Isocyanate composition, polyurethane foam, and method for producing polyurethane foam

Abstract

To provide: an isocyanate composition in which the density of a molded article, compression strength, adiabaticity (thermal conductivity) and combustibility (fire retardancy) of a polyurethane foam to be obtained do not deteriorate, even when having been stored for a certain period of time; and a method for producing the polyurethane foam.SOLUTION: An isocyanate composition includes a vinyl polymerizable compound (A) and an organic polyisocyanate (B). The vinyl polymerizable compound (A) has a specific vinyl polymerizable functional group, and is one or more vinyl polymerizable compounds having a specific composition in which a concentration of the vinyl polymerizable functional group contained in one molecule of the vinyl polymerizable compound (A) is 0.5 to 20 (mmol / g) based on a molecular weight of the vinyl polymerizable compound (A). A weight ratio of the vinyl polymerizable compound (A) to the organic polyisocyanate (B) is 1 / 99 to 40 / 60.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an isocyanate composition, a polyurethane foam, and a method for producing a polyurethane foam. [Background technology]

[0002] Due to its characteristics such as heat insulating performance, dimensional stability at low temperatures, and ease of application, polyurethane foam is used in a wide range of applications, including as insulation for building materials, refrigerators, freezers, etc., as structural materials, and as sprays for on-site construction applications. Depending on the application, these polyurethane foams are required to have not only mechanical strength but also strict flame retardancy. It is generally known that the use of a large amount of flame retardant deteriorates the heat insulating property (thermal conductivity) of polyurethane foam, and various methods have been studied to achieve both flame retardancy and heat insulating property. For example, Patent Document 1 discloses a method of producing a rigid polyurethane foam by premixing polyol and other additives including a flame retardant, and then adding a temperature-controlled organic polyisocyanate.

[0003] However, in order to shorten the construction time on site, particularly when used as a spray for on-site construction, the raw materials for polyurethane foam containing a flame retardant are mixed in advance (premixed) and stored for a certain period of time until use. The method disclosed in Patent Document 1 has problems such as the flame retardant reacting with the water blended during premixing, causing it to lose its function as a flame retardant, or causing side reactions with other blends. If these reactions or side reactions occur, the molded product density, compressive strength, heat insulation (thermal conductivity), and flammability (flame retardancy) of the resulting polyurethane foam will deteriorate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2015-199937 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention aims to provide an isocyanate composition and a method for producing a polyurethane foam, which will not deteriorate the molded product density, compressive strength, insulation properties (thermal conductivity), and flammability (flame retardancy) of the resulting polyurethane foam, even if some of the raw materials for the polyurethane foam are premixed and stored for a certain period of time until use. [Means for solving the problem]

[0006] As a result of extensive investigations, the present inventors arrived at the present invention. The present invention relates to an isocyanate composition comprising a vinyl polymerizable compound (A) and an organic polyisocyanate (B), wherein the vinyl polymerizable compound (A) has a vinyl polymerizable functional group represented by the following general formula (1), the concentration of the vinyl polymerizable functional group in one molecule of the vinyl polymerizable compound (A) is 0.5 to 20 (mmol / g), the vinyl polymerizable compound (A) is a compound in which a residue obtained by removing all or a part of the hydrogen atoms contained in the active hydrogen group from a compound having at least two active hydrogen groups selected from the group consisting of a hydroxyl group, an amino group, and a mercapto group is bonded to a monovalent unsaturated hydrocarbon group directly or via a carbonyl group, and the weight ratio (A) / (B) of the vinyl polymerizable compound (A) to the organic polyisocyanate (B) is 1 / 99 to 40 / 60; a polyurethane foam which is a reaction product of the isocyanate composition and a polyol composition (P); and a method for producing the polyurethane foam. JPEG2025041538000001.jpg18170 [In general formula (1), R represents hydrogen, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 21 carbon atoms.] Effect of the Invention

[0007] According to the present invention, it is possible to provide an isocyanate composition and a method for producing a polyurethane foam, which do not deteriorate the molded product density, compressive strength, insulation properties (thermal conductivity), and flammability (flame retardancy) of the resulting polyurethane foam, even if some of the raw materials for the polyurethane foam are premixed and stored for a certain period of time until use. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The present invention is an isocyanate composition comprising a vinyl polymerizable compound (A) and an organic polyisocyanate (B). The vinyl polymerizable compound (A) in the present invention has a vinyl polymerizable functional group represented by the following general formula (1), and the concentration of the vinyl polymerizable functional group in one molecule of the vinyl polymerizable compound (A) is 0.5 to 20.0 (mmol / g). The vinyl polymerizable compound (A) is a compound in which a residue obtained by removing all or a part of the hydrogen atoms contained in the active hydrogen group from a compound having at least two active hydrogen groups selected from the group consisting of a hydroxyl group, an amino group, and a mercapto group is bonded to a monovalent unsaturated hydrocarbon group directly or via a carbonyl group. JPEG2025041538000002.jpg18170 [In general formula (1), R represents hydrogen, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 21 carbon atoms.] Examples of the alkyl group having 1 to 15 carbon atoms in R include a methyl group, an ethyl group, etc. Examples of the aryl group having 6 to 21 carbon atoms include a phenyl group, a p-methylphenyl group, etc.

[0009] The concentration of the vinyl polymerizable functional group in one molecule of the vinyl polymerizable compound (A) is represented by the number of moles of the vinyl polymerizable functional group per one molar mass of the vinyl polymerizable compound (A), and is represented by the following formula [1]. Concentration of vinyl polymerizable functional groups = (Number of vinyl polymerizable functional groups in molecule / molecular weight) x 1000 [1] The concentration (mmol / g) of the vinyl polymerizable functional group in one molecule of the vinyl polymerizable compound (A) is 0.5 to 20.0, preferably 7.0 to 15.0, and more preferably 7.5 to 14.0. If the concentration of the vinyl polymerizable functional group in one molecule of the vinyl polymerizable compound (A) is less than 0.5, the flame retardancy of the resulting foam is insufficient. If it exceeds 20.0, the reactivity decreases and the curing of the urethane foam becomes slow. When two or more compounds are contained as (A), the number of vinyl polymerizable functional groups is the average number, and the molecular weight is a value calculated from the composition.

[0010] Examples of the vinyl polymerizable functional group represented by the general formula (1) include one or more selected from the group consisting of (meth)acryloyl group, allyl group, propenyl group, and 1-butenyl group. Among these, from the viewpoint of the flame retardancy of the foam, (meth)acryloyl group, allyl group, and propenyl group are preferred, and (meth)acryloyl group and allyl group are more preferred. Here, the (meth)acryloyl group means an acryloyl group and / or a methacryloyl group, and the same notation is used hereinafter.

[0011] The vinyl polymerizable compound (A) is a compound in which a residue obtained by removing all or a part of the hydrogen atoms contained in a compound having at least two active hydrogen groups selected from the group consisting of a hydroxyl group, an amino group, and a mercapto group is bonded to a monovalent unsaturated hydrocarbon group directly or via a carbonyl group, and two or more types of the compound may be used in combination.

[0012] Specific examples of the vinyl polymerizable compound (A) include the following (A1) to (A3). (A1) Unsaturated carboxylic acid ester or alkenyl ether of polyol Examples of polyols include polyhydric alcohols, polyhydric phenols, alkylene oxide (hereinafter abbreviated as AO) adducts of polyhydric alcohols or polyhydric phenols, AO adducts of amines, and polyester polyols derived from polyhydric alcohols and polycarboxylic acids or lactones. Examples of the unsaturated carboxylate include (meth)acrylic acid esters. Alkenyl ethers include allyl ethers.

[0013] (A2) Unsaturated carboxylic acid amidation or alkenylation of amine An example of the unsaturated carboxylic acid amide is (meth)acrylamide. The alkenyl group contained in the alkenyl product includes an allyl group.

[0014] (A3) Unsaturated carboxylic acid thioester or alkenyl thioether of polythiol Examples of unsaturated carboxylic acid thioesters include (meth)acrylic thioesters. Alkenyl thioethers include allyl thioethers.

[0015] Examples of the polyhydric alcohol used in the production of (A1) include dihydric alcohols having 2 to 20 carbon atoms (hereinafter sometimes abbreviated as C) [aliphatic diols (ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.), alicyclic diols (cyclohexanediol, cyclohexanedimethanol, etc.)]; C3 to 20 trihydric alcohols [aliphatic triols (glycerin, trimethylolpropane, trimethylolethane, hexanetriol, etc.)]; C5 to 20 tetrahydric to octahydric or higher polyhydric alcohols [aliphatic polyols (pentaerythritol, sorbitol, mannitol, etc.), intramolecular dehydration products of aliphatic polyols (sorbitan, etc.), intermolecular dehydration products of aliphatic polyols (diglycerin, dipentaerythritol, etc.)]; and sugars and derivatives thereof (sucrose, glucose, mannose, fructose, methyl glucoside, etc.).

[0016] Examples of the polyhydric phenol used in the production of (A1) include polyhydric phenols [monocyclic polyhydric phenols (hydroquinone, etc.), bisphenols (bisphenol A, bisphenol F, etc.)], trihydric to pentahydric polyhydric phenols [monocyclic polyhydric phenols (pyrogallol, phloroglucin, etc.), formalin low condensates of trihydric to pentahydric polyphenol compounds (number average molecular weight 1000 or less) (novolac resin, resol intermediates), etc.], hexahydric to decahydric or higher polyhydric phenols [hexahydric or higher polyhydric phenol compounds, formalin low condensates (number average molecular weight 1000 or less) (novolac resin, resol intermediates), etc.], formalin condensates of polyhydric phenols and alkanolamines (Mannich polyols), and combinations of two or more of these.

[0017] Among the polyols used in the production of (A1), examples of the amine in the AO adduct of amine include ammonia; alkanolamines having 2 to 20 carbon atoms [mono-, di-, or triethanolamine, isopropanolamine, aminoethylethanolamine, etc.]; alkylamines having 1 to 20 carbon atoms [methylamine, ethylamine, n-butylamine, octylamine, etc.]; alkylenediamines having 2 to 6 carbon atoms [ethylenediamine, hexamethylenediamine, etc.]; polyalkylenepolyamines having an alkylene group with a carbon number of 2 to 6 (degree of polymerization 2 to 8 ) [diethylenetriamine, triethylenetetramine, etc.]; aromatic amines having 6 to 20 carbon atoms [aniline, phenylenediamine, tolylenediamine, xylylenediamine, methylenedianiline, diphenyletherdiamine, naphthalenediamine, anthracenediamine, etc.]; alicyclic amines having 4 to 15 carbon atoms [isophoronediamine, cyclohexylenediamine, etc.]; heterocyclic amines having 4 to 15 carbon atoms [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, etc.], and combinations of two or more of these.

[0018] Examples of AO to be added to polyhydric alcohol, polyhydric phenol, or amine include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,3-, 1,4-, or 2,3-butylene oxide, α-olefin oxide (having 5 to 30 or more carbon atoms), styrene oxide, and the like, and a combination of two or more of these (when used in combination, any of random addition, block addition, and combinations thereof may be used). Among these AO, those having 2 to 8 carbon atoms are preferred, and those containing PO and / or EO as the main component and, if necessary, 20% by weight or less of other AO are more preferred. The addition reaction can be carried out by a conventional method known in the art. The number of moles of AO added per molecule is preferably 1 to 70, more preferably 1 to 50.

[0019] Among the polyols used in the production of (A1), the polyhydric alcohols used in the polyester polyol include the same as those described above, and examples of the polyvalent carboxylic acids include aliphatic polycarboxylic acids having 4 to 18 carbon atoms [succinic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, etc.], aromatic polycarboxylic acids having 8 to 18 carbon atoms [phthalic acid or its isomers, trimellitic acid, etc.], ester-forming derivatives of these polycarboxylic acids [acid anhydrides, lower alkyl esters in which the alkyl group has 1 to 4 carbon atoms, etc.], and combinations of two or more of these. Examples of lactones include ε-caprolactone, γ-butyrolactone, γ-valerolactone, and combinations of two or more of these. The polyol used in the production of (A1) preferably has 3 to 10 hydroxyl groups, and more preferably 3 to 6 hydroxyl groups.

[0020] Taking the case of (meth)acrylic acid ester and allyl ether as an example, (A1) can be obtained by (meth)acryloylating or allylating the above-mentioned polyol with a (meth)acrylic halide or an allyl halide. Examples of the (meth)acrylic halide include (meth)acryloyl chloride, (meth)acryloyl bromide, and (meth)acryloyl iodide, and examples of the allyl halide include allyl chloride, allyl bromide, allyl iodide, and a combination of two or more of these. Also, the above-mentioned polyol and (meth)acrylic acid may be used to carry out an esterification reaction by a known method. Also, the reaction may be one in which all or a part of the hydroxyl groups are reacted.

[0021] (A2) can be obtained, for example, by reacting a polyamine or alkanolamine with the above-mentioned (meth)acrylic halide or allyl halide.

[0022] The polythiol used in producing the unsaturated carboxylic acid thioester or alkenyl thioether of polythiol (A3) preferably has 2 to 4 thiol groups and 2 to 18 carbon atoms, and examples thereof include ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-propanedithiol, 1,4-benzenedithiol, 1,2-benzenedithiol, bis(4-mercaptophenyl)sulfide, 4-t-butyl-1,2-benzenedithiol, ethylene glycol dithioglycolate, trimethylolpropane tris(thioglycolate)thiocyanuric acid, di(2-mercaptoethyl)sulfide, di(2-mercaptoethyl)ether, and combinations of two or more of these. (A3) can be obtained by reacting these polythiols with the above-mentioned (meth)acrylic halides or allyl halides.

[0023] Among these vinyl polymerizable compounds (A), preferred are unsaturated carboxylic acid esters or alkenyl ethers of polyols (A1).

[0024] Among the unsaturated carboxylates or alkenyl ethers of polyols (A1), from the viewpoint of heat resistance, unsaturated carboxylates of polyhydric alcohols having 2 to 8 valences are preferred, and unsaturated carboxylates of polyhydric alcohols having 3 to 6 valences are more preferred.

[0025] The active hydrogen value of the vinyl polymerizable compound (A) is preferably 0 to 1200, and more preferably 0 to 500, from the viewpoint of the flame retardancy of the urethane foam. Here, the active hydrogen value means "56100 / molecular weight per active hydrogen", and when the group having active hydrogen is a hydroxyl group, it corresponds to the hydroxyl value. The hydroxyl value is mg of KOH equivalent to neutralizing 1 g of sample, and means "56100 / molecular weight per hydroxyl group". Here, 56100 indicates mg of 1 mole of KOH. The method for measuring the active hydrogen value may be any known method as long as it can measure the value defined above, and is not particularly limited. In the case of the hydroxyl value, for example, the method described in JIS K1557-1 may be mentioned.

[0026] The organic polyisocyanate (B) in the present invention may be any compound having two or more isocyanate groups in the molecule, and may be any compound that has been used in the manufacture of polyurethane foams. Examples of such isocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, modified products thereof (e.g., modified products containing urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, isocyanate groups, or oxazolidone groups), and mixtures of two or more of these.

[0027] Examples of aromatic polyisocyanates include aromatic diisocyanates having 6 to 16 carbon atoms (excluding carbon in NCO groups; the same applies to the following isocyanates), aromatic triisocyanates having 6 to 20 carbon atoms, and crude products of these isocyanates. Specific examples include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- or 4,4'-diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (crude MDI), naphthylene-1,5-diisocyanate, and triphenylmethane-4,4',4''-triisocyanate. Examples of the aliphatic polyisocyanate include aliphatic diisocyanates having 6 to 10 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having a carbon number of 6 to 16. Specific examples include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, and norbornane diisocyanate. Examples of the araliphatic polyisocyanate include araliphatic diisocyanates having a carbon number of 8 to 12. Specific examples include xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate.

[0028] Specific examples of modified polyisocyanates include urethane-modified MDI, carbodiimide-modified MDI, sucrose-modified TDI, and castor oil-modified MDI. Among these, from the viewpoint of foam physical properties, aromatic polyisocyanates are preferred, and more preferred is one or more selected from the group consisting of 2,4'- or 4,4'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, and modified products thereof. From the viewpoint of foam properties, the content of one or more selected from the group consisting of 2,4'- or 4,4'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, and modified products thereof in (B) is preferably 40% by weight or more, and more preferably 80% by weight or more.

[0029] In the isocyanate composition of the present invention, the weight ratio (A) / (B) of the vinyl polymerizable compound (A) to the polyisocyanate (B) is 1 / 99 to 40 / 60. If the weight ratio of the vinyl polymerizable compound (A) is less than 1 based on the total weight of the vinyl polymerizable compound (A) and the polyisocyanate (B), the flame retardancy is deteriorated and the total heat generation amount measured by the method described below is increased. If the weight ratio of the vinyl polymerizable compound (A) is more than 40 based on the total weight of the vinyl polymerizable compound (A) and the polyisocyanate (B), the curing property of the urethane foam is deteriorated and the compressive strength measured by the method described below is reduced. In addition, the flame retardancy is deteriorated and the total heat generation amount is increased. The weight ratio (A) / (B) of the vinyl polymerizable compound (A) to the polyisocyanate (B) is preferably 2 / 98 to 25 / 75, and more preferably 3 / 97 to 20 / 80.

[0030] The present invention is a polyurethane foam which is a reaction product of the above-mentioned isocyanate composition and polyol composition (P). The polyol composition (P) includes polyhydric alcohols (p1), polyether polyols (p2), polyester polyols (p3), other polyols (p4), and mixtures of two or more of these.

[0031] As the polyhydric alcohol (p1), the polyhydric alcohols exemplified above for use in the production of (A1) can be used.

[0032] Examples of the polyether polyol (p2) include AO adducts of compounds containing at least 2 (preferably 3 to 8) active hydrogen atoms (polyhydric alcohols, polyhydric phenols, ammonia, amines, polycarboxylic acids, phosphoric acids, etc.), and mixtures thereof. The polyhydric alcohols include those mentioned above.

[0033] Examples of polyhydric (dihydric to octahydric or higher) phenols include monocyclic polyhydric phenols (hydroquinone, resorcinol, pyrogallol, phloroglucine, etc.); polycyclic polyhydric phenols (dihydroxynaphthalene, etc.); bisphenol compounds (bisphenol A, -F, or S); and condensates of phenol and formaldehyde (novolak, resol, etc.).

[0034] Examples of the amine include aliphatic amines [monoamines (C1 to C20, for example, n-butylamine, octylamine), diamines (C2 to C10, for example, ethylenediamine, propylenediamine, hexamethylenediamine), polyalkylenepolyamines (C4 to C20, for example, diethylenetriamine, triethylenetetramine, pentaethylenehexamine), etc.]; aromatic (aliphatic) amines (mono- or polyamines of C6 to C20, for example, aniline, phenylenediamine, tolylenediamine, xylylene diamines, diethyltoluylenediamine, methylenedianiline, diphenyletherdiamine; alicyclic amines (C4 to 20, for example, isophoronediamine, cyclohexanediamine, dicyclohexylmethanediamine); heterocyclic amines (C4 to 20, for example, piperazine, aminoethylpiperazine and those described in JP-B-55-21044); alkanolamines (C2 to 20, for example, mono-, di- or triethanolamine, isopropanolamine, etc.).

[0035] Examples of the poly(divalent to tetravalent or higher) carboxylic acid include aliphatic polycarboxylic acids (C4 to C18, for example, succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid), aromatic polycarboxylic acids (C8 to C18, for example, terephthalic acid, isophthalic acid, orthophthalic acid, trimellitic acid, pyromellitic acid), alicyclic polycarboxylic acids (C8 to C15, for example, cyclohexane 1,4-dicarboxylic acid), and mixtures of two or more of these.

[0036] Examples of AO to be added to the active hydrogen-containing compound include C2 to C12 or more (preferably C2 to C8) such as ethylene oxide, 1,2-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran and 3-methyl-tetrahydrofuran (hereinafter abbreviated as EO, PO, BO, THF and MTHF, respectively), 1,3-propylene oxide, isoBO, C5 to C12 α-olefin oxide, substituted AO such as styrene oxide and epihalohydrin (epichlorohydrin, etc.), and combinations of two or more of these (random addition and / or block addition). Among these, PO and a combination of EO / PO are more preferred from the industrial viewpoint. The amount of AO added is preferably 1 to 10 mol, more preferably 2 to 6 mol, per active hydrogen atom.

[0037] Specific preferred examples of the polyether polyol include PO adducts of glycerin, trimethylolpropane, triethanolamine, pentaerythritol, sorbitol and sucrose, EO / PO adducts and mixtures thereof.

[0038] From the viewpoint of the mechanical properties of the polyurethane foam, the number average molecular weight (Mn) of (p2) is preferably from 150 to 3,000, more preferably from 200 to 2,500, and particularly preferably from 250 to 1,500. In the present invention, Mn is a molecular weight calculated from an active hydrogen number, which will be described later.

[0039] Examples of the polyester polyol (p3) include condensation reaction products of the above-mentioned polyhydric alcohols and / or polyether polyols with the above-mentioned polycarboxylic acids, their anhydrides, and ester-forming derivatives such as lower alkyl (alkyl group is C1 to C4) esters (adipic acid, sebacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc.), AO adducts of the above-mentioned carboxylic acid anhydrides, AO adducts of the above-mentioned condensation reaction products, polylactone polyols [such as those obtained by ring-opening polymerization of lactones (C4 to C10, for example ε-caprolactone, δ-valerolactone) using the above-mentioned polyhydric alcohols as an initiator], and polycarbonate polyols [such as reaction products of the above-mentioned polyhydric alcohols with alkylene carbonates (ethylene carbonate, etc.)].

[0040] Specific examples of (p3) include poly(1,4-butanediol adipate), poly(1,4-butanediol terephthalate), poly(ethylene glycol terephthalate), poly(diethylene glycol terephthalate), poly-ε-caprolactone polyol, and the like. Among (p3), from the viewpoint of flame retardancy, aromatic polyester polyols (p31) are preferred, aromatic polyester diols are more preferred, and condensation products of terephthalic acid or its lower alkyl (having 1 to 4 carbon atoms) esters with aliphatic diols having 2 to 20 carbon atoms are particularly preferred. From the viewpoint of the mechanical properties of the polyurethane foam, Mn of (p3) is preferably from 150 to 3,000, more preferably from 200 to 2,500, and particularly preferably from 250 to 1,500.

[0041] Other polyols (p4) include polymer polyols (hereinafter abbreviated as P / P) and hydroxyl group-containing vinyl polymers (polybutadiene polyols, partially saponified ethylene / vinyl acetate copolymers, etc.). P / P is obtained by in situ polymerization of ethylenically unsaturated monomers in a polyol (the abovementioned OH-terminated polyether polyols and / or polyester polyols, or mixtures of these with the abovementioned polyhydric alcohols). Ethylenically unsaturated monomers include acrylic monomers [(meth)acrylonitrile, alkyl (C1-20 or more) (meth)acrylates (methyl methacrylate, etc.)], hydrocarbon (hereinafter abbreviated as HC) monomers [aromatic unsaturated HC (styrene, etc.), aliphatic unsaturated HC (C2-20 or more alkenes, alkadienes, etc. (α-olefins, butadiene, etc.)], and combinations of two or more of these [combinations of acrylonitrile / styrene (weight ratio of 100 / 0 to 80 / 20), etc.)]. The P / P has a polymer content of, for example, 5 to 80% by weight or more, preferably 30 to 70% by weight.

[0042] Among hydroxyl group-containing vinyl polymers, polybutadiene polyols include OH-terminated butadiene homopolymers and copolymers (styrene / butadiene copolymers, acrylonitrile / butadiene copolymers, etc.) [those having a 1,2-vinyl structure, those having a 1,4-trans structure, those having a 1,4-cis structure, and those having two or more of these, etc.], as well as hydrogenated products thereof (hydrogenation rate is, for example, 20 to 100%), and the like.

[0043] From the viewpoint of the mechanical properties of the polyurethane foam, Mn of (p4) is preferably from 150 to 3,000, more preferably from 200 to 2,500, and particularly preferably from 250 to 1,500.

[0044] In the present invention, from the viewpoint of flame retardancy, it is preferable that 50% by weight or more of the polyol composition (P) is the aromatic polyester polyol (p31), and it is more preferable that 70% by weight or more of (P) is (p31).

[0045] The active hydrogen number of the polyol composition (P) is preferably from 50 to 1,900, more preferably from 160 to 1,850, and particularly preferably from 200 to 1,000, from the viewpoints of flame retardancy and foam physical properties.

[0046] The polyurethane foam of the present invention can be obtained by using the following method, in which the isocyanate composition containing the vinyl polymerizable compound (A) and the organic polyisocyanate (B) is reacted with the polyol composition (P) in the presence of a foaming agent to produce a polyurethane foam.

[0047] The present invention is a method for producing a polyurethane foam by reacting the isocyanate composition containing the vinyl polymerizable compound (A) and the organic polyisocyanate (B) with the polyol composition (P) in the presence of a foaming agent.

[0048] In the production method of the present invention, the isocyanate index (NCO INDEX) [(NCO group / active hydrogen atom-containing group) equivalent ratio × 100] in producing the polyurethane foam is preferably 70 or more and less than 500, more preferably 80 to 450, particularly preferably 90 to 420, and most preferably 100 to 400, from the viewpoint of the general physical properties and flame retardant performance of the polyurethane foam.

[0049] The blowing agent (C) used in the production process of the present invention includes water, hydrogen atom-containing halogenated hydrocarbons, low boiling point hydrocarbons, liquefied carbon dioxide gas, etc., and two or more of them may be used in combination. Specific examples of hydrogen atom-containing halogenated hydrocarbons include HCFC (hydrochlorofluorocarbon) type compounds (e.g., HFC-245fa and HFC-365mfc) and HFO (hydrofluoroolefin) type compounds (e.g., HFO-1336mzzZ, HFO-1233zdE). The low boiling point hydrocarbons include those having a boiling point of −5 to 70° C., and specific examples thereof include butane, pentane, and cyclopentane. Among these, pentane and cyclopentane are preferred, and cyclopentane is more preferred.

[0050] In the production method of the present invention, a flame retardant (D) can be used as necessary. Examples of the flame retardant (D) include phosphate esters, halogenated phosphate esters, aluminum hydroxide, antimony oxide, boron compounds, bromine compounds, chlorinated paraffins, and cyclic fatty acids. Among these, preferred are phosphate esters and halogenated phosphate esters.

[0051] The amount of the flame retardant (D) used in the production method of the present invention is less than 20% by weight, preferably 2 to 20% by weight, and more preferably 4 to 15% by weight, based on the total weight of the polyol composition (P) and the organic polyisocyanate (B), from the viewpoint of the heat insulating performance of the urethane foam.

[0052] In the production method of the present invention, other additives (E) can be used as necessary, and the reaction between the isocyanate composition and the polyol composition (P) can be carried out in the presence of the other additives (E). Among (E), examples of the radical polymerization initiator (E1) include water-soluble radical polymerization initiators such as azo compounds (e.g., 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(1-acetoxy-1-phenylethane, etc.), organic peroxides (e.g., dibenzoyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, dicumyl peroxide, etc.), and combinations of peroxides and dimethylaniline (redox catalysts). The amount of the radical polymerization initiator (E1) is preferably 10% by weight or less, more preferably 0.001 to 5% by weight, particularly preferably 0.005 to 3% by weight, and most preferably 0.01 to 2.5% by weight, based on the weight of the polyol composition (P). When it is 10% by weight or less, it is easy to proceed with the polymerization reaction simultaneously with the urethanization reaction, and when it is 0.001% by weight or more, a polyurethane foam with good curing properties is obtained.

[0053] Other additives (E) include foam stabilizers (E2) (dimethylsiloxane-based, polyether-modified dimethylsiloxane-based, etc.), isocyanurate catalysts (E3) (e.g., potassium octylate, quaternary ammonium salts, etc.), urethane catalysts (E4) (tertiary amine catalysts, e.g., triethylenediamine, N-ethylmorpholine, diethylethanolamine, N,N,N',N'-tetramethylhexamethylenediamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, diaminobicyclooctane, 1,2-dimethylimidazole, 1-methylimidazole, 1-isobutyl-2-methylimidazole, etc.), and the like. Examples of known additives include azoles, bis(dimethylaminoethyl)ethers, and 1,8-diazabicyclo-[5,4,0]-undecene-7, and the like, and / or metal catalysts (e.g., stannous octoate, dibutyl stannous dilaurate, lead octoate, and the like), colorants (dyes, content, and the like), plasticizers (phthalates, adipates, and the like), organic fillers (synthetic short fibers, hollow microspheres made of thermoplastic or thermosetting resins, and the like), antioxidants (hindered phenols, hindered amines, and the like), anti-aging agents (triazoles, benzophenones, and the like), and mold release agents (waxes, metal soaps, or mixtures thereof).

[0054] The amount of the other additives (E) added based on the weight of the polyol composition (P) is preferably 10% by weight or less for the foam stabilizer (E2), more preferably 0.01 to 7% by weight, particularly preferably 0.05 to 5% by weight, and most preferably 0.1 to 3% by weight. The amount of the urethanization catalyst (E4) is preferably 15% by weight or less, more preferably 0.01 to 10% by weight, particularly preferably 0.02 to 5.0% by weight, and most preferably 0.1 to 3.5% by weight. When the amount of the urethanization catalyst (E4) is 10% by weight or less, it is easy to proceed with the polymerization reaction simultaneously with the urethanization reaction, and when it is 0.01% by weight or more, a polyurethane foam with good curing properties is obtained. The colorant is preferably 2% by weight or less, more preferably 1% by weight or less. The plasticizer is preferably 50% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less. The organic filler is preferably 50% by weight or less, more preferably 40% by weight or less, and particularly preferably 30% by weight or less. The antioxidant is preferably 1% by weight or less, more preferably 0.01 to 0.5% by weight. The anti-aging agent is preferably 1% by weight or less, more preferably 0.01 to 0.5% by weight. The release agent is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 3% by weight or less.

[0055] In the method for producing a polyurethane foam of the present invention, the above-mentioned isocyanate composition containing the vinyl polymerizable compound (A) and the organic polyisocyanate (B) is reacted with the polyol composition (P).

[0056] A specific example of the method for producing the polyurethane foam of the present invention is as follows. When using a mold, a vinyl polymerizable compound (A) and an organic polyisocyanate (B) are mixed in a predetermined amount to prepare an isocyanate composition. Then, using a polyurethane foaming machine or a stirrer, a mixture (foaming liquid) is rapidly mixed with a predetermined amount of the isocyanate composition and a mixture of a predetermined amount of the polyol composition (P), a foaming agent (C), and if necessary, a flame retardant (D) and other additives (E) to form a mixture. The mixture is poured into a mold, cured for a predetermined time, and then demolded to obtain a polyurethane foam. The mold may be either an open mold (free foaming) or a closed mold (molded foaming), and may be at room temperature or under heating (for example, 30 to 80°C). In addition, other methods that can be used include a method of continuously foaming the foaming liquid prepared in the same manner as when using a mold on a continuous conveyor, a method of pouring the mixed liquid between surface materials such as gypsum board and plywood to cause foaming, and a method of spraying the foaming liquid onto a base material to cause foaming (spray foaming). When the composition is used as a heat insulating agent for buildings, the spray foaming method is preferred from the viewpoint of heat insulating properties when applied to buildings. The urethane reaction is preferably carried out by the one-shot method, since the viscosity of the stock solution in which the components are mixed becomes high in the prepolymer method. The method of the present invention can also be applied to molding by the RIM (reaction injection molding) method, and can also be used to obtain polyurethane foam by the mechanical froth method.

[0057] The density (kg / m) of the molded polyurethane foam obtained by the production method of the present invention 3 In mold foaming, the core density with skin is preferably 80 or less, more preferably 15 to 78, particularly preferably 20 to 75, and most preferably 25 to 70. In free foaming, the core density is preferably 50 or less, more preferably 10 to 65, particularly preferably 15 to 63, and most preferably 20 to 61.

[0058] The vinyl polymerizable functional group concentration (mmol / g) in the polyurethane foam obtained by the production method of the present invention is preferably 0.05 or more from the viewpoint of flame retardancy, more preferably 0.06 to 10.0, even more preferably 0.07 to 8.00, particularly preferably 0.08 to 5.00, and most preferably 0.10 to 2.50. The vinyl polymerizable functional group concentration (mmol / g) in the polyurethane foam can be calculated from the blend amounts of the raw materials as follows. Vinyl polymerizable functional group concentration in polyurethane foam (mmol / g) = [Number of vinyl polymerization groups in one molecule of (A) / number average molecular weight of (A)] x amount of (A) / [amount of (P) + amount of (A) + amount of (D) + amount of (E) + amount of (B)] x 1000

[0059] The compressive strength (N / cm 2 ) for rigid molded foam is preferably 10.0 or more, more preferably 15.0 or more, and further preferably 17.0 or more. The compressive strength of polyurethane foam is measured by the method described in JIS K7220 (rigid foamed plastics--determination of compressive properties).

[0060] The thermal conductivity (mW / m K) of the polyurethane foam obtained by the production method of the present invention is preferably 27.0 or less, more preferably 24.0 or less, and further preferably 23.0 or less, in the case of a rigid molded foam. The thermal conductivity of the polyurethane foam is measured by the method described in JIS A1412-2 (Method of measuring thermal resistance and thermal conductivity of thermal insulating materials-Part 2: Heat flow meter method (HFM method)).

[0061] The total calorific value (MJ / m) of the polyurethane foam obtained by the production method of the present invention 2 From the viewpoint of flame retardancy, the total calorific value is preferably 10.0 or less after a heating time of 5 minutes, more preferably 8.0 or less after a heating time of 5 minutes, and particularly preferably 8.0 or less after a heating time of 5 minutes and 8.0 or less after a heating time of 10 minutes. The total calorific value of the polyurethane foam is obtained by a heat generation test using a cone calorimeter in accordance with ISO5660. EXAMPLES

[0062] The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

[0063] The raw materials for the polyurethane foams in Examples 1 to 7 and Comparative Examples 1 to 3 are as follows. (1) Polyol Composition (P) (P-1) Polyester polyol obtained from phthalic acid and ethylene glycol (number average active hydrogen-containing functional group number 2, hydroxyl value 250) (2) Vinyl polymerizable compound (A) (A-1) A vinyl polymerizable compound having 10.1 (mmol / g) vinyl polymerizable functional groups in the molecule, obtained by reacting pentaerythritol with acrylic acid. (A-2) A vinyl polymerizable compound with 11.4 (mmol / g) vinyl polymerizable functional groups in the molecule, obtained by reacting pentaerythritol with acrylic acid. (A-3) A vinyl polymerizable compound having 4.8 (mmol / g) vinyl polymerizable functional groups in the molecule, obtained by reacting pentaerythritol with methacrylic acid. (A-4) A vinyl polymerizable compound obtained by reacting glycerin with acrylic acid, with an intramolecular vinyl polymerizable functional group of 11.8 (mmol / g) (3) Foaming agent (C) (C-1) Water (C-2) HFO-1233zdE (4) Flame retardants (D) (D-1) Trichloropropyl phosphate (manufactured by Daihachi Chemical Co., Ltd.) (5) Additives (E) (E2-1) Foam stabilizer "SH-193" (Dow Corning Toray Co., Ltd.) (E3-1) Catalyst "Dabco K-15" (Air Products Japan Co., Ltd.) (E3-2) Catalyst "DabcoTMR7" (Air Products Japan Co., Ltd.) (E4-1) Catalyst "Dabco33LV" (Air Products Japan Co., Ltd.) (6) Organic polyisocyanate (B) (B-1) Crude MDI "MR-200" (manufactured by Tosoh Corporation), NCO%=31.5

[0064] (Examples 1 to 7, Comparative Examples 1 to 3) The polyurethane foams of Examples 1 to 7 and Comparative Examples 1 to 3 were produced by the following method. A polyol premix was prepared by mixing the polyol composition (P), the blowing agent (C), the flame retardant (D), and other additives (E) in the amounts shown in Table 1. Next, a vinyl polymerizable compound (A) and an organic polyisocyanate (B) were mixed in the amounts shown in Table 1 to prepare an isocyanate premix (isocyanate composition). In Comparative Example 1, the vinyl polymerizable compound (A) was mixed into the polyol premix, not into the isocyanate premix. The polyol premix and isocyanate premix immediately after preparation were adjusted to 20±5°C, and rapidly mixed at 8000 rpm for 7 seconds using a Homo Disper (Primix Corporation).The mixture was then quickly poured into a 300×300×50 mm mold adjusted to 70°C, and mold foaming was performed to obtain a polyurethane foam molded product. In addition, for Examples 1 to 7 and Comparative Example 1, the prepared polyol premix and isocyanate premix were transferred to a sealed container, and in the cases where they were stored in a thermostatic chamber at 40°C for 7 days and for 14 days, they were mixed and molded to foam in the same manner as described above to obtain molded polyurethane foam products.

[0065] The molded products obtained in each of the Examples and Comparative Examples were measured for molded product density, compressive strength, heat insulation (thermal conductivity) and flammability, and the results are shown in Table 1. The measurement results for Examples 1 to 7 and Comparative Example 1 are shown in the following format: (value for molded product obtained from premix immediately after preparation) / (value for molded product obtained from premix stored in a constant temperature bath at 40°C for 7 days after preparation) / (value for molded product obtained from premix stored in a constant temperature bath at 40°C for 14 days after preparation).

[0066] <Method of measuring molded product density> After obtaining a molded product by the above method, the elasticity was calculated according to the following formula. Molded product density (kg / m 3 ) = Weight of molded product (g) / Volume of molded product (cm 3 ) x 1000

[0067] <Method of measuring compressive strength> According to JIS K7220, a sample piece of 50 x 50 x 35 mm was cut out from the molded product. The sample piece was compressed by 10% of its thickness to measure the compressive stress. The compressive stress was then divided by the cross-sectional area to obtain the compressive strength.

[0068] <Method of measuring thermal conductivity> According to JIS A1412-2, a sample piece of 200 × 200 × 40 mm was cut out from the molded product. Then, the thermal conductivity was measured using a thermal conductivity measuring instrument "AUTO-Λ HC-074" (manufactured by Eiko Seiki Co., Ltd.).

[0069] <Method of measuring flammability (cone calorimeter)> A sample piece of 100 x 100 x 40 mm was cut out from the center of the molded product. In accordance with ISO5660, the total heat generation was measured after heating for 5 and 10 minutes using a "Cone Calorimeter C3" (manufactured by Toyo Seiki Seisakusho Co., Ltd.).

[0070] [Table 1]

[0071] As shown in Table 1, the polyurethane foams of Examples 1 to 7 are excellent in molded article density, compressive strength, heat insulation (thermal conductivity) and flammability (flame retardancy). On the other hand, in Comparative Example 1 in which the vinyl polymerizable compound (A) was added to the polyol premix, the compressive strength decreased and the thermal conductivity increased (thermal insulation decreased) due to side reactions in the polyol premix. In Comparative Example 2, the weight ratio (A) / (B) of the vinyl polymerizable compound (A) to the organic polyisocyanate (B) is less than 1 / 99, and therefore the flame retardancy is insufficient (the total heat generation is high). In Comparative Example 3, the weight ratio (A) / (B) of the vinyl polymerizable compound (A) to the organic polyisocyanate (B) exceeds 40 / 60, so that the curability is insufficient, the compressive strength is low, and the flame retardancy is also insufficient. [Industrial Applicability]

[0072] Since the polyurethane foam of the present invention has excellent heat insulating properties (thermal conductivity), it can be suitably used, for example, as a construction heat insulating agent, and in particular, it can be suitably used for sandwich panels, boards, siding or spray applications.

Claims

1. An isocyanate composition comprising a vinyl polymerizable compound (A) and an organic polyisocyanate (B), the vinyl polymerizable compound (A) has a vinyl polymerizable functional group represented by the following general formula (1), and the concentration of the vinyl polymerizable functional group in one molecule of the vinyl polymerizable compound (A) is 0.5 to 20 (mmol / g), the vinyl polymerizable compound (A) is a compound in which a residue obtained by removing all or a part of the hydrogen atoms contained in a compound having at least two active hydrogen groups selected from the group consisting of a hydroxyl group, an amino group, and a mercapto group is bonded to a monovalent unsaturated hydrocarbon group directly or via a carbonyl group, The isocyanate composition has a weight ratio (A) / (B) of the vinyl polymerizable compound (A) to the organic polyisocyanate (B) of 1 / 99 to 40 / 60. [In general formula (1), R represents hydrogen, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 21 carbon atoms.]

2. A polyurethane foam which is the reaction product of the isocyanate composition according to claim 1 and a polyol composition (P).

3. A method for producing a polyurethane foam, comprising reacting an isocyanate composition containing a vinyl polymerizable compound (A) and an organic polyisocyanate (B) with a polyol composition (P) in the presence of a foaming agent (C), comprising the steps of: the vinyl polymerizable compound (A) has a vinyl polymerizable functional group represented by the following general formula (1), and the concentration of the vinyl polymerizable functional group in one molecule of the vinyl polymerizable compound (A) is 0.5 to 20 (mmol / g), the vinyl polymerizable compound (A) is a compound in which a residue obtained by removing all or a part of the hydrogen atoms contained in a compound having at least two active hydrogen groups selected from the group consisting of a hydroxyl group, an amino group, and a mercapto group is bonded to a monovalent unsaturated hydrocarbon group directly or via a carbonyl group, The method for producing a polyurethane foam, wherein the weight ratio (A) / (B) of the vinyl polymerizable compound (A) to the organic polyisocyanate (B) is 1 / 99 to 40 / 60. [In general formula (1), R represents hydrogen, an alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 21 carbon atoms.]

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