Polyol composition for polyurethane foam production, reaction solution set for polyurethane foam production, polyurethane foam, and method for producing polyurethane foam

Abstract

To provide a highly versatile technique that can reduce the thermal conductivity of polyurethane foam.SOLUTION: A polyol composition for polyurethane foam production includes a polyol and a solution including a urea compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to a polyol composition for the manufacture of polyurethane foam, a reaction solution set for the manufacture of polyurethane foam, polyurethane foam, and a method for manufacturing polyurethane foam. [Background technology]

[0002] Patent Document 1 discloses a method for producing rigid polyurethane foam by reacting a predetermined amount of aromatic polyester diol with a raw material containing a specific vinyl polymerizable compound. It is stated that this method makes it possible to obtain a foam with excellent heat insulation properties (thermal conductivity) without degrading the flammability (flame retardancy) of the rigid polyurethane foam. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2015-199937 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] However, the method described in Patent Document 1 has the drawback of lacking versatility because the types and amounts of raw materials that can be used as polyols are limited. This disclosure is made in view of the above circumstances and aims to provide a highly versatile technology that can reduce the thermal conductivity of polyurethane foam. This disclosure can be implemented in the following forms. [Means for solving the problem]

[0005] A polyol composition for the manufacture of polyurethane foam, comprising a polyol and a solution of a urea compound. [Effects of the Invention]

[0006] According to this disclosure, a highly versatile technology can be provided that can reduce the thermal conductivity of polyurethane foam. [Modes for carrying out the invention]

[0007] Herein lies a preferred example of this disclosure. The solvent of the solution is a solvent having an -OH group, a polyol composition for the manufacture of polyurethane foam. A polyol composition for the manufacture of polyurethane foam, wherein the solvent of the solution is water. • A polyol composition containing hydrohaloolefin for the manufacture of polyurethane foam. A polyol composition for the manufacture of polyurethane foam, containing alkanes with 4 to 8 carbon atoms. A reaction solution set for the manufacture of polyurethane foam, comprising the above-mentioned polyol composition for the manufacture of polyurethane foam and an isocyanate component. • Polyurethane foam obtained from the above-mentioned reaction solution set for the manufacture of polyurethane foam. A method for producing polyurethane foam, comprising mixing the above-mentioned polyol composition for the manufacture of polyurethane foam with an isocyanate component.

[0008] The disclosure is described in detail below. In this specification, when a numerical range is indicated using "-", it includes both the lower and upper limits unless otherwise specified. For example, the expression "10-20" includes both the lower limit "10" and the upper limit "20". In other words, "10-20" has the same meaning as "10 or more and 20 or less".

[0009] 1. Polyol composition for the manufacture of polyurethane foam Polyol composition for the manufacture of polyurethane foam (hereinafter also referred to as polyol composition) comprises a polyol and a solution of a urea compound.

[0010] (1) Polyol The polyol is not particularly limited. Various polyols may be used individually or in combination of two or more. The number-average molecular weight, number of functional groups, and hydroxyl value of the polyol are not particularly limited. Preferably, the polyol has a number-average molecular weight of 350-3000, 2-8 functional groups, and a hydroxyl value (OHV) of 150 mgKOH / g-500 mgKOH / g.

[0011] Examples of polyols include polyether polyols, polyester polyols, polyether ester polyols, polycarbonate diols, and polyols with a carbon-carbon bond in the main chain. Among these, polyether polyols are preferred from the viewpoint of hydrolysis resistance. Examples of polyether polyols include polyoxypropylene-polyoxyethylene polyols, polymer polyols, and polyoxytetramethylene glycol. Examples of polyester polyols include aliphatic or aromatic polycondensed polyester polyols and polycaprolactone polyols. Examples of polyols with a carbon-carbon bonded main chain include polyolefin polyols such as polybutadiene polyols and isoprene polyols, plant-derived polyols, and acrylic polyols.

[0012] (1.1) Polyether polyol Examples of polyether polyols include polyether polyols obtained by adding one or more of the following initiators (compounds) to one or more of the following: ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, epichlorohydrin, styrene oxide, etc., or polytetramethylene ether glycol. Among the following initiators, it is preferable that at least one of the initiators be an alcohol with four to eight functionalities, from the viewpoint of imparting appropriate hardness to the polyurethane foam and improving flame resistance.

[0013] (1.1.1) Initiator (1.1.1.1) Polyhydric alcohol and alkylene oxide adduct of polyhydric alcohol Examples of polyhydric alcohols: 〔Difunctional alcohol〕 Ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol 〔Trifunctional alcohol〕 Glycerol, trimethylolpropane 〔Tetrafunctional alcohol〕 Pentaerythritol 〔Hexafunctional alcohol〕 Sorbitol 〔Octafunctional alcohol〕 Sucrose (1.1.1.2) Alkylene oxide adduct of polyhydric phenols Examples of alkylene oxide adduct of polyhydric phenols: Alkylene oxide adduct of bisphenol A (1.1.1.3) Polyhydric hydroxy compounds Examples of polyhydric hydroxy compounds: Phosphoric acid, benzene phosphoric acid, polyphosphoric acid (such as tripolyphosphoric acid and tetrapolyphosphoric acid), etc. (1.1.1.4) Phenol-aniline-formaldehyde ternary condensation product (1.1.1.5) Aniline-formaldehyde condensation product (1.1.1.6) Polyamines Examples of polyamines: Ethylenediamine, diethylenetriamine, triethylenetetramine, methylene bis orthochloroaniline, 4,4- and 2,4'-diphenylmethanediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, etc. (1.1.1.7) Alkanolamines Examples of alkanolamines: Triethanolamine, diethanolamine, etc.

[0014] (1.1.2) Polymer polyol Polymer polyol is a polyol obtained by graft-polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, alkyl methacrylate, etc. onto the aforementioned polyether polyol.

[0015] (1.2) Polyester polyol Polyester polyols are obtained by condensation of one or more compounds having at least two hydroxyl groups with one or more compounds having at least two carboxyl groups, or are ring-opening polymers of cyclic esters such as caprolactone and methylvalerolactone.

[0016] (1.2.1) Examples of compounds having at least two hydroxyl groups Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3- and 1,4-butanediol, tetramethylene glycol, neopentyl glycol, methylpentanediol, butylethylpropanediol, hexamethylene glycol, decamethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol

[0017] (1.2.2) Examples of compounds having at least two carboxyl groups Malonic acid, maleic acid, succinic acid, adipic acid, tartaric acid, pimelic acid, azelaic acid, sebacic acid, oxalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, hemeltic acid

[0018] (1.3) Polycarbonate diol Examples of polycarbonate polyols include those obtained by transesterification reactions between low molecular weight polyols such as butanediol and hexanediol and low molecular weight carbonates such as propylene carbonate and diethyl carbonate.

[0019] (1.4) Polyolefin-based polyols Examples of polyolefin-based polyols include polybutadiene polyols, polyisoprene polyols, hydrogenated polybutadiene polyols, and hydrogenated polyisoprene polyols.

[0020] (1.5) Plant-derived polyols In addition to the polyols listed above, plant-derived polyols may also be included as polyols. Examples of plant-derived polyols include castor oil polyols, soybean oil polyols, palm oil polyols, palm kernel oil polyols, coconut oil polyols, cashew oil polyols, olive oil polyols, cottonseed oil polyols, safflower oil polyols, sesame oil polyols, sunflower oil polyols, and linseed oil polyols. Plant-derived polyols typically have 2 to 3 hydroxyl functional groups per molecule. Examples of castor oil-based polyols include castor oil, reaction products of castor oil and polyols, and esterification reaction products of castor oil fatty acids and polyols. Examples of polyols to be reacted with castor oil or castor oil fatty acids include divalent polyols such as ethylene glycol, diethylene glycol, and propylene glycol, or trivalent or higher polyols such as glycerin, trimethylolpropane, hexanetriol, and sorbitol. Examples of soybean oil-based polyols include polyols derived from soybean oil, such as reaction products of soybean oil and polyols, and esterification reaction products of soybean oil fatty acids and polyols. The polyols used to react with soybean oil or soybean oil fatty acids can be the same as those used for castor oil. The same applies to palm oil-based polyols, cashew oil-based polyols, etc., as to soybean oil-based polyols. The various polyols exemplified as plant-derived polyols may be used individually or in combination of two or more.

[0021] (2) Solution of urea compound The polyol composition contains a urea compound solution to reduce the thermal conductivity of the polyurethane foam. The use of the urea compound solution is also expected to improve the flame retardancy of the resulting polyurethane foam. Examples of urea compounds include urea and thiourea. Urea is a compound represented by the chemical formula CO(NH2)2. Thiourea is a compound represented by the chemical formula CS(NH2)2. Urea compounds may be used individually or in combination of two or more. A solution of a urea compound is a liquid mixture containing the urea compound and a solvent. By including the urea compound in a liquid mixture with a solvent rather than as a solid in the polyol composition, the urea compound can be suitably dispersed in the polyurethane foam raw material.

[0022] The following explains the presumed reason for the reduced thermal conductivity of polyurethane foam. It is presumed that the presence of a urea compound solution in the polyol composition shortens the rise time when the polyol composition reacts with the isocyanate component. This shortening of the rise time is thought to lead to a decrease in thermal conductivity, as the cell diameter of the polyurethane foam becomes smaller and communication between cells is suppressed. Another way to shorten the rise time when the polyol composition reacts with the isocyanate component is to increase the amount of catalyst added. However, increasing the amount of catalyst increases the overall reactivity, which may shorten the cream time when the polyol composition reacts with the isocyanate component, potentially impairing the moldability of the polyurethane foam. On the other hand, in a configuration where the polyol composition contains a solution of a urea compound, the cream time when the polyol composition reacts with the isocyanate component is not shortened as much as the rise time. Therefore, even when a solution of a urea compound is included, the moldability of the polyurethane foam can be ensured. Thus, solutions of urea compounds are particularly useful as a means of reducing the thermal conductivity while ensuring the moldability of polyurethane foam.

[0023] The solvent is not particularly limited. Examples of solvents include solvents containing -OH groups and solvents containing ester bonds (e.g., plasticizers). The solvent is preferably a solvent containing -OH groups. Specifically, the solvent is preferably selected from the group consisting of water, monohydric or polyhydric alcohols having 1-6 carbon atoms, polyethylene glycols, and polypropylene glycols. The solvent is more preferably water, which has high solubility for urea compounds and can also be used as a foaming agent. In other words, the solution of the urea compound is preferably an aqueous solution of the urea compound. Examples of monohydric alcohols having 1-6 carbon atoms include ethanol, propanol, isopropanol, butanol, and isobutanol, while examples of polyhydric alcohols include ethylene glycol, propylene glycol, isoprene glycol, 1,3-butylene glycol, hexylene glycol, trimethylolpropane, glycerin, and sorbitol. The molecular weight of polyethylene glycols or polypropylene glycols can be appropriately selected depending on the amount of urea compound, etc. From the viewpoint of solubility of the urea compound, the molecular weight of polyethylene glycols is preferably less than 200. Similarly, from the viewpoint of solubility of the urea compound, the molecular weight of polypropylene glycols is preferably less than 200. Examples of polyethylene glycols or polypropylene glycols include diethylene glycol and dipropylene glycol. The concentration of the urea compound solution is preferably 5% or higher, and more preferably 10% or higher, 20% or higher, 30% or higher, or 35% or higher. There is no particular upper limit to the concentration of the urea compound solution. For example, the concentration of the urea solution is 52% or lower at 20°C when the solvent is water. The concentration (%) of the urea solution is calculated as (mass of urea compound / mass of solution) × 100.

[0024] The content of the urea compound in the polyol composition is not particularly limited. From the viewpoint of reducing the thermal conductivity of the polyurethane foam, the content of the urea compound is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1.0 part by mass or more, per 100 parts by mass of polyol. On the other hand, from the viewpoint of maintaining the various physical properties of the polyurethane foam and from the viewpoint of manufacturing costs, it is preferably 8 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less. From these viewpoints, the total amount of urea compound blended is preferably 0.05 parts by mass or more and 8 parts by mass or less per 100 parts by mass of polyol, more preferably 0.1 parts by mass or more and 5 parts by mass or less, and even more preferably 0.5 parts by mass or more and 3 parts by mass or less per 100 parts by mass of polyol.

[0025] (3) Foaming agent (optional ingredient) The polyol composition preferably contains a blowing agent. The blowing agent is preferably one or more selected from the group consisting of water, hydrohaloolefins, and alkanes having 4 to 8 carbon atoms.

[0026] It is preferable that at least water be used as the foaming agent. The water used as the foaming agent is preferably present as a solvent in the solution of the urea compound. From the viewpoint of ensuring the amount of urea compound in the polyol composition, the water content is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1.0 part by mass or more, per 100 parts by mass of polyol. On the other hand, from the viewpoint of reducing thermal conductivity, the water content is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less. From these viewpoints, the water content is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, and even more preferably 1.0 part by mass or more and 12 parts by mass or less, per 100 parts by mass of polyol.

[0027] Examples of hydrohaloolefins include hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs). Examples of hydrofluoroolefins include fluoroalkenes with 3-6 carbon atoms. Examples of hydrochlorofluoroolefins include chlorofluoroalkenes with 3-6 carbon atoms. More specifically, examples include trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorotrifluoropropene such as HFO-1233, chlorodifluoropropene such as HCFO-1242zf, and chlorotetrafluoropropene such as HCFO-1224yd. More specifically, examples include 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,1,1-trifluoropropene, 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 1,1,1,3,3,3-hexafluorobuto-2-ene, 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,1,2,3-pentafluoropropene (HFO-1225yez), 1-chloro-3,3,3-trifluoropropene (HFO-1233zd), and 1,1,1,4,4,4-hexafluorobuto-2-ene. Among these, HFO-1233zd is preferred. These hydrohaloolefins may be used individually or in combination of two or more types.

[0028] From the viewpoint of miniaturizing cells and reducing thermal conductivity, the hydrohaloolefin content is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more, per 100 parts by mass of polyol. On the other hand, from the viewpoint of cost and suppressing catalyst deactivation, the hydrohaloolefin content is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 45 parts by mass or less. From these viewpoints, the hydrohaloolefin content is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, and even more preferably 20 parts by mass or more and 45 parts by mass or less, per 100 parts by mass of polyol.

[0029] Examples of alkanes having 4 to 8 carbon atoms include cyclic alkanes such as cyclopentane and cyclohexane, as well as n-pentane and isopentane. Among these, cyclopentane is preferred. These 4-8 carbon alkanes may be used individually or in combination of two or more. From the viewpoint of refining the cells and reducing thermal conductivity, the content of C4-C8 alkanes is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of polyol. On the other hand, from the viewpoint of cost, the content of hydrohaloolefins is preferably 50 parts by mass or less, more preferably 35 parts by mass or less, and even more preferably 25 parts by mass or less. From these viewpoints, the content of hydrohaloolefins is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 35 parts by mass or less, and even more preferably 10 parts by mass or more and 25 parts by mass or less, per 100 parts by mass of polyol.

[0030] (4) Catalyst (optional component) The polyol composition may contain a catalyst. Conventional known catalysts can be used without particular limitation. Various catalysts may be used individually or in combination of two or more. Amine catalysts can be used as catalysts. Specific examples of amine catalysts are shown below. Monoamines such as N,N-dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, triethylamine, and N,N-dimethylbenzylamine; cyclic monoamines such as pyridine, N-methylmorpholine, and N-ethylmorpholine; diamines such as N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N,N',N'-tetramethylhexanediamine, methylene-bis(dimethylcyclohexylamine), and N,N,N',N'-tetraethylethylenediamine; triamines such as N,N,N',N',N"-pentamethyldiethylenetriamine, N,N,N',N',N"-pentamethyldipropylenetriamine, and 2,4,6-tris(dimethylaminomethyl)phenol; bis(2-dimethyl Examples include ether diamines such as aminoethyl ether, 2-(N,N-dimethylamino)ethyl-3-(N,N-dimethylamino)propyl ether, and 4,4'-oxydimethylenedimorpholine; cyclic polyamines such as triethylenediamine, N,N'-dimethylpiperazine, N,N'-diethylpiperazine, N,N-dimethylaminoethylmorpholine, 1-methylimidazole, 1-isobutyl-2-methylimidazole, and 1-butoxy-2-methylimidazole; and alkanolamines such as N,N,N'-trimethylaminoethylethanolamine, N,N,N'-trimethylaminopropylethanolamine, 2-(2-dimethylamino-ethoxy)ethanol, N,N-dimethylaminoethanol, N,N-trimethyl-1,3-diamino-2-propanol, and N-methyl-N'-(2-hydroxyethyl)-piperazine. The total amount of amine catalyst in the polyol composition is not particularly limited. From the viewpoint of sufficiently promoting the polyurethane formation reaction, the total amount of amine catalyst is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.5 parts by mass or more, per 100 parts by mass of polyol. On the other hand, from the viewpoint of maintaining the various physical properties of the polyurethane foam and from the viewpoint of manufacturing costs, it is preferably 8 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less. From these viewpoints, the total amount of amine catalyst is preferably 0.05 parts by mass or more and 8 parts by mass or less per 100 parts by mass of polyol, more preferably 0.1 parts by mass or more and 5 parts by mass or less, and even more preferably 0.5 parts by mass or more and 3 parts by mass or less, per 100 parts by mass of polyol.

[0031] Metal catalysts (organometallic catalysts) can be used as catalysts. Specific examples of metal catalysts are shown below. Examples include organometallic compounds such as dibutyltin oxide, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin oleyl malate, dibutyltin dibutyl malate, dibutyltin acetyl acetate, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl distanoxane, tin octoate, tin stearate, bismuth octoate, and bismuth versate. The total amount of metal catalyst in the polyol composition is not particularly limited. For example, the total amount of metal catalyst can be 0.01 parts by mass or more and 0.50 parts by mass or less per 100 parts by mass of polyol.

[0032] An isocyanate trimerization catalyst may be used as a catalyst as appropriate. When an isocyanate trimerization catalyst is used, the total amount of isocyanate trimerization catalyst in the polyol composition is not particularly limited. For example, the total amount of isocyanate trimerization catalyst can be 0.01 parts by mass or more and 0.50 parts by mass or less per 100 parts by mass of polyol.

[0033] (5) Other ingredients (optional ingredients) The polyol composition may also contain additives such as flame retardants, solvents, foam stabilizers, surfactants, colorants, and antioxidants. Flame retardants known to be used in the manufacture of polyurethane foam can be used. Examples include tris(2,3-dichloropropyl)phosphonate, aluminum hydroxide, metal / amine complexes, ammonium polyphosphate, phosphine, neopentyl bromide polyether, dibromopropanol, and dibromo-neopentyl glycol. A solvent may be used as needed to ensure uniform mixing of the components in the polyol composition. Examples of solvents include ethylene glycol, propylene glycol, and dipropylene glycol. These solvents may also be present as solvents in the urea compound solution. A foam stabilizer known in the manufacture of polyurethane foam can be used. Examples of foam stabilizers include silicone-based foam stabilizers such as siloxane-polyalkylene oxide copolymers. Surfactants, colorants, and antioxidants can be those known in the manufacture of polyurethane foam, and are not particularly limited. The content of these additives can be appropriately adjusted according to the desired physical properties of the resulting polyurethane foam, within a range that does not affect the foaming and resinification reactions of the polyurethane resin. The total amount of additives can be, for example, 1 to 30 parts by mass per 100 parts by mass of polyol.

[0034] 2. Reaction solution set for polyurethane foam manufacturing A reaction solution set for manufacturing a two-component polyurethane foam may be constructed using the above polyol composition. For example, the reaction solution set for manufacturing polyurethane foam comprises the above polyol composition as solution A and an isocyanate component as solution B.

[0035] (2.1) Isocyanate components The isocyanate component is not particularly limited. Preferably, at least one isocyanate selected from the group consisting of aromatic isocyanates, alicyclic isocyanates, and aliphatic isocyanates. A combination of one or more aliphatic isocyanates and one or more aromatic isocyanates is also possible. Furthermore, the isocyanate component may be a bifunctional isocyanate having two isocyanate groups in one molecule, or a trifunctional or more isocyanate having three or more isocyanate groups in one molecule, and may be used alone or in combination of several. For example, difunctional isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, and 3,3'-dimethoxy-4,4'-biphenylenediisocyanate. Examples include aromatic isocyanates such as phenylenediisocyanate, alicyclic isocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and methylcyclohexane diisocyanate, and aliphatic isocyanates such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylenediisocyanate, methylene diisocyanate, and lysine isocyanate. Furthermore, examples of isocyanates with three or more functions include 1-methylbenzol-2,4,6-triisocyanate, 1,3,5-trimethylbenzol-2,4,6-triisocyanate, biphenyl-2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, methyldiphenylmethane-4,6,4'-triisocyanate, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, triphenylmethane-4,4',4"-triisocyanate, polymeric MDI, and the like. In addition, other urethane prepolymers, carbodiimide-modified isocyanates, isocyanurate-modified isocyanates, and burette-modified isocyanates can also be used.

[0036] The reaction solution set for polyurethane foam manufacturing can be used by mixing the polyol composition (Solution A) and the isocyanate component (Solution B) in a predetermined mixing ratio. The mixing ratio of the polyol composition and the isocyanate component is not particularly limited. The mixing ratio of the polyol composition and the isocyanate component can be determined according to the isocyanate index. The isocyanate index is preferably 80 to 300, and more preferably 105 to 115. The isocyanate index (INDEX) is the value obtained by multiplying the number of moles of the isocyanate component per mole of active hydrogen groups contained in the polyol composition by 100, and is calculated as [(Isocyanate equivalent of isocyanate component / Equivalent of active hydrogen in polyol composition) × 100].

[0037] 3. Method for manufacturing polyurethane foam The method for producing polyurethane foam is not particularly limited. For example, one method for producing polyurethane foam involves mixing the above-mentioned polyol composition (liquid A) with an isocyanate component (liquid B). The method for mixing liquid A and liquid B in the manufacture of polyurethane foam is not particularly limited. For example, liquid A and liquid B can be mixed using a small mixer, or a low-pressure or high-pressure foaming machine for injection foaming, a low-pressure or high-pressure foaming machine for slab foaming, a low-pressure or high-pressure foaming machine for continuous lines, or a spray foaming machine for spray application, which are commonly used when manufacturing polyurethane foam. When foaming and molding polyurethane foam, a predetermined amount of the mixed liquid obtained by mixing liquid A and liquid B should be injected into the mold at a predetermined liquid temperature.

[0038] 4. Polyurethane foam The polyurethane foam is obtained from a reaction liquid set for producing polyurethane foam. The reaction liquid set for producing polyurethane foam may be used for on-site foaming, or may be used when producing polyurethane foam by mixing liquid A and liquid B in a manufacturing factory.

[0039] The polyurethane foam may be any of a flexible polyurethane foam, a semi-rigid polyurethane foam, and a rigid polyurethane foam. From the perspective of heat insulation properties, the polyurethane foam is preferably a rigid polyurethane foam. In the present disclosure, the polyurethane foam includes a polyisocyanurate foam.

[0040] The physical properties of the obtained polyurethane foam can be appropriately set according to the intended use and the like. The polyurethane foam preferably has the following physical properties. (4.1) Apparent overall density The apparent overall density (conforming to JIS K7222:2005) is 20 kg / m 2 , 2 , 2 , , , , , 2 , -120 kg / m 3 is preferable, 25 kg / m <00The physical properties of the obtained polyurethane foam can be appropriately set according to the intended use and the like. The polyurethane foam preferably has the following physical properties. (4.1) Apparent overall density The apparent overall density (conforming to JIS K7222:2005) is 20 kg / m 2 , 2 , 2 , , , , , 2 , -120 kg / m 3 is preferable, 25 kg / m 3 -80 kg / m 3 is more preferable, 30 kg / m 3 -60 kg / m 3 is even more preferable. (4.2) Thermal conductivity The thermal conductivity (conforming to JIS A 1412-2:1999) is preferably 0.030 W / mK or less, more preferably 0.025 W / mK or less, and even more preferably 0.023 W / mK or less. The lower limit value of the thermal conductivity is not particularly limited. The thermal conductivity is usually ≥ 0.018 W / mK. (4.3) Compressive strength The compressive strength (conforming to JIS K7220:2006) is preferably ≥ 5 N / cm 2 or more, more preferably ≥ 7.5 N / cm 2 or more, and even more preferably ≥ 9.5 N / cm 2 The physical properties of the obtained polyurethane foam can be appropriately set according to the intended use and the like. The polyurethane foam preferably has the following physical properties. (4.1) Apparent overall density The apparent overall density (conforming to JIS K7222:2005) is 20 kg / m 2 , 2 , 2 , , , , , <00CO00000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000o000000000000000000000o000000000000000000000000000000000000000000000000000o000000000000 -120 kg / m 3 is preferable, 25 kg / m 3 -80 kg / m 3 is more preferable, 30 kg / m 3 -60 kg / m 3 is even more preferable. (4.2) Thermal conductivity or more. The upper limit value of the compressive strength is not particularly limited. The upper limit value of the compressive strength is usually ≤ 100 N / cm 2 or less. (4.4) Flexural strength The bending strength (according to JIS K 7221-2:2006) is 10 N / cm 2 The above is preferable, 20 N / cm 2 The above is more preferable: 30 N / cm 2 The above is even more preferable. The upper limit of the bending strength is not particularly limited. The upper limit of the bending strength is usually 200 N / cm. 2 The following applies: (4.5) Closed cell ratio Polyurethane foam may have a closed-cell structure or an open-cell structure. When it has a closed-cell structure, the closed-cell ratio (according to ASTM D 2856) is preferably 70% or more, more preferably 80% or more, and even more preferably 85% or more. There is no particular upper limit to the closed-cell ratio, for example, it is 100% or less. The test specimen for measurement was cut from the center (core) of the foam.

[0041] The applications of polyurethane foam are not particularly limited. Because polyurethane foam possesses the physical properties described above, it is effective as an insulating material. In addition, polyurethane foam is suitable as a packaging material, filler, and cushioning material. [Examples]

[0042] 1. Preparation of polyol composition (Solution A) A polyol composition was prepared using the proportions shown in Table 1. Details of each ingredient are as follows: • Polyether polyol 1: A polyether polyol initiated with pentaerythritol, molecular weight 550, hydroxyl value 410 mg KOH / g • Polyether polyol 2: A polyether polyol initiated with sucrose, molecular weight 650, hydroxyl value 450 mg KOH / g • Polyether polyol 3: A polyether polyol initiated with glycerin, molecular weight 1000, hydroxyl value 168 mg KOH / g • Polyether polyol 4: A polyether polyol initiated with toluenediamine, molecular weight 561, hydroxyl value 400 mg KOH / g • Polyether polyol 5: A polyether polyol initiated with toluenediamine, molecular weight 561, hydroxyl value 400 mg KOH / g • Polyester polyol: A polyester polyol using phthalic anhydride and diethylene glycol, molecular weight 360, hydroxyl value 315 mgKOH / g • Flame retardant: Tris(2,3-dichloropropyl)phosphonate • Foam stabilizer 1: Silicone-based surfactant, SZ1677, manufactured by Toray Dow Corning. • Foam stabilizer 2: Silicone-based surfactant, SF2937F, manufactured by Toray Dow Corning. Amine catalyst 1: N,N-dimethylcyclohexylamine • Amine catalyst 2: N,N,N',N'-tetramethylethylenediamine • Amine catalyst 3:1-methylimidazole • Amine catalyst 4: Bis(2-dimethylaminoethyl) ether • Isocyanate trimerization catalyst: N,N',N"-Tris(dimethylaminopropyl)hexahydrotriazine • Cyclopentane (CP) • Hydrohaloolefin: Hydrofluoroolefin HFO-1233zd, Solstice LBA, manufactured by Honeywell. ·water • Urea compound solution: 40% urea aqueous solution In Table 1, the numbers in parentheses in the column for urea compound solutions represent the amounts (parts by mass) of urea and water in the urea solution.

[0043] [Table 1]

[0044] The following raw materials were used as the isocyanate component (Solution B). • Isocyanate components: Polymeric MDI, Foamlite 200B, manufactured by BASF INOAC Polyurethane Corporation.

[0045] Polyurethane foam was obtained by mixing the above polyol composition (Solution A) and the above isocyanate component (Solution B) and free foaming. Solution A and Solution B were mixed in the ratio (Solution A / Solution B, mass ratio) shown in Table 2.

[0046] Free foaming was performed using the following procedure. The polyol composition (Solution A) and the isocyanate component (Solution B) were adjusted to predetermined liquid temperatures. In Example 1 and Comparative Example 1, the liquid temperatures of Solution A and Solution B were adjusted to 25°C. In Examples 2 and 3 and Comparative Examples 2 and 3, the liquid temperatures of Solution A and Solution B were adjusted to 20°C. A plastic box measuring 150mm x 150mm x 200mm was used as a mold for free foaming. A mixture of the polyol composition (Solution A) and the isocyanate component (Solution B) was free-foamed in the mold described above to obtain polyurethane foam. A 100mm x 100mm x 100mm test piece was cut from the obtained polyurethane foam, and its free density was measured.

[0047] The reactivity (cream time, gel time, rise time) between the polyol composition (Solution A) and the isocyanate component (Solution B) was measured using the following method. Cream Time: In the above mixture, the time it took for the liquid to become cloudy and rise to a creamy consistency was measured as the cream time (seconds). Gel time: In the above mixture, the time it took for the mixture to thicken and begin to gel was measured as the gel time (seconds). Rise time: In the above mixture, the time until the foam rise due to effervescence stops was measured as the rise time (seconds). In the above measurements, the time at which mixing of the polyol composition (Solution A) and the isocyanate component (Solution B) began was set as zero seconds. The determination was made by visual inspection.

[0048] Polyurethane foam was obtained by mixing the above polyol composition (Solution A) and the above isocyanate component (Solution B) and molding foaming. Solution A and Solution B were mixed in the ratio (Solution A / Solution B, mass ratio) shown in Table 2. A mold with dimensions of 300 mm × 300 mm × 50 mm was used as the mold for molding foaming.

[0049] [Table 2]

[0050] 2. Evaluation Method (1) Free density, apparent total density The free density of polyurethane foam obtained by free foaming was measured in accordance with JIS K7222:2005. The apparent total density of polyurethane foam obtained by mold foaming was measured in accordance with JIS K7222:2005. (2) Thermal conductivity In accordance with JIS A1412-2:1999, a 300mm x 300mm x 50mm polyurethane foam obtained by mold foaming was cut to a size of 200mm x 200mm x 25mm. Subsequently, the thermal conductivity was measured using a thermal conductivity measuring instrument "AUTO-Λ HC-074" manufactured by Eiko Seiki Co., Ltd. (3) Compression strength The compressive strength of the polyurethane foam obtained by mold foaming was measured in accordance with JIS K7220:2006. (4) Bending strength The flexural strength of the polyurethane foam obtained by mold foaming was measured in accordance with JIS K 7221-2:2006. (5) Closed cell ratio The closed-cell ratio of polyurethane foam obtained by mold foaming was measured in accordance with ASTM D 2856. (6) Burning distance and burning time The burning distance and burning time were measured in accordance with the flammability test specified in JIS A 9521.

[0051] 3. Results The results are shown in Table 2. Examples 1-3 show the results when using a polyol composition containing a urea compound solution. Comparative Examples 1-3 show the results when using a polyol composition without a urea compound solution. When comparing the examples and comparative examples with the same foaming agent formulation, the thermal conductivity of the examples was lower than that of the comparative examples. Specifically, the thermal conductivity of Example 1, which used water as the foaming agent, was 24.31 mW / mK, which was lower than the thermal conductivity of Comparative Example 1, which was 24.58 mW / mK. The thermal conductivity of Example 2, which used cyclopentane and water as the foaming agents, was 20.09 mW / mK, which was lower than the thermal conductivity of Comparative Example 2, which was 20.62 mW / mK. The thermal conductivity of Example 3, which used hydrohaloolefin and water as the foaming agents, was 20.72 mW / mK, which was lower than the thermal conductivity of Comparative Example 3, which was 21.52 mW / mK. Therefore, it was confirmed that the thermal conductivity of polyurethane foam can be reduced by using a polyol composition containing a urea compound solution. Furthermore, when comparing the examples and comparative examples with the same foaming agent formulation, the rise time of the examples was shorter than that of the comparative examples. On the other hand, the cream time of Example 2 was equivalent to that of Comparative Example 2, and although the cream times of Examples 1 and 3 were slightly shorter than those of Comparative Examples 1 and 3, respectively, they were not shortened as much as the rise time. Therefore, it was confirmed that even when a solution of a urea compound is added to the polyol composition, sufficient cream time can be secured for the reaction between the polyol composition and the isocyanate component, thus eliminating problems with injection into the mold and improving moldability.

[0052] According to the above examples, a highly versatile technology that can reduce the thermal conductivity of polyurethane foam can be provided.

[0053] This disclosure is not limited to the embodiments detailed above, and various modifications or changes are possible within the scope of this disclosure.

Claims

1. A polyol composition for the manufacture of polyurethane foam, comprising a polyol, an aqueous urea solution, and a hydrofluoroolefin, A polyol composition for manufacturing polyurethane foam, wherein the urea content is 1.7 parts by mass or more and 8 parts by mass or less per 100 parts by mass of the polyol.

2. A polyol composition for the manufacture of polyurethane foam, comprising a polyol, an aqueous urea solution, and cyclopentane, A polyol composition for manufacturing polyurethane foam, wherein the urea content is 1.7 parts by mass or more and 8 parts by mass or less per 100 parts by mass of the polyol.

3. A polyol composition for manufacturing rigid polyurethane foam, comprising a polyol, an aqueous urea solution, and a hydrohaloolefin, A polyol composition for manufacturing rigid polyurethane foam, wherein the urea content is 1.7 parts by mass or more and 8 parts by mass or less per 100 parts by mass of the polyol.

4. A polyol composition for manufacturing rigid polyurethane foam, comprising a polyol, an aqueous urea solution, and an alkane having 4-8 carbon atoms, A polyol composition for manufacturing rigid polyurethane foam, wherein the urea content is 1.7 parts by mass or more and 8 parts by mass or less per 100 parts by mass of the polyol.

5. A polyol composition for manufacturing rigid polyurethane foam, comprising a polyol and an aqueous urea solution, The urea content is 1.7 parts by mass or more and 8 parts by mass or less per 100 parts by mass of the polyol, in a polyol composition for manufacturing rigid polyurethane foam (excluding those containing plant-derived polyols).

6. A polyol composition for manufacturing a rigid polyurethane foam according to any one of claims 1 to 5, comprising an amine catalyst or an isocyanate trimerization catalyst.

7. A reaction solution set for manufacturing polyurethane foam, comprising a polyol composition for manufacturing polyurethane foam according to any one of claims 1 to 5, and an isocyanate component.

8. A polyurethane foam obtained from the reaction solution set for manufacturing polyurethane foam according to claim 7.

9. A method for producing polyurethane foam, comprising mixing a polyol composition for producing polyurethane foam according to any one of claims 1 to 5 with an isocyanate component.

10. A polyurethane foam obtained from a reaction solution set for manufacturing polyurethane foam, comprising a polyol composition for manufacturing polyurethane foam according to any one of claims 1 to 5, and an isocyanate component containing an aromatic isocyanate, A polyurethane foam that satisfies any of the following conditions (1) to (3). (1) Compressive strength (according to JIS K7220:2006) is 5 N / cm ２ That's all. (2) Bending strength (according to JIS K7221-2:2006) of 10 N / cm ２ That's all. (3) Closed cell ratio (according to ASTM D 2856) is 70% or higher

11. A method for producing polyurethane foam, comprising mixing a polyol composition for producing polyurethane foam according to any one of claims 1 to 5 with an isocyanate component containing an aromatic isocyanate, A method for manufacturing a polyurethane foam, wherein the polyurethane foam satisfies any of the following (1) to (3). (1) Compressive strength (according to JIS K7220:2006) is 5 N / cm ２ That's all. (2) Bending strength (according to JIS K 7221-2:2006) of 10 N / cm ２ That's all. (3) Closed cell ratio (according to ASTM D 2856) is 70% or higher

12. A polyurethane foam obtained from a reaction solution set for manufacturing polyurethane foam, comprising a polyol composition for manufacturing polyurethane foam according to any one of claims 1 to 5 and an isocyanate component, Polyurethane foam with a closed-cell ratio (according to ASTM D 2856) of 70% or more.

13. A method for producing polyurethane foam, comprising mixing a polyol composition for producing polyurethane foam according to any one of claims 1 to 5 with an isocyanate component, A method for manufacturing polyurethane foam having a closed-cell ratio (according to ASTM D 2856) of 70% or more.

Images