary ammonium salt (manufactured by Tosoh Corporation, product name: TOYOCATTRV) Metal salt (Tosoh Corporation, product name: DABCO K-15) (7) Foaming agent ·water HFO-1233zd (hydrofluoroolefin) (Honeywell, product name: Solstice LBA)

[0090] Example 1 First, a polyisocyanate compound and a solid flame retardant were weighed into a 500 mL polypropylene beaker in the proportions shown in Table 1 and stirred with a hand mixer at 20°C for 10 minutes to obtain a polyisocyanate composition. A polyol compound, a blowing agent, a catalyst, a flame retardant, and a foam stabilizer were weighed into a 500 mL polypropylene beaker in the proportions shown in Table 1 and stirred with a hand mixer at 20°C for 10 minutes to obtain a polyol composition. Immediately thereafter, these polyisocyanate compositions and polyol compositions (two-component polyurethane foam-forming compositions) were each stored at 23°C for 3 days (54 hours).

[0091] Next, the stored two-component polyurethane foam-forming compositions (the polyol composition and the polyisocyanate composition) were each adjusted to a temperature of 10°C, and then the polyisocyanate composition was added to the polyol composition to prepare a foaming raw material composition (polyurethane foam-forming composition).The mixture was then immediately stirred for 5 seconds in a laboratory spar to initiate the reaction and foaming, thereby producing a polyurethane foam.

[0092] (Examples 2 to 29, Comparative Examples 1 to 13) Polyurethane foams were obtained in the same manner as in Example 1, except that the blending ratios were changed to those shown in Tables 1 to 7.

[0093] (Reference examples 1~13) Polyurethane foams were obtained in the same manner as in Example 1, except that the blending ratios were changed as shown in Tables 1 to 7 and the storage conditions for the polyisocyanate composition and polyol composition were changed to 10°C for 3 hours.

[0094] <Gel Time> The gel time (gt) (seconds) of each foaming raw material composition prepared in Examples, Comparative Examples, and Reference Examples was measured from the start of mixing the polyol composition and the polyisocyanate composition at a temperature of 23°C, as gelation progressed. A thin glass or metal rod was lightly inserted into the top of the foaming liquid concentrate composition during foaming, and then quickly pulled out, and the time until the foaming liquid concentrate composition began to form strings was measured. The results are shown in Tables 1 to 7.

[0095] <Time Elapsed from Preparation of Polyisocyanate Composition and Polyol Composition to Foaming> The elapsed time from preparation of the polyisocyanate composition and the polyol composition to foaming was measured from the time when the polyisocyanate composition and the polyol composition were prepared until they were mixed together. The results are shown in Tables 1 to 7.

[0096] <Difference in gel time depending on water content> When the solid flame retardant and water coexist in a polyol composition containing a trimerization catalyst, the solid flame retardant tends to deactivate the tertiary ammonium compound and / or quaternary ammonium salt, resulting in a delayed gel time. Furthermore, the delay in gel time tends to be proportional to the water content, from the viewpoint of the solubility of the solid flame retardant in water.

[0097] Therefore, the gel time of the foaming raw material compositions prepared in Reference Examples 1 to 13 (solid flame retardant was blended into the polyol composition and stored at 10°C for 3 hours) was used as the standard gel time, and the difference between this standard gel time and the gel time of the foaming raw material compositions prepared in Examples 1 to 29, Comparative Examples 1 to 13, and Comparative Examples 10 and 11 (solid flame retardant was blended into the polyisocyanate composition and stored at 23°C for 3 days (54 hours)) was determined under the same water content conditions, and the storage stability was evaluated according to the following criteria. The results are shown in Tables 1 to 7. [Evaluation criteria] A: 1s or less B: More than 1s but less than 2s C: More than 2s but less than 3s D:3s super

[0098] <Total heat generation> The gross calorific value of the polyurethane foams prepared in each Example and Comparative Example was evaluated by the following method. A polyol composition obtained by mixing a polyol compound, a blowing agent, a catalyst, a flame retardant, and a foam stabilizer in the same proportions as in each Example and Comparative Example, and a polyisocyanate composition obtained by mixing a polyisocyanate compound and a solid flame retardant, were added to a polypropylene beaker at a liquid temperature of 20°C so that the total amount was 200 g. The mixture was stirred for 5 seconds with a laboratory spar to prepare a foaming raw material composition (polyurethane foam-forming composition). Immediately thereafter, the foaming raw material composition was sprayed into a mold measuring 150 mm x 150 mm x 150 mm to obtain a polyurethane foam. The polyurethane foam was cut into a length of 100 mm, width of 100 mm, and thickness of 25 mm to prepare a cone calorimeter test sample. This cone calorimeter test sample was used to measure the radiant heat intensity of 50 kW / m according to the test method described in ISO-5660. 2 The total calorific value (total calorific value after heating for 10 minutes) was measured by a cone calorimeter test when the samples were heated for 10 minutes under the above conditions, and the results were evaluated according to the following criteria. The results are shown in Tables 1 to 7. The cone calorimeter test was carried out using a CONE-III (manufactured by Toyo Seiki Seisakusho, Ltd.). [Evaluation criteria] (Phosphinic acid flame retardant) A: 7MJ / m 2 below B: 7MJ / m 2 Super 8MJ / m 2 below C:8MJ / m 2 Super 10MJ / m 2 below D: 10MJ / m 2 Super (Ammonium polyphosphate, melamine polyphosphate) A: 9.8 MJ / m 2 below B: 9.8MJ / m 2 Super 10.2MJ / m 2 below C: 10.2MJ / m 2 Super (zinc borate) A: 9.4 MJ / m 2 below B: 9.4 MJ / m 2 Super

[0099] <Overall rating> The foaming raw material compositions were comprehensively evaluated based on the gel time difference of the foaming raw material compositions and the total calorific value of the polyurethane foam, according to the following criteria. The results are shown in Tables 1 to 7. [Evaluation criteria] A: Only A is evaluated for the difference in gel time and total calorific value at the same water content. B: The evaluation of the difference in gel time and total calorific value at the same water content does not include D or C, but includes one or more Bs. C: The evaluation of the difference in gel time and total calorific value at the same water content does not include D, but includes one or more Cs. D: Evaluation of gel time difference and total calorific value at the same water content includes D

[0100] [Table 1]

[0101] [Table 2]

[0102] [Table 3]

[0103] [Table 4]

[0104] [Table 5]

[0105]

Table 6

[0106]

Table 7

Claims

1. A polyurethane foam-forming composition comprising a polyol composition and a polyisocyanate composition, The polyisocyanate composition is a polyurethane foam-forming composition comprising a polyisocyanate compound and at least one solid flame retardant selected from the group consisting of organic salt-based flame retardants and inorganic salt-based flame retardants.

2. 2. The polyurethane foam-forming composition according to claim 1, wherein the content of the solid flame retardant is 1 to 20 mass %, based on the mass of polyurethane foam solids in the polyurethane foam-forming composition.

3. 2. The polyurethane foam-forming composition according to claim 1, wherein the solid flame retardant is at least one selected from the group consisting of phosphinate-containing flame retardants, phosphate-containing flame retardants, borate-containing flame retardants, and antimonate-containing flame retardants.

4. 10. The polyurethane foam-forming composition of claim 1, wherein the polyurethane foam-forming composition comprises a liquid flame retardant.

5. 5. The polyurethane foam-forming composition according to claim 4, wherein the content of the liquid flame retardant is 1 to 30 mass %, based on the mass of polyurethane foam solids in the polyurethane foam-forming composition.

6. the polyurethane foam-forming composition may optionally contain a solid flame retardant other than the solid flame retardant, 5. The polyurethane foam-forming composition according to claim 4, wherein the total amount of the solid flame retardant, the liquid flame retardant, and the other solid flame retardant is 5 to 50 mass %, based on the mass of polyurethane foam solids in the polyurethane foam-forming composition.

7. 5. The polyurethane foam-forming composition according to claim 4, wherein the liquid flame retardant is a phosphate ester-based flame retardant.

8. The polyurethane foam-forming composition of claim 1, having an isocyanate index in the range of 200 to 700.

9. the polyurethane foam-forming composition comprises a blowing agent; the blowing agent comprises water; 2. The polyurethane foam-forming composition according to claim 1, wherein the water content in the polyurethane foam-forming composition is 0.01 to 1.0 mass %, based on the mass of polyurethane foam solids in the polyurethane foam-forming composition.

10. A polyurethane foam, which is a foam of the polyurethane foam-forming composition according to any one of claims 1 to 9.

11. Radiant heat intensity 50kW / m according to the test method described in ISO-5660 ２ The total heat generated when heated for 10 minutes under the conditions of ２ 11. The polyurethane foam of claim 10, wherein:

12. A polyisocyanate composition for use in a polyurethane foam-forming composition, comprising a polyol composition and a polyisocyanate composition, The polyisocyanate composition comprises a polyisocyanate compound and at least one solid flame retardant selected from the group consisting of organic salt-based flame retardants and inorganic salt-based flame retardants.

13. 13. The polyisocyanate composition according to claim 12, wherein the solid flame retardant is at least one selected from the group consisting of phosphinate-containing flame retardants, phosphate-containing flame retardants, borate-containing flame retardants, and antimonate-containing flame retardants.

14. The polyisocyanate composition according to claim 12 or 13, wherein the content of the solid flame retardant is 1 to 30 mass% based on the total amount of the polyisocyanate composition.

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