Composition for producing foam, foam, and heat insulating material for piping

Abstract

To provide a foam excellent in moldability and having a low density, and a resin composition which is a raw material of the foam.SOLUTION: The present disclosure provides a composition for making a foam comprising an isocyanate-terminated prepolymer and an alkanolamine. The present disclosure also provides a foam obtained from the foam-producing composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a foam-making composition, a foam, and a pipe insulation material. [Background technology]

[0002] Urethane foams are used in construction, as heat-insulating materials for ships transporting oil and gas, and for electrical appliances such as refrigerators, etc. As a technique for improving the flame retardancy of urethane foams, for example, Patent Document 1 discloses a urea resin composition containing a polyisocyanate compound, a polyamine compound, a trimerization catalyst, a blowing agent, a foam stabilizer, and a flame retardant, and a polyurea foam having excellent flame retardancy that is a foam of the composition.

[0003] Patent Document 2 discloses a resin composition characterized by containing: a resin component containing an isocyanate-terminated prepolymer having at least two isocyanate groups, obtained by reacting a compound having two or more active hydrogens with a polyisocyanate; a trimerization catalyst; a flame retardant; a blowing agent; and a foam stabilizer; and a resin composition and a foam thereof.

[0004] Patent Document 3 discloses a resin composition characterized by containing: a resin component containing an isocyanate-terminated prepolymer having at least two isocyanate groups, obtained by reacting a compound having two or more active hydrogens with a polyisocyanate; a polyamine; a trimerization catalyst; a flame retardant; a blowing agent; and a foam stabilizer; and a resin composition and a foam thereof. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2022 / 004832 [Patent Document 2] Japanese Patent Publication No. 2022-13710 [Patent Document 3] Japanese Patent Application Publication No. 2022-22979 Summary of the Invention [Problem to be solved by the invention]

[0006] When molding a foam, it is necessary to close the mold after injecting the raw materials into it. However, with conventional formulations, the reaction proceeds quickly (i.e., the time it takes for foaming to begin (cream time; CT) is fast), so foaming occurs immediately after the raw materials are injected, and the foam does not reach the edges of the mold, resulting in molding defects or the formation of voids. Furthermore, simply reducing the amount of catalyst to delay the reaction results in the foam becoming denser.

[0007] Therefore, an object of the present disclosure is to provide a foam that has excellent moldability and low density, and a resin composition that is a raw material for the foam. [Means for solving the problem]

[0008] The present disclosure (1) is a foam-producing composition comprising an isocyanate-terminated prepolymer and an alkanolamine. The present disclosure (2) is the composition for producing a foam according to the disclosure (1), wherein the isocyanate-terminated prepolymer is made from at least one raw material selected from the group consisting of polyols and polyamines. The present disclosure (3) is a foam-producing composition according to the disclosure (1) or (2), which is for molding. The present disclosure (4) is a foam obtained from the foam-producing composition according to any one of the present disclosures (1) to (3). The present disclosure (5) is a pipe insulating material comprising the foam according to the present disclosure (4). [Effects of the Invention]

[0009] According to the present disclosure, it is possible to provide a foam having excellent moldability and low density, and a resin composition that is the raw material for the foam. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present disclosure provides a foam obtained by reacting a resin component containing an isocyanate-terminated prepolymer having at least two isocyanate groups, preferably obtained from an active hydrogen compound having two or more active hydrogens and a polyisocyanate; and an alkanolamine. In this specification, the term "resin component" refers to the isocyanate-terminated prepolymer. When the isocyanate-terminated prepolymer contains unreacted polyisocyanate with the active hydrogen compound having two or more active hydrogens, this is also considered a resin component. When the isocyanate-terminated prepolymer contains an alkanolamine, this is also considered a resin component.

[0011] The foam of the present disclosure, the method for producing the foam, the physical properties of the foam, and the uses of the foam will be described below in this order.

[0012] <Foam> <Overall structure> The foam according to the present disclosure is preferably a closed-cell foam, and the density of the foam is preferably 10 to 70 kg / m 3 is preferably 10 to 65 kg / m 3 More preferably, it is 10 to 60 kg / m 3 More preferably, it is 10 to 55 kg / m 3 It is even more preferable that the 3 It is particularly preferable that the density is 10 to 45 kg / m 3 The density of the foam is measured by the method described in JIS K7222:2005 "Foamed plastics and rubber - Determination of apparent density."

[0013] <Chemical structure> (Isocyanurate ring content (isocyanurate ratio)) The isocyanurate ratio in the foam according to the present disclosure is preferably 20% or more and 50% or less, more preferably 25% or more and 48% or less, even more preferably 30% or more and 45% or less, and particularly preferably 35% or more and 42% or less. Here, the isocyanurate ratio is a value calculated by the following formula 1.

[0014] (Formula 1) Isocyanurate ratio (%) = {P1 / (P1+P2+P3+P4)} x 100

[0015] Here, P1 is the peak area attributable to the isocyanurate structure in the absorption spectrum of the foam obtained by infrared spectroscopy. P2 is the peak area attributable to the C=O of the urea structure in the absorption spectrum of the foam obtained by infrared spectroscopy. P3 is the peak area attributable to the C=O of the urethane structure and the isocyanurate structure in the absorption spectrum of the foam obtained by infrared spectroscopy. P4 is the peak area attributable to the NH of the urethane structure and the urea structure in the absorption spectrum of the foam obtained by infrared spectroscopy.

[0016] More specifically, P1 is a compound having a wave number of 1410 cm included in the absorption spectrum of the foam obtained by infrared spectroscopy. -1 P1 is the peak area derived from the isocyanurate structure in the vicinity. -1 P1 indicates the content of isocyanurate structures formed by the reaction of isocyanate groups derived from the raw materials.

[0017] P2 is the wavenumber 1595 cm included in the absorption spectrum of the foam obtained by infrared spectroscopy. -1 P2 is the peak area derived from the C=O of the nearby urea structure. -1 P2 indicates the content of urea structures formed by the reaction of isocyanate groups derived from the raw materials.

[0018] P3 is the wavenumber 1710 cm included in the absorption spectrum of the foam obtained by infrared spectroscopy. -1 P3 is the peak area derived from the C=O of the urethane structure and isocyanurate structure in the vicinity. -1P3 indicates the content of urethane structures and isocyanurate structures formed by the reaction of isocyanate groups derived from the raw materials.

[0019] P4 is the wavenumber 1510 cm included in the absorption spectrum of the foam obtained by infrared spectroscopy. -1 P4 is the peak area derived from the NH contained in the nearby urethane structure and urea structure. -1 P4 indicates the content of urethane and urea structures obtained by infrared spectroscopy after the reaction of isocyanate groups derived from the raw materials.

[0020] Therefore, the sum of P1 to P4 indicates the total number of isocyanate groups derived from the raw materials that have reacted. Therefore, the isocyanurate conversion rate is a value that indicates the proportion of isocyanurate structures among the isocyanate groups derived from the raw materials that have reacted.

[0021] (Residual isocyanate group content (remaining NCO%)) The residual NCO% in the foam according to the present disclosure is preferably 20% or less, more preferably 17% or less, and particularly preferably 15% or less, where the residual NCO% is a value calculated by the following method.

[0022] The residual NCO% of a foam is determined by measuring the absorption peak heights of the foam and the polyisocyanate raw material based on the isocyanate group (NCO) using infrared spectroscopy. That is, the residual NCO% is calculated by dividing the peak height measured for the foam by the peak height measured for the isocyanate raw material. More specifically, it is calculated using the following measurement procedure and formula 2.

[0023] (Formula 2) Remaining NCO (%) = {x / y} x 100 x: Measured value in foam (peak height) y: Measured value (peak height) for isocyanate raw material NCO-based absorption peak position: approximately 2300 cm -1

[0024] (Measurement procedure) 1. Measure the IR of the isocyanate raw material only. 2.Measure the IR of the foam. 3. Each chart is 750cm -1 Normalize by the peak intensity (match the peak height). 4. Obtain the peak height based on NCO from the normalized chart and calculate the remaining NCO% using the above formula 2.

[0025] <<Foam manufacturing method>> <Foam raw materials> The foam raw materials according to the present disclosure are at least an isocyanate-terminated prepolymer and an alkanolamine. Here, the term "isocyanate-terminated prepolymer" refers to a compound having at least two isocyanate groups, which is obtained from an active hydrogen compound having two or more active hydrogens and a polyisocyanate.

[0026] Therefore, the raw materials for the foam according to the present disclosure include active hydrogen compounds having two or more active hydrogens and polyisocyanates, which are raw materials for isocyanate-terminated prepolymers. Furthermore, other components than those mentioned above, such as catalysts, flame retardants, blowing agents, foam stabilizers, dispersants, and active hydrogen compounds having two or more active hydrogens other than alkanolamines (e.g., polyols and polyamines), may also be used as the raw materials. Each raw material is described in detail below.

[0027] (Isocyanate-terminated prepolymer) An isocyanate-terminated prepolymer is a compound having at least two isocyanate groups, obtained from a compound having two or more active hydrogens and a polyisocyanate. The weight-average molecular weight of the prepolymer is preferably in the range of 300 to 5,000, more preferably 300 to 4,000, even more preferably 400 to 3,000, and particularly preferably 500 to 2,000. The weight-average molecular weight of the prepolymer can be measured by gel permeation chromatography (GPC) (standard polymer = polystyrene). The isocyanate-terminated prepolymer can be obtained, for example, by blending an excess amount of polyisocyanate relative to the number of moles of the compound having two or more active hydrogens (see, for example, Japanese Patent Nos. 5,121,699 and 4,883,490).

[0028] Compounds with two or more active hydrogen atoms Examples of compounds having two or more active hydrogens, which are one of the raw materials for the isocyanate-terminated prepolymer, include low-molecular-weight diols such as ethylene glycol and diethylene glycol, polyols, polyhydric phenols, polyamines, alkanolamines, and polythiols. The compound having two or more active hydrogens is preferably at least one selected from the group consisting of polyols, polyamines, and polythiols, and is preferably a polyol and / or a polyamine. These will be explained in order below.

[0029] The polyol is not particularly limited, and examples thereof include polyester polyol, polycarbonate polyol, polyether polyol, polyester ether polyol, etc. Among these, polyester polyol is preferred, and polyester polyols using aliphatic dicarboxylic acids as a single raw material are particularly preferred.

[0030] The polyester polyol is not particularly limited, and examples thereof include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; and acid esters or acid anhydrides thereof with ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, and the like. Examples of suitable polyols include polyester polyols such as polypropylene glycol obtained by a dehydration condensation reaction with 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, or a mixture thereof; and polylactone diols obtained by ring-opening polymerization of lactone monomers such as ε-caprolactone and methylvalerolactone.

[0031] Examples of polycarbonate polyols include those obtained by reacting at least one polyhydric alcohol such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, or diethylene glycol with diethylene carbonate, dimethyl carbonate, diethyl carbonate, or the like.

[0032] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc., which are obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide, tetrahydrofuran, etc., and copolyethers thereof. Polyether polyols can also be obtained by polymerizing the above-mentioned cyclic ethers using polyhydric alcohols such as glycerin and trimethylolethane.

[0033] Examples of polyester ether polyols include those obtained by a dehydration condensation reaction of aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; or acid esters or acid anhydrides thereof with glycols such as diethylene glycol or propylene oxide adducts, or mixtures thereof.

[0034] The polyhydric phenols are not particularly limited, and examples thereof include monocyclic polyhydric phenols such as pyrogallol and hydroquinone; and bisphenols such as bisphenol A, bisphenol F, and bisphenol sulfone.

[0035] The polyamine is not particularly limited, and examples thereof include aliphatic polyamines, aromatic polyamines, and alicyclic polyamines. Specific examples include 4,4-methylenebis(N-sec-butylaniline), 4,4-methylene-bis(2-methylcyclohexylamine), 4,4'-diamino-3,3'-dichlorodiphenylmethane, trimethylene-bis(4-aminobenzoate), 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, polytetramethylene oxide-di-p-aminobenzoate, 2,2',6,6'-tetraethyl-4,4'-methylenedianiline, 4,4'-methylenebis(2-isopropyl-6-methylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 4,4'-methylenebis(3-chloro-2,6-diethylaniline), 3,5-diethyltoluene-2,4-diamine, and dimethylthiotoluenediamine.

[0036] The polythiol is not particularly limited, and examples thereof include bis-(2-hydrothioethyloxy)methane, dithioethylene glycol, dithioerythritol, and dithiothreitol.

[0037] The alkanolamine is not particularly limited, and examples thereof include diethanolamine, ethanolisopropanolamine, diisopropanolamine, ethanol-2-hydroxybutylamine, isopropanol-2-hydroxybutylamine, triethanolamine, N-methylaminoethanol, N-normal butylaminoethanol, N-tert-butylaminoethanol, N-ethylaminoethanol, N-benzylaminoethanol, and N-(2-hydroxyethyl)piperazine.

[0038] The hydroxyl value of the polyol and polyhydric phenol is preferably 50 to 1000 mgKOH / g, more preferably 80 to 850 mgKOH / g, and even more preferably 100 to 700 mgKOH / g, where the hydroxyl value is a value measured in accordance with JIS-K0070.

[0039] The mercapto value (SH value; mgKOH / g) of the polythiol is preferably 50 to 1000 mgKOH / g. The mercapto value of the polythiol is determined by the following method. First, a sample is weighed into a 100 mL (milliliter) sample bottle (the mass is accurately read in grams to four decimal places), and 5 mL of acetic anhydride-tetrahydrofuran solution (containing 4 g of acetic anhydride per 100 mL of solution) and 10 mL of 4-dimethylaminopyridine-tetrahydrofuran solution (containing 1 g of 4-dimethylaminopyridine per 100 mL of solution) are accurately added to completely dissolve the sample. The solution is then stirred at room temperature for 1 hour. Next, 1 mL of ultrapure water is accurately added, and the solution is stirred at room temperature for 30 minutes. The solution is then titrated with a 0.5 M potassium hydroxide-ethanol solution (indicator: phenolphthalein). The SH value is calculated using the following formula:

[0040] (Formula 3) SH value (mgKOH / g) = 28.05 × (BA) / S (In the formula, S represents the amount of sample taken (g), A represents the amount of 0.5M potassium hydroxide-ethanol solution (mL) required for titrating the sample, and B represents the amount of 0.5M potassium hydroxide-ethanol solution (mL) required for the blank test.)

[0041] The amine value of the polyamine is preferably 50 to 1000 mgKOH / g, more preferably 50 to 800 mgKOH / g. The amine value of the polyamine is measured by the total amine value measurement method described in JIS K1557-7:2011 "Plastics - Test methods for polyurethane raw polyols - Part 7: Determination of basicity (indication of nitrogen content and total amine value)."

[0042] Two or more types of compounds having active hydrogen may be used in combination.

[0043] Polyisocyanate The polyisocyanate is not limited as long as it is a compound having a plurality of isocyanate groups, and may be any of aromatic, aliphatic, and alicyclic. For example, bifunctional polyisocyanates include 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), hydrogenated MDI, xylylene diisocyanate, and 3,3'-dimethyl Aromatic diisocyanates such as 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, polymethylene polyphenyl polyisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, tetramethylxylene diisocyanate (TMXDI), cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate Alicyclic ones such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, lysine diisocyanate, and other alkylene-based ones; trifunctional or higher polyisocyanates include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, biphenyl-2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, methyldiphenylmethane, and the like. Examples of the isocyanate include methyl methyl ether-4,6,4'-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, triphenylmethane-4,4',4"-triisocyanate, polymeric MDI, lysine ester triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, bicycloheptane triisocyanate, 1,8-diisocyanatomethyl octane, and the like; and may also include modified products and derivatives thereof.These polyisocyanates can be used alone or in combination. Among these, MDI, TDI, or modified or derivatives of MDI or TDI are preferred, with monomeric MDI and crude MDI being more preferred.

[0044] Other ingredients As described above, the essential raw materials for the isocyanate-terminated prepolymer of the present disclosure are a compound having two or more active hydrogens and a polyisocyanate. However, as long as two or more isocyanate groups are present at the terminals of the prepolymer (e.g., isocyanate groups at both ends of the main chain, an isocyanate group at one end of the main chain plus an isocyanate group in a side chain, or isocyanate groups in multiple side chains), a polymerizable component that forms part of the prepolymer skeleton, a component for modifying the side chain, etc., may also be used. Note that, as described above, "terminal" does not mean only both ends, but is a concept that two or more isocyanate groups may be present anywhere in the skeleton.

[0045] Here, the isocyanate group content (NCO%) of the resin component containing the isocyanate-terminated prepolymer is preferably 10 to 35 mass%, more preferably 15 to 30 mass%, and even more preferably 17 to 28 mass%. The NCO% of the resin component is measured in accordance with Method A (toluene / dibutylamine, hydrochloric acid method) of JIS K1603-1:2007 "Test methods for aromatic isocyanates in plastics - polyurethane raw materials, Part 1: Determination of isocyanate group content."

[0046] The viscosity of the resin component containing the isocyanate-terminated prepolymer at 25°C is preferably 100 to 20,000 mPa·s, more preferably 200 to 18,000 mPa·s, even more preferably 300 to 16,000 mPa·s, even more preferably 500 to 12,000 mPa·s, particularly preferably 1,000 to 10,000 mPa·s, and particularly preferably 2,000 to 8,000 mPa·s. By setting the viscosity within the above range, a good balance can be achieved between properties such as residual weight and volume change rate at high temperatures and flame resistance.

[0047] (catalyst) The catalyst includes a trimerization catalyst. Examples of the trimerization catalyst include metal oxides such as lithium oxide, sodium oxide, and potassium oxide; alkoxides such as sodium methoxy, sodium ethoxy, sodium propoxy, sodium butoxy, potassium methoxy, potassium ethoxy, potassium propoxy, and potassium butoxy; organic metal salts such as potassium acetate, potassium octoate, potassium caprylate, and iron oxalate; 2,4,6-tris(dimethylaminomethyl)phenol, N,N',N"-tris(dimethylaminopropyl)hexahydrotriazine, and triethylenediamine; Examples of suitable additives include tertiary amines such as ethyleneimine and 1,3,5-tris(dimethylaminopropyl)hexahydro-s-triazine; ethyleneimine derivatives; acetylacetone chelates of alkali metals, aluminum, and transition metals, quaternary ammonium salts; and nitrogen-containing heterocyclic compounds such as diazabicycloundecene (DBU). These can be used alone or in combination. Of these, it is more preferable to use organic metal salts, quaternary ammonium salts, and nitrogen-containing heterocyclic compounds. Furthermore, the additives may contain a foaming catalyst or a resinification catalyst.

[0048] Examples of foaming catalysts include tertiary amines or organic acid salts thereof such as N,N,N',N',N"-pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl)ether, N,N,N',N',N"-pentamethyldipropylenetriamine, N,N-dimethylaminoethoxyethanol, N,N,N'-trimethylaminoethoxyethanol, N,N,N',N'',N'''-hexamethyltriethylenetetramine, N,N,N',N"-tetramethyl-N"-(2-hydroxylethyl)triethylenediamine, and N,N,N',N"-tetramethyl-(2-hydroxylpropyl)triethylenediamine; morpholine compounds; and piperazine compounds, and one or more of these can be used.

[0049] Examples of the resinification catalyst include N,N,N',N',N"-pentamethyldiethylenetriamine, triethylenediamine (TEDA), triethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, tertiary amines or organic acid salts thereof such as N,N,N',N'-tetramethylguanidine and 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, bismuth tris(2-ethylhexanoate), bismuth tris(neodecanoate), bismuth tris(palmitate), bismuth tetramethylheptanedioate, bismuth octoate, bismuth naphthenate, dibutyltin dilaurate, Organic metals such as dibutyltin dimaleate, dibutyltin diacetate, dioctyltin diacetate, tin octoate, and dimethyltin dimercaptide, imidazoles such as titanium-(2-ethylhexoxide), 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, and 1-isobutyl-2-methylimidazole, or N-methyl-N'-(2-dimethylimidazole) Examples of suitable bis(dimethylaminoethyl)piperazine include N,N'-dimethylpiperazine, N-methylpiperazine, N-methylmorpholine, N-ethylmorpholine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,1'-((3-(dimethylamino)propyl)imino)bis(2-propanol), bismuth 2-ethylhexanoate, N,N-dimethylaminoethanol, and bis(dimethylaminoethyl)ether, and one or more of these can be used.

[0050] (Flame retardant) As the flame retardant, red phosphorus is preferred. Furthermore, it is preferred to use at least one selected from the group consisting of phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, and metal hydroxides in combination with red phosphorus. In addition to these, other flame retardants may also be included. Specific examples of phosphate esters include aromatic phosphate esters such as triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(t-butylated phenyl)phosphate, tris(i-propylated phenyl)phosphate, and 2-ethylhexyl diphenyl phosphate; aromatic condensed phosphate esters such as 1,3-phenylene bis(diphenyl phosphate), 1,3-phenylene bis(dixylenyl)phosphate, resorcinol bis(diphenyl)phosphate, and bisphenol A bis(diphenyl phosphate); halogen-containing phosphate esters such as tris(dichloropropyl)phosphate, tris(β-chloropropyl)phosphate, and tris(chloroethyl)phosphate; and halogen-containing condensed phosphate esters such as 2,2-bis(chloromethyl)trimethylenebis(bis(2-chloroethyl)phosphate) and polyoxyalkylenebisdichloroalkylphosphate.Examples of the phosphate-containing flame retardant include monophosphates, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen 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 monohydrogen 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; and aluminum salts such as aluminum monophosphate, aluminum diphosphate, aluminum triphosphate, aluminum phosphite, and aluminum hypophosphite. Examples of polyphosphates include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate.Examples of bromine-containing flame retardants include pentabromodiphenyl ether; octabromodiphenyl ether; decabromodiphenyl ether; TBBA compounds such as tetrabromobisphenol A (TBBA), TBBA-epoxy oligomer, TBBA-polycarbonate oligomer, TBBA-bis(dibromopropyl ether), and TBBA-bis(aryl ether); polybenzene ring compounds such as bisphenylpentamethane, 1,2-bis(2,4,6-tribromophenoxy)ethane, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, 2,6-dibromophenol, and 2,4-dibromophenol; brominated styrene compounds such as brominated polystyrene and polybrominated styrene; phthalic acid compounds such as ethylenebistetrabromophthalimide; and cyclic aliphatic compounds such as hexabromocyclododecane. Examples of boron-containing flame retardants include borax; boron oxides such as diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide; boric acid compounds such as boric acid, lithium borate, sodium borate, potassium borate, cesium borate, magnesium borate, calcium borate, barium borate, zirconium borate, zinc borate, aluminum borate, and ammonium borate. Examples of boron-containing flame retardants include antimony oxides such as antimony trioxide and antimony pentoxide; antimonates such as sodium antimonate and potassium antimonate; and pyroantimonates such as sodium pyroantimonate and potassium pyroantimonate. Examples of metal hydroxides include aluminum hydroxide and magnesium hydroxide. Other flame retardants that can be used include known flame retardants. Examples of other flame retardants include chlorine compounds such as chlorinated paraffin, nitrogen compounds such as hindered amines and melamine cyanurate, cellulose, fumed silica, etc. These can be used alone or in combination.

[0051] (foaming agent) Examples of the blowing agent include water, hydrocarbons (preferably C4 to C6), hydrofluorocarbons, and the like. Examples include olefins and carbon dioxide. Specifically, cyclopentane, HFO(13 36mzz), HFO (1233zd), etc. These may be used alone or The foaming agent may contain water or may not contain water. However, when at least one of the foaming agents is water, the amount of the foaming agent is 100 parts by mass of the resin component. The amount is preferably 2 parts by mass or less, and more preferably 1 part by mass or less. It is particularly preferable that the amount is 0.75 parts by mass or less.

[0052] (Foam stabilizer) Examples of foam stabilizers include silicone compounds such as polyalkylsiloxane-polyoxyethylene-polyoxypropylene graft copolymers and polyalkylsiloxane-polyoxyethylene-polyoxypropylene linear block copolymers; and nonionic surfactants such as fluorine-based hydrocarbon compounds, acrylic-polyoxyalkylene copolymers, polyoxyethylene-polyoxypropylene copolymers, acetylene diol compounds, polyoxyethylene fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene phenyl ethers, polyoxyethylene phenyl ethers, polyoxyethylene alkyl phenyl ethers, glycerin fatty acid esters, sorbitan fatty acid esters, and sucrose fatty acid esters. These can be used alone or in combination.

[0053] (dispersant) Examples of dispersants include phosphate esters, fatty acid esters, polyether phosphate ester amines, aliphatic polycarboxylic acids, unsaturated carboxylic acid polymers, long-chain aminoamides, polyester acid amide amine salts, nonionic surfactants, etc. These can be used alone or in combination.

[0054] (alkanolamines) The alkanolamine is not particularly limited, and examples thereof include diethanolamine, ethanolisopropanolamine, diisopropanolamine, ethanol-2-hydroxybutylamine, isopropanol-2-hydroxybutylamine, triethanolamine, N-methylaminoethanol, N-normal butylaminoethanol, N-tert-butylaminoethanol, N-ethylaminoethanol, N-benzylaminoethanol, and N-(2-hydroxyethyl)piperazine. In particular, primary amines and secondary amines such as N-normal butylaminoethanol are preferred. These may be used alone or in combination.

[0055] The active hydrogen number of the alkanolamine is preferably 50 to 1500 mgKOH / g, more preferably 200 to 1300 mgKOH / g, and even more preferably 500 to 1000 mgKOH / g. The active hydrogen number is calculated as [(56100 × number of functional groups) / molecular weight].

[0056] (Other ingredients) The foam-producing composition according to the present disclosure may further contain other components in addition to the above-described components, such as known additives, such as antioxidants, ultraviolet absorbers, antibacterial agents, tackifiers, and compatibilizers.

[0057] The foam-producing composition can be prepared, for example, by adding and mixing the various components. In this case, in addition to the isocyanate-terminated prepolymer, other resin components such as alkanolamines, polyols other than alkanolamines, and polyamines may also be blended.

[0058] Isocyanate Index The isocyanate index of the foam-producing composition according to the present disclosure is preferably 150 to 800, more preferably 200 to 600, and even more preferably 200 to 500. Here, the isocyanate index refers to the value obtained by multiplying the ratio of the number of moles of all active hydrogens in the composition to the number of moles of isocyanate groups (NCO) in the polyisocyanate by 100 ({number of moles of NCO / number of moles of active hydrogen} × 100).

[0059] <Method of manufacturing foam> The foam according to the present disclosure can be produced, for example, by premixing an isocyanate-terminated prepolymer, an alkanolamine, a trimerization catalyst, a blowing agent, a foam stabilizer, and a flame retardant to prepare a resin composition for producing a foam, followed by foaming and curing. Known methods can be used for mixing, foaming, and curing the resin composition.

[0060] When used in a spraying method, a mixed solution in which a raw material not having an isocyanate group has been mixed in advance with a raw material having an isocyanate group can be mixed in a spraying device immediately before application of the foam. When used in molding, the prepared resin composition is injected into a mold, foamed and cured in the mold, and then released from the mold to obtain a molded product.

[0061] The amount of the isocyanate-terminated prepolymer is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and even more preferably 10 to 90% by mass, based on the total mass of the resin components. The amount of the compound having two or more active hydrogens, which is a raw material for the isocyanate-terminated prepolymer, is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, even more preferably 13 to 40% by mass, and even more preferably 15 to 30% by mass, based on the total mass of the resin components. When a polyamine is included as the compound having two or more active hydrogens, the amount of the polyamine is preferably 5 to 80% by mass, more preferably 10 to 50% by mass, even more preferably 13 to 30% by mass, even more preferably 14 to 25% by mass, and even more preferably 15 to 20% by mass, based on the total mass of the resin components. When a polyol is included as the compound having two or more active hydrogens, the amount of polyol blended is preferably 5 to 80 mass %, more preferably 10 to 50 mass %, even more preferably 15 to 40 mass %, and even more preferably 20 to 30 mass %.

[0062] The amount of polyisocyanate added is preferably 20 to 95 mass %, more preferably 30 to 90 mass %, even more preferably 40 to 85 mass %, and particularly preferably 50 to 80 mass %, based on the total mass of the resin components.

[0063] The amount of alkanolamine blended is preferably 0.01 to 15 mass%, more preferably 0.1 to 10 mass%, even more preferably 0.5 to 5 mass%, and particularly preferably 0.5 to 3.0 mass%, based on the total mass of the resin components. By setting the amount of alkanolamine blended within the above range, the CT can be delayed without reducing the amount of catalyst, and improvement in moldability can be expected. If the CT is delayed simply by reducing the amount of catalyst, the density of the foam increases, making it difficult to reduce the weight.

[0064] The amount of foam stabilizer to be added may be preferably 0 to 10 parts by mass with respect to 100 parts by mass of the resin component.

[0065] The amount of the trimerization catalyst to be blended is, for example, 0.1 parts by mass or more and 15 parts by mass or less, preferably 1 part by mass or more and 10 parts by mass or less, more preferably 1.5 parts by mass or more and 8.0 parts by mass or less, and even more preferably 1.8 parts by mass or more and 6.0 parts by mass or less, relative to 100 parts by mass of the resin component.

[0066] The amount of resinification catalyst to be blended is, for example, 0 parts by mass or more and 15 parts by mass or less, preferably 0.1 parts by mass or more and 10.0 parts by mass or less, and more preferably 0.2 parts by mass or more and 7.0 parts by mass or less, relative to 100 parts by mass of the resin component.

[0067] The amount of foaming catalyst to be added is preferably 0 to 5 parts by mass with respect to 100 parts by mass of the resin component.

[0068] The amount of red phosphorus to be added is preferably 0 to 30 parts by mass, and more preferably 2 to 20 parts by mass, relative to 100 parts by mass of the resin component.

[0069] The blending amount of the flame retardant other than red phosphorus is preferably 0 to 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of the resin component.

[0070] Foaming start time (cream time; CT) When a foam is molded, if the reaction proceeds too quickly, the fluidity of the resin composition decreases, resulting in problems such as the foam not reaching the edges of the mold (metal mold), resulting in molding defects or the formation of voids. Therefore, from the viewpoint of moldability, the resin composition for producing a foam according to the present disclosure does not have a specific upper limit for CT, but it is preferably 5 minutes or less, or 3 minutes or less, more preferably 5 seconds to 30 seconds, even more preferably 6 seconds to 20 seconds, even more preferably 7 seconds to 17 seconds, and particularly preferably 10 seconds to less than 17 seconds. A CT within the above range can provide a foam-producing composition with excellent moldability. The CT is measured by placing the resin composition after stirring in a foaming box (a wooden box with internal dimensions of 16 cm × 16 cm × 16 cm) and visually measuring the time from stirring until the resin composition begins to rise due to the initiation of foaming. Rise time (RT) The resin composition for producing a foam according to the present disclosure has no particular upper limit for RT, but it is preferably 20 minutes or less, 15 minutes or less, 10 minutes or less, or 5 minutes or less, more preferably 30 seconds or more and 200 seconds or less, even more preferably 40 seconds or more and 150 seconds or less, even more preferably 50 seconds or more and 150 seconds or less, and particularly preferably 60 seconds or more and less than 110 seconds. RT is measured by placing the resin composition after stirring in a foaming box (a wooden box with internal dimensions of 16 cm × 16 cm × 16 cm) and visually measuring the time from stirring until the resin composition stops rising due to the completion of foaming. Resinization start time (gel time; GT) The resin composition for producing a foam according to the present disclosure has no particular upper limit for GT, but it is preferably 20 minutes or less, 15 minutes or less, 10 minutes or less, or 5 minutes or less. It is more preferably 30 to 200 seconds, more preferably 50 to 180 seconds, even more preferably 60 to 180 seconds, even more preferably 70 to less than 120 seconds, and particularly preferably 80 to less than 120 seconds. The GT is measured by placing the resin composition after stirring in a foam box (a wooden box with internal dimensions of 16 cm x 16 cm x 16 cm) and measuring the time it takes for the resin composition to change to a resinous state after stirring. The "change to a resinous state" is determined by feeling resistance when a wire (2 mm diameter, straight) is inserted into the resin composition.

[0071] <Physical properties of foam> <Volume change rate> Foams tend to expand easily at high temperatures (e.g., 300°C). If the volume change rate during expansion is small, the spread of fire due to deformation of the adherend is suppressed. Therefore, the volume change rate (300°C, 5 minutes) of the foam according to the present disclosure is preferably less than 80% of the original volume, more preferably less than 60%, even more preferably less than 50%, even more preferably less than 40%, even more preferably less than 30%, and even more preferably less than 20%. Furthermore, the lower limit of the volume change rate (300°C, 5 minutes) of the foam is preferably greater than -40%, more preferably greater than -30%, and even more preferably greater than -20% of the original volume. The volume change rate values ​​are values ​​measured according to the method described in the examples.

[0072] <Dimensional change rate> The dimensional (thickness) change rate (150°C, 1 week) of the foam according to the present disclosure is preferably less than 15% based on the original thickness, more preferably less than 13%, even more preferably less than 10%, even more preferably less than 7%, even more preferably less than 5%, and even more preferably less than 3%. The lower limit of the dimensional (thickness) change rate (150°C, 1 week) of the foam is preferably greater than -15% based on the original thickness, more preferably greater than -13%, even more preferably greater than -10%, even more preferably greater than -7%, even more preferably greater than -5%, and even more preferably greater than -3%. The dimensional change rate values ​​are measured according to the method described in the Examples. Furthermore, from the viewpoint of obtaining a foam having a more suitable dimensional (thickness direction) change rate (150°C, 1 week), it is preferable to contain a polyamine as the compound having two or more active hydrogens, which is one of the raw materials of the above-mentioned isocyanate-terminated prepolymer.

[0073] <Foam Applications> The foams according to the present disclosure are used in architectural applications (walls, ceilings, roofs, floors, piping, etc.), fixtures (windows, shoji screens, sliding doors, sliding screens, transoms, etc.), ships and storage tanks for oil and gas transportation, vehicles (engines, batteries, ceilings, floors, door panels, etc.), aircraft, transport aircraft, insulated bags for transporting pharmaceuticals, freezers and refrigerators, plant facilities, and electrical appliances such as refrigerators, as insulation materials, thermal insulation materials, and heat resistance mitigation materials for retaining walls, as underground filling reinforcement materials for land subsidence prevention work and road construction, injection repair materials for civil engineering applications such as tunnels, bridges, and floating piers, structural fillers for unnecessary basements, etc., energy absorbers, waterproofing materials, water-stopping materials, buoyancy materials, food containers and packaging materials, transport packaging materials, etc. Furthermore, in wooden and reinforced concrete buildings, etc., the foams can be used as spray-applied foams because of their ease of insulation application. Among these, the foams of the present disclosure are suitable for use as pipe covers and insulation, particularly as molded pipe insulation.

[0074] The resin composition that is the foam-producing composition of the present disclosure may be divided into two or more parts. When dividing the resin composition into two or more parts, the components should be divided so that curing does not start when each component of the resin composition is divided into two or more parts, but the curing reaction starts after the components are mixed.

[0075] Another aspect of the present disclosure is a system, which is a combination or reaction system for forming a resin composition, including a first liquid (base) containing a resin component including an isocyanate-terminated prepolymer and a second liquid (curing agent) containing an alkanolamine. The second liquid may further contain a trimerization catalyst. Here, one or more selected from a flame retardant, a blowing agent, a foam stabilizer, and a dispersant may be contained in the first liquid or the second liquid, or may be provided separately from the first liquid and the second liquid. Preferably, at least the trimerization catalyst, the flame retardant, the blowing agent, and the foam stabilizer are contained in the second liquid.

[0076] Yet another aspect of the present disclosure is a system, which is a combination or reaction system for forming a resin composition, including a first liquid (main component) containing a resin component including an isocyanate-terminated prepolymer, a second liquid (curing agent) containing an alkanolamine, and a third liquid containing a catalyst (particularly a trimerization catalyst). Here, one or more additives selected from a flame retardant, a blowing agent, a foam stabilizer, and a dispersant may be contained in any of the first to third liquids. Preferably, one or more additives selected from a flame retardant, a blowing agent, a foam stabilizer, and a dispersant are contained in the third liquid. Particularly preferably, at least the trimerization catalyst, the flame retardant, the blowing agent, and the foam stabilizer are contained in the third liquid.

[0077] The system for forming the resin composition is provided as an apparatus, such as a caulking gun or a spray container, including a first container for containing the first liquid and a second container for containing the second liquid (and a third container for containing the third liquid). The system and apparatus may be used to inject the resin composition into a mold for molding, or may be used to inject the resin composition into a spray device in a spraying method. [Example]

[0078] <<Preparation of Resin Composition>> <Raw materials> (prepolymer) Polyamine: 4,4-methylenebis(N-sec-butylaniline) (amine value: 526) Polyol: Phthalate ester polyol (OH value: 250, functionality: 2) Polyisocyanate I-1: Monomeric MDI (manufactured by BASF INOAC Polyurethanes, product name: Lupranate (registered trademark) MI, viscosity: 5 to 15 mPa·s at 25°C; NCO% ≧ 33.3%) Polyisocyanate I-2: Crude MDI (manufactured by BASF INOAC Polyurethanes, product name: Lupranate (registered trademark) M20S, viscosity: 170 to 250 mPa·s @ 25°C; NCO%: 30 to 32%) Polyisocyanate I-3: Crude MDI (manufactured by BASF INOAC Polyurethanes, product name: Lupranate (registered trademark) M11S, viscosity: 100 to 150 mPa·s @ 25°C; NCO%: 30 to 32%) Polyisocyanate I-4: Crude MDI (manufactured by BASF INOAC Polyurethanes, product name: Lupranate (registered trademark) M5S, viscosity: 40 to 60 mPa·s @ 25°C; NCO%: 31.4 to 32.6%) (Polyamine) 4,4-methylenebis(N-sec-butylaniline) (amine value: 526) (alkanolamines) N-butylmonoethanolamine (active hydrogen number: 957 mg KOH / g; molecular weight: 117.19) (Polyol) Phthalate ester polyol (Flame retardant) FL-1:TMCPP (halogen-containing phosphate ester) FL-2: Red phosphorus FL-3: Cellulose (manufactured by Rettenmeyer Japan, product name: ARBOCEL (registered trademark) UFC-100) FL-4: Fumed silica (manufactured by Nippon Aerosil Co., Ltd., product name: AELOSIL (registered trademark) 100) (dispersant) Unsaturated carboxylic acid polymer (BYK, product name: BYK P-100) (trimerization catalyst) CT-1: Tertiary amine catalyst (N,N',N"-tris(dimethylaminopropyl)hexahydrotriazine) CT-2: Quaternary ammonium salt (triethylmethylammonium 2-ethylhexane salt) (resinification catalyst) Bismuth 2-ethylhexylate (Foam stabilizer) Silicone surfactant (Momentive Performance Materials Japan, product name: L-6888) (foaming agent) Hydrofluoroolefin (boiling point: 33°C)

[0079] <Preparation of prepolymer> A predetermined amount of polyisocyanate shown in Table 1 was charged at 25°C into a 5 L polyethylene vessel equipped with a mechanical stirrer, anchor-type stirring blades, and a nitrogen inlet tube, and the liquid temperature of the isocyanate was adjusted to 25°C. A predetermined amount of polyol or polyamine shown in Table 1 was added stepwise to the vessel so that the liquid temperature did not exceed 80°C. Once the addition of the polyol or polyamine was complete, the vessel was stirred at a stirring speed of 60 rpm for 2 hours to react the isocyanate with the polyol or polyamine, thereby obtaining an isocyanate-terminated prepolymer.

[0080] The isocyanate group content (NCO%) of the obtained prepolymer was measured in accordance with JIS K1603-1 (Method A) and confirmed to be the specified NCO%. The viscosity (mPa·s) of the isocyanate-terminated prepolymer at 25°C was measured in accordance with JIS K7117-2. Furthermore, for some examples, the weight-average molecular weight of the prepolymer was measured by gel permeation chromatography (GPC). GPC was performed using a Tosoh Corporation GPC device (trade name: TOSOH HLC-8320GPC EcoSEC) with polystyrene as the standard polymer. The results are shown in Table 1.

[0081] <Preparation of Resin Composition and Foam> The polyamine, alkanolamine, trimerization catalyst, flame retardant, blowing agent, foam stabilizer, and other additives were weighed out in the amounts shown in Table 1 for each Example and Comparative Example and placed in a 500 mL polypropylene disposable cup to prepare a mixture for each Example and Comparative Example. Each mixture was stirred and mixed at 2000 rpm for 5 minutes using a mixer equipped with a propeller-type stirring blade to obtain a first composition for each Example and Comparative Example. The resulting first composition and a weighed-out second composition (prepolymer and optional polyisocyanate) in the amounts shown in Table 1 were each placed separately in a thermostatic chamber at 20°C and the temperature was adjusted to 20±2°C. The first composition and second composition for each Example and Comparative Example were combined in a mixer equipped with a propeller-type stirring blade and stirred and mixed at 3000 rpm for 5 seconds. The resulting mixture was poured into a 30 x 30 x 2 cm mold previously maintained at 55°C, foamed, and cured to obtain a foam for each Example and Comparative Example.

[0082] <Evaluation> <Isocyanate Index (INDEX)> The isocyanate index (INDEX) was calculated for the first composition and the second composition of each of the examples and comparative examples. The results are shown in Table 1.

[0083] <density> The apparent density of the foams of each Example and Comparative Example 24 hours after foaming was measured by the method described in JIS K7222:2005 "Foamed plastics and rubber - Determination of apparent density." The results are shown in Table 1.

[0084] <Measurement of isocyanurate conversion rate> The foams of each Example and Comparative Example, 24 hours after foaming, were subjected to infrared absorption spectrum measurement using a Fourier transform infrared spectrometer (FT-IR, manufactured by JASCO Corporation, model FT / IR-4200). Measurements were performed by the ATR method using a diamond prism, with 50 measurements accumulated. The isocyanurate group content in the foam was calculated using the above formula 1. The foams cured in the mold were cut approximately in half, and measurements were taken at two points in the center of the cross section, with the average value being shown. The results are shown in Table 1.

[0085] <Residual isocyanate group content (remaining NCO%)> The residual NCO% in the foams of each Example and Comparative Example was measured 24 hours after foaming. The foams cured in the mold described above were cut approximately in half, and measurements were taken at two points in the center of the cross section, and the average value was calculated. The results are shown in Table 1.

[0086] <Volume change rate (300°C, 5 minutes)> A sample (unheated sample) measuring 5 cm in length, 5 cm in width, and 2.5 cm in thickness was cut from the center of each foam of each Example and Comparative Example 24 hours after foaming, and left to stand in an electric furnace heated to 300°C for 5 minutes, after which the volume change rate was measured. The volume of the unheated sample and the volume after heating to 300°C were measured, and the volume change rate, assuming the volume of the unheated sample to be 100%, was calculated using the following equation 4. The volume change rate is a positive value when the sample expanded due to heating, and a negative value when the sample contracted due to heating. The results are shown in Table 1 (average value of N = 2).

[0087] (Formula 4) Volume change rate (%) = {(M1-M0) / M0} x 100 (where M0 is the volume of the unheated sample (cm 3), M1 is the volume of the sample after heating at 300°C (cm 3 ) represents.

[0088] <Dimensional change rate (150℃, 1 week)> Samples (unheated samples) measuring 10 cm in length, 10 cm in width, and 2.5 cm in thickness were cut out from the center of the foams of Examples 1 to 5, 9, and 10 and Comparative Examples 1 to 3 24 hours after foaming, and were left to stand in an oven heated to 150°C for one week, after which the dimensional change in the thickness direction was measured. The thickness of the unheated sample and the thickness after heating were measured, and the dimensional change, assuming the thickness of the unheated sample to be 100%, was calculated using the following equation 5. The dimensional change shows a positive value when the thickness increased due to heating, and a negative value when the thickness decreased. The results are shown in Table 1.

[0089] (Formula 5) Dimensional change rate (%) = {(T1-T0) / T0} x 100 (In the formula, T0 represents the thickness (cm) of the unheated sample, and T1 represents the thickness (cm) of the sample after heating at 150°C for one week.)

[0090] ≪Judgment criteria≫ Cream Time (CT) 10 seconds≦CT<17 seconds: 2 points CT≧17 seconds: 1 point 5 seconds≦CT<10 seconds: 0 points CT<5 seconds: -1 point Rise Time (RT) 60 seconds≦RT<110 seconds: 2 points RT≧110 seconds: 1 point 40 seconds≦RT<60 seconds: 0 points RT<40 seconds: -1 point Gel Time (GT) 70 seconds≦GT<120 seconds: 2 points GT≧120 seconds: 1 point 50 seconds≦GT<70 seconds: 0 points GT<50 seconds:-1 point ·density 50kg / m 3 Less than: 2 points 50kg / m 3More than 65kg / m 3 Less than: 1 point 65kg / m 3 Above: 0 points

[0091] [Table 1] *1: Mass ratio to the total amount of resin *2: Mass ratio to prepolymer

Claims

1. A foam-making composition comprising an isocyanate-terminated prepolymer and an alkanolamine.

2. The foam-producing composition according to claim 1 , wherein the isocyanate-terminated prepolymer is made from at least one material selected from the group consisting of polyols and polyamines.

3. The foam-producing composition according to claim 1 , which is for molding.

4. A foam obtained from the foam-producing composition according to any one of claims 1 to 3.

5. A pipe insulation material comprising the foam according to claim 4.

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