Polyol compositions, polyurethanes, and polyurethane foams

Abstract

To provide a polyol composition that is excellent in polyurethane moldability (viscosity rise) and foam stability (increase in cell diameter and antifoaming).SOLUTION: A polyol composition contains: a polyol containing a polyalkylene oxide (A) that contains an alkylene oxide residue having three or more carbon atoms with a number average molecular weight of 800 or more as calculated from hydroxyl values and a degree of unsaturation of 0.010 meq / g or less; and an organometallic compound (B) that is at least one selected from the group consisting of Fe compound, Cu compound, Al compound, Mn compound, Ti compound, and Zr compound with its content being 0.1-1000 ppm. The polyol composition is liquid at room temperature.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to polyol compositions, polyurethanes, and polyurethane foams. [Background technology]

[0002] Polyurethane foam is mainly produced by the reaction of isocyanates and polyols, and is widely used as cushioning material for vehicles and furniture, insulation material and structural material in buildings, storage tanks, ships, etc., as well as automotive interior materials such as steering wheels and shoe soles.

[0003] Examples of polyols used in polyurethane foam include polytetramethylene glycol, polyester polyols, and polyalkylene oxides. Polyurethane foams using polyalkylene oxides, which are produced by addition polymerization of alkylene oxides such as propylene oxide, exhibit excellent hydrolysis resistance, cold resistance, and flexibility.

[0004] The number of air nuclei in the liquid of a polyol composition affects the size of the bubbles during polyurethane foam molding, influencing the physical properties of the urethane foam. When the bubble size becomes finer, the ribs become thinner, which can reduce mechanical properties. However, polyalkylene oxides tend to incorporate many air nuclei and are easily refined, making it difficult to obtain foam with the desired bubble diameter. Furthermore, compared to polytetramethylene glycol, polyester polyols, etc., they are generally liquid and have low viscosity, which can make molding difficult during urethane foam molding due to excessively low viscosity.

[0005] A known method for controlling the liquid properties of polyol compositions involves adding thixotropic agents such as urea derivatives (Patent Document 1). However, this method has drawbacks, such as inhibiting urethane foaming and reducing its mechanical properties and flame retardancy.

[0006] In other words, there was a need for a polyol composition that exhibited excellent polyurethane moldability (increased viscosity) and foaming properties (increased bubble diameter and defoaming), and whose properties were promising for the resulting polyurethane foam. [Patent Document 1] Japanese Patent Publication No. 2015-155486 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The present invention has been made in view of the above-mentioned background art, and its objective is to provide a polyol composition that is excellent in polyurethane moldability (increase in viscosity) and foaming properties (increase in bubble diameter and defoaming). [Means for solving the problem]

[0008] The inventors of the present invention, after diligently studying to solve the above problems, discovered that the above problems can be solved by combining a polyalkylene oxide having a specific degree of unsaturation with a specific organometallic compound-based thickener in a specific ratio, and thus completed the present invention.

[0009] In other words, the present invention relates to the following polyol compositions. [1] A polyol composition comprising a polyalkylene oxide (A) containing an alkylene oxide residue having 3 or more carbon atoms, a number-average molecular weight calculated from the hydroxyl value of 800 or more, and a degree of unsaturation of 0.010 meq / g or less, and one or more organometallic compounds (B) selected from the group consisting of Fe compounds, Cu compounds, Al compounds, Mn compounds, Ti compounds and Zr compounds, wherein the content of organometallic compounds (B) is in the range of 0.1 to 1000 ppm, and the composition is liquid at room temperature. [2] The polyol composition according to [1], wherein the organometallic compound (B) is an Al compound. [3] The polyol composition according to [1] or [2] further comprising a phosphorus compound in the range of 0.1 to 1000 ppm. [4] A polyol composition according to any one of [1] to [3], wherein the haze at a thickness of 100 μm is less than 5%. [5] A polyol composition according to any one of [1] to [4], wherein the number of Gardner colors is in the range of 1 to 3. [6] A polyol composition according to any one of [1] to [5], wherein the number average molecular weight calculated from the hydroxyl value of polyalkylene oxide (A) is in the range of 1,500 to 100,000. [7] A polyol composition according to any one of [1] to [6], wherein the weight ratio of oxyethylene groups and oxypropylene groups in the polyalkylene oxide (A) is in the range of 1:99 to 49:51, and the primary ratio of hydroxyl groups is 40 to 99%. A polyurethane comprising a reaction product of a polyol composition described in any of [8][1] to [7] and an isocyanate compound. Polyurethane foam made of the polyurethane described in [9][8]. [Effects of the Invention]

[0010] One embodiment of the present invention provides a polyol composition that exhibits excellent reactivity, good viscosity for superior handling, excellent polyurethane moldability and foaming properties (increase in bubble diameter and defoaming) during polyurethane foam molding, and is expected to have good mechanical properties. [Modes for carrying out the invention]

[0011] The present invention will be described in detail below.

[0012] A polyol composition according to one aspect of the present invention comprises a polyol containing a polyalkylene oxide (A) having an alkylene oxide residue with 3 or more carbon atoms, a number-average molecular weight calculated from the hydroxyl value of 800 or more, and a degree of unsaturation of 0.010 meq / g or less, and one or more organometallic compounds (B) selected from the group consisting of Fe compounds, Cu compounds, Al compounds, Mn compounds, Ti compounds, and Zr compounds, wherein the content of organometallic compounds (B) is in the range of 0.1 to 1000 ppm.

[0013] <Polyol> The polyalkylene oxide (A) contained in the polyol contains an alkylene oxide residue having 3 or more carbon atoms, has a number average molecular weight calculated from the hydroxyl value of 800 or more, and an unsaturation degree of 0.010 meq / g or less, and is not particularly limited. Examples of the alkylene oxide residue having 3 or more carbon atoms include residues of alkylene oxides having 3 to 12 carbon atoms such as propylene oxide, butylene oxide, and styrene oxide, and contain one or more kinds of alkylene oxide residues. Since the polyol composition is likely to exhibit good foamability and is likely to obtain a polyurethane foam with uniform and good cell diameters, it is preferable to contain a polyalkylene oxide (A) containing an oxyethylene group and an oxypropylene group in the polyol.

[0014] As the polyalkylene oxide (A), for example, it is preferable that one or more active hydrogen-containing compounds R[-H]m are used and an alkylene oxide adduct obtained by adding two or more kinds of 3-membered ring alkylene oxides having 2 to 12 carbon atoms is used, and it is also preferable that it is a polyalkylene oxide represented by the following general formula (1).

[0015] [Chemical formula]

[0016] [In the above general formula (1), R is an m-valent group obtained by removing m active hydrogens from an active hydrogen-containing compound (R[-H] m )), Z is an alkylene group or cycloalkylene group having 2 to 12 carbon atoms, and A is an alkylene group having 3 carbon atoms. When there are a plurality of Z or A, each may be the same or different. m is an integer of 2 to 100, p is an integer of 0 to 500, q is an integer of 1 to 1000, and r is an integer of 1 to 500.] Active hydrogen-containing compound (R[-H] mAlthough it is not particularly limited as long as it has an active hydrogen group, for example, water, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6 - hexanediol, tripropylene glycol, triethylene glycol, bifunctional diols such as polyoxyalkylene diols such as Sannix PP - 200, PP - 400, PP - 600, PP - 1000 manufactured by Sanyo Chemical Industries, bisphenols such as bisphenol A, bisphenol F, bisphenol AD, dihydroxybenzenes such as catechol, resorcinol, hydroquinone, compounds having two active hydrogen groups such as amines such as methylamine, ethylamine, propylamine, butylamine, glycerin, trimethylolpropane, 1,2,6 - hexanetriol, triols such as trifunctional low - molecular - weight polyols such as Sannix GP - 250, GP - 400, GP - 600, GP - 1000 manufactured by Sanyo Chemical Industries, tetraols such as pentaerythritol, diglycerin, hexols, ammonia, amines such as ethanolamine, diethanolamine, triethanolamine and other compounds having three or more active hydrogens can be mentioned. Active hydrogen - containing compound (R[-H] m ) As such, one kind or a mixture of two or more kinds selected from these can be used.

[0017] Active hydrogen - containing compound (R[-H] m ) The alkylene oxide to be added to the active hydrogen - containing compound is not particularly limited as long as it is a compound having one or more epoxy rings in the molecule. For example, alkylene oxides having 2 to 12 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide can be mentioned, and one kind or two or more kinds of alkylene oxides may be used.

[0018] Among these, one kind or two or more kinds of alkylene oxides containing alkylene oxides having 2 to 3 carbon atoms such as propylene oxide and ethylene oxide, which are easily available industrially, are preferable, and two kinds of alkylene oxides, propylene oxide and ethylene oxide, are more preferable.

[0019] In the above general formula (1), the ZO is preferably a polyether structure derived from an alkylene oxide having 2 to 12 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide, or styrene oxide, because it easily exhibits good urethane foam moldability. More preferably, it is a polyether structure derived from one or more alkylene oxides selected from ethylene oxide and propylene oxide, and most preferably, it is a polyether structure selected from ethylene oxide and propylene oxide.

[0020] In the above general formula (1), p is an integer between 0 and 500, preferably an integer between 0 and 100, and more preferably p=0.

[0021] Examples of Z in the above general formula (1) include the structure shown in the following general formula (2).

[0022] [ka]

[0023] [In the above general formula (2), R2, R3, R4, and R5 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. However, the total number of carbon atoms in R2 to R5 cannot exceed 10. Also, any two of R2 to R5 may bond to form a cycloalkyl group.] Furthermore, the AO in the above general formula (1) is preferably a polyether structure derived from a C3 alkylene oxide such as propylene oxide, because it is easy to maintain good viscosity in liquid form and is likely to exhibit a uniform and good bubble diameter when formed into a polyurethane foam.

[0024] Examples of A in the above general formula (1) include the structure shown in the following formula.

[0025] [ka]

[0026] In the above general formula (1), q is an integer between 1 and 1000, preferably between 10 and 500, and more preferably between 15 and 100.

[0027] In the general formula (1) above, r is an integer between 0 and 500. Preferably, r is an integer between 0 and 100 because it is less likely to solidify at low temperatures and has good handling properties, and even more preferably, r is between 1 and 50 because it has good foam-stable and defoam-defoam properties.

[0028] In the general formula (1) above, the relationship between p, q, and r is preferably such that p+q>r (where p+q is 10 to 1000, q is 10 to 1000, and r is 0 or 1 to 100) is satisfied, as this makes it easier to exhibit a uniform and good bubble diameter, prevents the polyurethane from crystallizing easily, and facilitates the development of flexibility at low temperatures. More preferably, p+q>2r (where p+q is 15 to 300, q is 15 to 300, and r is 0 or 1 to 100) is satisfied, and most preferably, 10r>p+q>2r (where p+q is 30 to 150, q is 30 to 150, and r is 5 to 50) is satisfied.

[0029] The weight ratio of oxyethylene groups to oxypropylene groups in polyalkylene oxide (A) is not particularly limited, but is preferably in the range of 1 / 99 to 49 / 51, more preferably in the range of 5 / 95 to 35 / 65, and most preferably in the range of 10 / 90 to 25 / 75. This weight ratio of oxyethylene groups to oxypropylene groups can be determined by the integral ratio of 1H NMR measured by conventional methods.

[0030] The primary ratio of hydroxyl groups in polyalkylene oxide (A) is not particularly limited, but is preferably in the range of 40 to 99%, more preferably in the range of 60 to 95%, and most preferably in the range of 70 to 90%.

[0031] In particular, when using polyols other than polyalkylene oxide (A) in combination at a concentration of 30% by weight or more, it is preferable that the primary ratio be in the range of 75-90%.

[0032] The primary ratio of hydroxyl groups in polyalkylene oxide (A) can be calculated by pretreatment using a conventional method with trifluoroacetic anhydride, etc., and then measuring the integral ratio of 1H NMR using a standard method.

[0033] Two or more types of polyalkylene oxide (A) may be used in combination, in which case a combination of a diol with m=2 and a triol or tetraol with m=3 or 4 is preferred.

[0034] Furthermore, when using two or more types of polyalkylene oxide (A) in combination, it is more preferable that each has the above structure, but it is also suitable to use the polyalkylene oxide (A) with the higher content if its molecular structure has the above structure.

[0035] The degree of unsaturation of polyalkylene oxide (A) is 0.010 meq / g or less. Preferably, it is in the range of 0.0005 to 0.005 meq / g, and most preferably in the range of 0.001 to 0.004 meq / g.

[0036] When using two or more types of polyalkylene oxide (A) in combination, it is preferable that the degree of unsaturation of each is within the above range, but it is also suitable to use the polyalkylene oxide (A) with the higher content if its degree of unsaturation is within the above range.

[0037] When polyalkylene oxide (A) with an unsaturation degree of 0.010 meq / g or less is not used, it contains low molecular weight monools and has a large amount of unsaturated groups. Furthermore, even when organometallic compounds are used, the thickening effect is canceled out, resulting in a decrease in viscosity and a tendency to drip. This makes it difficult to mold and use. In addition, the resulting polyurethane foam tends to have small air bubbles, and has many dangling chains and low molecular weight components derived from the unsaturated structure and monool components, resulting in inferior mechanical properties, flame retardancy, rebound elasticity, and other physical properties, making it difficult to use.

[0038] In this invention, the "degree of unsaturation (meq / g)" of polyalkylene oxide (A) refers to the total amount of unsaturated groups contained per gram of polyol, and refers to the value measured in accordance with the NMR method described in the Journal of Polymer Science, 1993, 50, 2, 121-126, preferably with 500 or more scans. Values ​​measured in accordance with the method specified in JIS K1557 6.7 may not be accurately measured due to impurities. The degree of unsaturation of polyalkylene oxide (A) is an indicator of the amount of monool present in polyalkylene oxide (A), and an increase in this degree of unsaturation leads to an increase in low molecular weight components and a decrease in viscosity. In addition, the average number of functional groups of polyalkylene oxide (A) may decrease, which can lead to a termination reaction when used as a polyurethane raw material, thus reducing the urethane formation reactivity and potentially leading to a decrease in the molecular weight of polyurethane and an increase in uncrosslinked low molecular weight components.

[0039] The number-average molecular weight (M) of the polyalkylene oxide (A) used in the polyol composition of the present invention, calculated from its hydroxyl value, is 800 or more, preferably in the range of 1500 to 100000, more preferably in the range of 1500 to 15000, and most preferably in the range of 2500 to 7500.

[0040] If the number-average molecular weight (M) of the polyalkylene oxide (A) is within the above range, the resulting polyol composition tends to exhibit good viscosity and its reactivity for urethane formation is less likely to decrease, thus easily exhibiting good moldability and urethane properties.

[0041] When using two or more types of polyalkylene oxide (A) in combination, it is preferable that the molecular weights of each are within the above range, but it is also preferable to use the polyalkylene oxide (A) with the higher content if its molecular weight is within the above range.

[0042] In the present invention, the number-average molecular weight (M) calculated from the hydroxyl value of the polyol refers to the value calculated using the following formula (4) based on the hydroxyl value (OHV, in mgKOH / g) of the polyol.

[0043]

number

[0044] Here, "OHV" is the value measured in accordance with JIS K1557 6.4. Furthermore, "number of hydroxyl groups per molecule" refers to the number of active hydrogen atoms per molecule of the active hydrogen-containing initiator used as a raw material in the production of each polyol. If the number of active hydrogen atoms in the initiator cannot be determined for commercially available products, the nominal number of functional groups is used.

[0045] The viscosity of the polyalkylene oxide (A) used as the polyol at 25°C is not particularly limited and can be appropriately selected depending on the application, but is preferably in the range of 0.1 to 2000 Pa·s (25°C), and more preferably in the range of 0.2 to 200 Pa·s (25°C). A viscosity of polyalkylene oxide (A) in the range of 0.1 to 2000 Pa·s (25°C) is preferable because it is easier to mold.

[0046] In this invention, "viscosity" at 25°C refers to the value measured with a cone-plate rotational viscometer as specified in JIS K1557-5 6.2.3. Specifically, it refers to the viscosity at a shear rate of 0.1 (1 / s), but if the viscosity does not fall within the measurement range, the shear rate range may be adjusted within the range of 0.01 to 10 (1 / s) to bring it within the measurement range.

[0047] The molecular weight distribution determined by gel permeation chromatography (GPC) using polystyrene as the polyalkylene oxide (A) as the polyol is preferably 1.039 or less, as this facilitates uniform urethane formation, excellent moldability, and uniform crosslinking of the resulting polyurethane foam, resulting in remarkably good moldability. More preferably, it is in the range of 1.003 to 1.039, even more preferably in the range of 1.005 to 1.029, and most preferably in the range of 1.006 to 1.019.

[0048] Furthermore, when using a combination of a bifunctional polyalkylene oxide (A1) and a trifunctional or more polyalkylene oxide (A2) as polyalkylene oxide (A), it is more preferable that the molecular weight distributions (Mw / Mn) of polyalkylene oxide (A1) and polyalkylene oxide (A2), determined by gel permeation chromatography (GPC) using polystyrene as a standard substance, are within the above range. However, if the molecular weight distribution (Mw / Mn) of the polyalkylene oxide (A) with the higher content is within the above range, it can be suitably used.

[0049] The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) using polystyrene as a standard substance is preferably the molecular weight distribution analyzed by measuring under conditions where four columns packed with a 3 μm particle size packing material are connected in series, a resistance tube is connected to the reference side, and tetrahydrofuran is used as the developing solvent, and the molecular weight distribution (Mw / Mn) is calculated using a cubic approximation curve calibration curve using standard polystyrene.

[0050] There are no particular limitations on the method for producing polyalkylene oxide (A) used as a polyol, but because the urethaneization of the polyol composition proceeds uniformly and moldability is good, it can be produced, for example, by ring-opening polymerization of alkylene oxide in the presence of an active hydrogen-containing compound, a base compound, and a Lewis acid compound.

[0051] In particular, because the urethaneization of the polyol composition proceeds uniformly and moldability is excellent, it is preferable to produce it by ring-opening polymerization of alkylene oxide in the presence of an active hydrogen-containing compound, an iminophosphozenium salt catalyst, and a Lewis acid. More preferably, in order to have a narrower molecular weight distribution and good moldability, it is preferable to reduce impurities that can cause by-products in addition to the above conditions and to carry out the reaction at a low temperature of 110°C or below with a catalyst system that produces by-products with a low boiling point. Most preferably, in addition to the above conditions, by-products are sufficiently removed under reduced pressure and produced by adsorption treatment onto a solid.

[0052] While there are no particular limitations on the iminophosphazenium salt catalyst, it is preferable to use a catalyst system that combines an iminophosphazenium salt and a Lewis acid because alkylene oxides have a wide range of applicability, high polymerization activity, and tend to have a low degree of unsaturation.

[0053] Here, the Lewis acid is not particularly limited, but examples include aluminum compounds, zinc compounds, boron compounds, etc. Among these, organoaluminum, aluminoxane, and organozinc are preferred because they serve as alkylene oxide polymerization catalysts with excellent catalytic performance, and organoaluminum is more preferred.

[0054] Examples of aluminum compounds include organoaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trin-normalhexylaluminum, triethoxyaluminum, triisopropoxyaluminum, triisobutoxyaluminum, triphenylaluminum, diphenylmonoisobutylaluminum, and monophenyldiisobutylaluminum; aluminoxanes such as methylaluminoxane, isobutylaluminoxane, and methyl-isobutylaluminoxane; and inorganic aluminum such as aluminum chloride, aluminum hydroxide, and aluminum oxide.

[0055] Among these, trimethylaluminum, triethylaluminum, triisobutylaluminum, trin-normalhexylaluminum, triethoxyaluminum, and triisopropoxyaluminum are preferred because their by-products have a low boiling point of 100°C or less during catalytic active species preparation, making them easy to remove and suppressing polyalkylene oxides derived from Lewis acids that can broaden the molecular weight distribution. The compounds produced as by-products during catalytic active species preparation can be determined from the structure of the Lewis acid. For example, in the case of trimethylaluminum, it is methane formed by the addition of H to the methyl group of the substituent on the aluminum; in the case of triisobutylaluminum, it is isobutane formed by the addition of H to the isobutyl group of the substituent on the aluminum; and in the case of triisopropoxyaluminum, it is isopropanol formed by the addition of H to the isopropoxy group.

[0056] Examples of zinc compounds include organozincs such as dimethylzinc, diethylzinc, and diphenylzinc; and inorganic zincs such as zinc chloride and zinc oxide.

[0057] Examples of boron compounds include triethylborane, trimethoxyborane, triethoxyborane, triisopropoxyborane, triphenylborane, tris(pentafluorophenyl)borane, and trifluoroborane.

[0058] The iminophosphazenium salt can be any compound having an imino group and a PN bond, and is not particularly limited, but examples include compounds represented by the following general formula (see, for example, Japanese Patent Application Publication No. 2011-132179).

[0059] [ka]

[0060] [In the above general formula (3), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R1 and R2 may be bonded to each other to form a ring structure, or R1s may be bonded to each other, or R2s to each other to form a ring structure. X - This represents a hydroxy anion, an alkoxy anion with 1 to 4 carbon atoms, a carboxy anion, an alkyl carboxy anion with 2 to 5 carbon atoms, or a bicarbonate anion. The ratio of iminophosphazenium salt to Lewis acid is not particularly limited and can be arbitrary as long as it exhibits its function as an alkylene oxide polymerization catalyst, but for example, it is in the range of iminophosphazenium salt:Lewis acid = 1:0.002 to 500 (molar ratio).

[0061] While there are no particular limitations on the polymerization temperature when producing polyalkylene oxides, a range of 70 to 150°C is preferred, more preferably 90 to 130°C, and most preferably 90 to 115°C, because the polyalkylene oxide does not decompose easily, the molecular weight distribution does not spread widely, and catalytic activity is easily exhibited.

[0062] One embodiment of the present invention is a polyol composition characterized by being liquid at room temperature. In this invention, if the polyol precipitates as particulate matter or if particles settle at room temperature, it is considered a solid-liquid mixture and is not included in the invention. If the polyol is dispersed or uniformly dispersed, it is judged to be liquid regardless of its color.

[0063] The viscosity of the polyol composition of the present invention can be appropriately selected depending on the application and is not particularly limited, but is preferably in the range of 0.5 to 10 Pa·s, and more preferably in the range of 0.9 to 5 Pa·s.

[0064] The polyol may, in addition to the polyalkylene oxide (A), include other polyols, without departing from the spirit of the present invention. The other polyols are not particularly limited, but are compounds having one or more hydroxyl groups, and specifically include polyoxytetramethylene glycol, polycarbonate polyols, polyester polyols, Mannich polyols, polyolefin polyols, acrylic polyols, and low molecular weight polyols such as butanediol and 3-methyl-1,5-pentanediol.

[0065] Since the polyol composition readily exhibits good urethane reactivity and good viscosity, it is preferable to use 10% by weight or more of such polyalkylene oxide (A) in the polyol, more preferably 40% by weight or more, and most preferably 97% by weight or more.

[0066] In particular, when forming urethane foam using a polyol composition, it is preferable to include 10% by weight or more of polyalkylene oxide (A), which contains oxyethylene groups in addition to oxypropylene groups, in the polyol. This inhibits crystallization in the urethane foam even when used in combination with crystalline polyols, and significantly improves flexibility at low temperatures. However, when used in ordinary urethane cured products without forming urethane foam, the composition is not particularly limited because it exhibits excellent defoaming properties regardless of whether or not it contains oxyethylene groups in addition to oxypropylene groups.

[0067] <Organometallic compounds (B), other additives> In one aspect of the present invention, a polyol composition must contain one or more organometallic compounds (B) selected from the group consisting of Fe compounds, Cu compounds, Al compounds, Mn compounds, Ti compounds, and Zr compounds in a range of 0.1 to 1000 ppm in order to suppress the refinement of the bubble diameter of the polyurethane foam and to exhibit high mechanical properties.

[0068] By including the above-mentioned organometallic compound in a specific amount in the polyol composition, moldability is improved and bubbles with a good shape can be stably formed.

[0069] In particular, the term refers to compounds that exhibit a clear viscosity-increasing effect on liquid compositions such as polyols, and is preferably an organometallic compound that exhibits a thixotropic effect. Furthermore, these organometallic compounds may react with the polyol in the polyol composition.

[0070] Such organometallic compounds are not particularly limited, but examples include alkylated and alkoxylated forms of the above metal species, chelated forms such as acetylacetonate and ethylacetoacetate, acylated forms such as octylate and stearate, hydroxides, chlorides, brominated forms, and mixtures thereof, among organoaluminum compounds, organotitanium compounds, organozirconium compounds, organozirconium compounds, organozirconium compounds, organozirconium compounds, organozirconium compounds, and the like. Specifically, examples include alkylaluminum, alkoxyaluminum, alkoxytitanium, titanium chelate compounds, titanium acylates, alkoxyzirconium, zirconium chelate compounds, and zirconium acylates. Furthermore, because they readily exhibit thixotropic effects, it is preferable that they are liquid at room temperature or miscible with polyalkylene oxides.

[0071] The thickening effect of the organometallic compound (B) is not particularly limited, but it is preferably a compound that exhibits a thickening effect of 1% or more at a content of 1000 ppm or less relative to polyalkylene oxide (A), more preferably a compound that exhibits a thickening effect of 2 to 15% or more at a content of 1000 ppm or less, and most preferably a compound that exhibits a thickening effect in the range of 4 to 10% at a content of 1000 ppm or less.

[0072] These organometallic compounds react or coordinate with hydroxyl groups at the polyol termini in a polyol composition under conditions with few unsaturated groups, acting as crosslinking agents. This is thought to result in characteristic viscosity increase, and their interaction leads to dissolution and transparency. It is believed that a significant effect is achieved by including them in specific structural combinations and compositional ratios.

[0073] It is preferable that the organometallic compound does not visually precipitate as particles in the polyalkylene oxide (A) within the above content range and can maintain a uniformly dispersed state, and it is preferable that the haze at a thickness of 100 μm is less than 5% when it is used as a polyol composition.

[0074] Furthermore, if a large amount of highly colorable organometallic compounds (such as Fe compounds) is included, the polyol composition becomes heavily colored, which deteriorates the visibility of the solution and the color of the resulting urethane foam. Therefore, it is preferable to include organometallic compounds (B) in an amount such that the Gardner color number is in the range of 1 to 3. In particular, it is even more preferable that the Gardner color number of the polyol composition is in the range of 1 to 2, as this significantly improves the appearance of the resulting urethane foam and enhances its design.

[0075] These organometallic compounds (B) are preferable to be dissolved in the polyol composition, reacting with or coordinating with hydroxyl groups at the polyol termini to act as crosslinking agents, for example, by adding the organometallic compound (B), dissolved or dispersed in a solvent, to polyalkylene oxide (A), followed by desolventring and dehydrating condensation.

[0076] By using the above organometallic compound (B), the resinification reaction and foaming reaction are less likely to be inhibited, viscosity increases, improving moldability and providing excellent foaming properties. As a result, polyurethane foam with good cell diameter and excellent mechanical properties can be obtained.

[0077] Examples of organometallic compounds (B) include organoaluminum compounds, organotitanium compounds, organozirconium compounds, organoiron compounds, organocopper compounds, organomanganese compounds, etc. Specifically, examples include one or more organometallic compounds selected from the group consisting of Fe compounds, Cu compounds, Al compounds, Mn compounds, Ti compounds, and Zr compounds, such as alkoxides, hydroxides, chlorides, brominateds, alkylated compounds, etc. For example, tetraisopropyl titanate, tetran-butyl titanate, butyl titanate dimer, tetraoctyl titanate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, titanium phosphate compounds, titanium octylene glycolate, titanium triethanolamine, n-propyl zirconate, n-butyl zirconate, zirconium tetraacetyl Examples include polyacetate, zirconium monoacetylacetonate, zirconium stearate, aluminum ethylate, aluminum isopropylate, aluminum diisopropylate monosecondary butyrate, aluminum secondary butyrate, aluminum bisethylacetoacetate monosecondary butyrate, aluminum monoacetylacetonate bisoleylacetoacetate, aluminum ethylacetoacetate disecondary butyrate, aluminum ethylacetoacetate diisopropylate, aluminum trisethylacetoacetate, aluminum alkylacetoacetate diisopropylate, aluminum bisethylacetoacetate monoacetylacetonate, and aluminum trisacetylacetonate, iron acetate, and manganese acetate. These organometallic compounds may react with polyols and other components in the polyol composition.

[0078] In particular, it is preferable to include one or more organometallic compounds containing an Al compound, as this tends to result in good bubble diameter and good mechanical properties. Specifically, examples include aluminum ethylate, aluminum isopropylate, aluminum diisopropylate monosecondary butyrate, aluminum secondary butyrate, aluminum bisethyl acetate monosecondary butyrate, aluminum monoacetylacetonate bisoleyl acetate, aluminum ethyl acetate disecondary butyrate, aluminum ethyl acetate diisopropylate, aluminum trisethyl acetate, aluminum alkyl acetate diisopropylate, aluminum bisethyl acetate monoacetylacetonate, and aluminum trisacetylacetonate.

[0079] The above organometallic compound (B) may have altered chemical composition other than metal atoms, such as ligand components, due to urethane formation reactions, as long as it is contained as the corresponding metal atom component. Furthermore, regardless of the state in which the metal component is contained, such as particulate or uniformly dispersed, it is preferable that it does not contain 1% or more by weight of elemental metals or particles with an average particle size of 50 μm or larger, as these may disrupt the bubble structure in the polyurethane foam, and more preferably, it does not contain 0.1% or more by weight.

[0080] The content of organometallic compound (B) is in the range of 0.1 to 1000 ppm in the polyol composition, preferably in the range of 0.5 to 100 ppm, and more preferably in the range of 1 to 50 ppm.

[0081] When the content of organometallic compound (B) is less than 0.1 ppm, the thickening effect is minimal, it does not exhibit good moldability, and it is difficult to use because it cannot suppress the refinement of the bubble size.

[0082] Furthermore, if the concentration exceeds 1000 ppm, it becomes gel-like, making stirring difficult and significantly degrading moldability. It also becomes difficult to suppress particle precipitation, resulting in cloudiness and a lack of significant thickening effect, making it difficult to use. Moreover, it tends to delay the urethane reaction, worsening the productivity of urethane foam, and it is difficult to achieve the desired cell wall density by breaking down the air bubbles, making it difficult to obtain polyurethane foam with good mechanical properties, thus making it difficult to use.

[0083] The content of organometallic compound (B) in the polyol composition may be calculated from the metal content (weight %) of the metal compound used as a raw material and the content of metal atoms determined by analysis of the polyol composition, without taking into account any structural changes of the organometallic compound.

[0084] The organometallic compound (B) in the polyol composition can also be included by leaving behind catalyst residue used in the production of polyol (A).

[0085] Specifically, if Lewis acid catalyst residue precipitates in particulate form, it is difficult to obtain a thickening effect and the mixture tends to become cloudy. Therefore, by using an organometallic Lewis acid catalyst and leaving the Lewis acid catalyst in a specific ratio after polymerization, it is preferable to leave a small amount of Lewis acid catalyst residue in the range of 0.1 to 1000 ppm, which allows for good transparency while acting as a thickener to increase the viscosity of the polyol composition and improve the moldability of the urethane. In particular, it is preferable to contain Lewis acid catalyst residue in the range of 0.5 to 100 ppm, and most preferably in the range of 1 to 50 ppm, as this tends to result in better transparency of the polyol composition. To adjust the content of the organometallic compound, it may be added again after removing the Lewis acid catalyst. Although not particularly limited, when adding organometallic compound (B) after removing the Lewis acid catalyst, it is preferable to crosslink it with the polyol (alkoxide formation) as needed to obtain a similar thickening effect and improve the moldability of the urethane foam.

[0086] On the other hand, when organometallic compounds are used as Lewis acid catalysts, if they remain in concentrations exceeding 1000 ppm, the soluble form tends to undergo crosslinking at low temperatures, forming a gel that is difficult to stir and significantly degrades moldability. Furthermore, particles precipitate, causing turbidity and reducing the viscosity-enhancing effect. Additionally, it promotes foam breakage, making it difficult to achieve a significant improvement in moldability, thus making it difficult to use.

[0087] The polyol composition may contain other additives, and is not particularly limited, but examples of suitable additives include foam stabilizers, viscosity modifiers such as viscosity reducers and viscosity enhancers, urethane catalysts, fillers, flame retardants, antioxidants, UV absorbers, light stabilizers, antifungal agents, antibacterial agents, VOC catchers, mold release agents, foaming agents, and plasticizers.

[0088] The foam stabilizer is not particularly limited, and examples include known surfactants such as nonionic surfactants like organosiloxane-polyoxyalkylene copolymers and silicone-grease copolymers, as well as organosilicone surfactants. However, it is preferable to include one or more phosphorus compounds because it is easier to suppress the refinement of the bubble diameter while maintaining a high degree of foam solidification, and thus easier to improve the mechanical properties of the polyurethane foam.

[0089] Furthermore, in order to suppress the refinement of the air cell diameter of the polyurethane foam and to exhibit high mechanical properties, it is preferable to include the above-mentioned organometallic compound (B) as an essential component, along with a phosphorus compound. The phosphorus compound content is preferably in the range of 0.1 to 1000 ppm in the polyol composition, more preferably in the range of 0.5 to 500 ppm, and most preferably in the range of 1 to 50 ppm.

[0090] As the phosphorus compound, any compound having one or more P atoms in the compound can be preferably used without particular limitation, but an ionic phosphorus compound having a P-N bond is preferable. Particularly, since the suppression effect on the refinement of air bubbles is high and the mechanical properties of the polyurethane foam tend to be improved, a basic ionic phosphorus compound having a P-N bond is preferable, and examples thereof include iminophosphazene derivatives or salts thereof, phosphazene derivatives or salts thereof. As the iminophosphazenium salt, for example, an iminophosphazenium salt compound represented by the following general formula (3) having an imino group and a P-N bond can be mentioned, and it can be most preferably used.

[0091]

Chemical Formula

[0092] [In the above general formula (3), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Note that R1 and R2 may be bonded to each other to form a ring structure, or R1s or R2s may be bonded to each other to form a ring structure. X - represents Cl - , Br - , F - and other halogen anions, hydroxy anions, alkoxy anions having 1 to 4 carbon atoms, carboxy anions, alkyl carboxy anions having 2 to 5 carbon atoms, hydrogen carbonate anions, PO4 3- , HPO4 2- , H2PO4 - , SO4 2- , HSO4 - , NO3 - and other inorganic acid anions.] The phosphorus compound preferably contained in the polyol composition of the present invention is preferably liquid or soluble in the polyol.

[0093] The phosphorus compound can also be contained by leaving the catalyst residue used in the production of the polyol (A).

[0094] Specifically, it is preferable to remove the iminophosphozenium salt catalyst, but it can also be suitably used even if some remains after neutralization or other methods as needed. Adding a phosphorus compound or reacting it with a polyol component after removing the iminophosphozenium salt catalyst is preferable because it easily yields similar effects. In particular, when used for non-foaming applications, bubbles tend to become large, and it is easier to obtain molded products with good moldability (excellent defoaming properties) by having the bubbles disappear during molding. Therefore, it is preferable to leave a small amount of iminophosphozenium salt catalyst or its salt in the range of 0.1 to 1000 ppm, more preferably 0.5 to 500 ppm, and most preferably 5 to 100 ppm.

[0095] On the other hand, concentrations exceeding 1000 ppm are undesirable because they excessively accelerate the urethane reaction, resulting in poor moldability and potentially leading to excessively large air bubbles in the resulting urethane resin, which can degrade its physical properties.

[0096] Other thickening agents that can be used in combination include known thickening agents and rheology control agents. Examples include fine powder thickening agents such as carbon black and fine silica, hydrogenated castor oil wax and fatty acid amide wax, and urea-based rheology control agents such as BYK-410, BYK-415, BYK-420, and BYK-430 manufactured by Bic Chemie. However, these may worsen urethane reactivity and flame retardancy. Therefore, when other thickening agents are included in addition to the organometallic compound (B), their content is preferably less than 25% by weight of the polyol composition, and more preferably in the range of 0.1 to 1000 ppm.

[0097] The antioxidants are not particularly limited, and examples include thioether compounds, phosphorus-based antioxidants, hindered phenol compounds, and other compounds that have the effect of suppressing the oxidation of polymer chains. Trade names include Irganox from Ciba Corporation and Adeka Stab from Adeka Corporation.

[0098] In particular, hindered phenol-based antioxidants are preferred as antioxidants, and it is especially preferable to use one or more antioxidants selected from 2,6-di-t-butyl-4-methylphenol (BHT), IRGANOX-1010, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076, and IRGANOX-1081 manufactured by Ciba Japan, as these provide good antioxidant properties for urethane.

[0099] Suitable urethane catalysts include organometallic catalysts and amine catalysts. Examples include Al compounds, organolead compounds, organotin compounds, bismuth compounds such as bismuth octylate, tertiary amines, and quaternary ammonium salts. Preferably, one or more catalysts selected from organotin compounds and tertiary amine catalysts are used. <Polyurethane> Polyurethane according to one aspect of the present invention is obtained by reacting the above-mentioned polyol composition with a raw material such as polyisocyanate, with the addition of a blowing agent, foam stabilizer, viscosity modifier, urethane catalyst, etc., as needed.

[0100] Furthermore, a polyurethane foam according to one aspect of the present invention is made of the above-mentioned polyurethane, and can form a polyurethane foam with excellent physical properties, as the air cell diameter is less likely to become fine.

[0101] Furthermore, the polyol composition of the present invention exhibits excellent defoaming properties, and by reacting it with raw materials such as polyisocyanate without using a foaming agent, and by adding viscosity modifiers, urethane catalysts, etc. as needed, a polyurethane with a superior appearance can be formed. <Polyisocyanate> The above polyisocyanates are not particularly limited, but are compounds having one or more isocyanate groups per molecule at any location within the molecule. Specifically, these include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tetramethylxylene diisocyanate, 1,6-hexamethylene diisocyanate, and 4,4'-di Examples include cyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, pentamethylene diisocyanate, norbornane diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate-methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, isocyanate-containing prepolymers obtained by reaction of these with polyols, and mixtures of two or more of these. Furthermore, modified isocyanates (for example, modified isocyanurate containing urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, isocyanurate groups, amide groups, imide groups, uretonimine groups, uretdione groups, or oxazolidone groups) and condensates (sometimes called polynuclear compounds) such as polymethylene polyphenylene polyisocyanates (polymeric MDI) are also included.

[0102] In particular, it is preferable to use one or more modified isocyanates selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and modified isocyanates thereof, as this tends to result in good moldability of the resulting polyurethane foam.

[0103] The amount of polyisocyanate used when producing polyurethane is not particularly limited as long as it does not impair the spirit of the present invention, but is preferably in the range of 1 to 200 parts by weight per 100 parts by weight of polyol, more preferably in the range of 10 to 100 parts by weight, and most preferably in the range of 30 to 70 parts by weight. When producing polyurethane, the addition ratio of polyisocyanate is not particularly limited, but it is preferable that the addition amount is in the range of 0.6 to 1.1 (molar ratio) such that the ratio of the total amount of NCO groups in the polyisocyanate (B) to the total amount of OH groups in the active hydrogen-containing compound containing the polyol (referred to as the NCO / OH ratio) is 0.5 to 1.5.

[0104] <Application> The aforementioned polyol composition can be suitably used in various applications where polyurethane is commonly used, such as polyurethane foams including flexible polyurethane foam, semi-rigid polyurethane foam, and rigid polyurethane foam, as well as polyurethane cured products, and in non-urethane applications. While not particularly limited, examples of applications include insulation and structural materials in architecture and civil engineering; insulation for freezers, refrigerators, and refrigerated display cases in electrical equipment; insulation for LPG and LNG tankers and pipelines in plants and ships; insulation for refrigerated storage and vehicles, and instrument panels in vehicles. It is also preferably used in bedding, bicycle saddles, motorcycle seats, automobile seats, cushioning materials, sound-absorbing materials, vibration-damping materials, flooring materials, sports surfaces, racing tracks, floor coverings, balls, steering wheels, headrests, gear lever knobs, armrests, helmet interiors, protector cushioning parts, vehicle cushioning materials, shoe materials such as high heels, sandals, and multi-purpose shoes, sealing materials, waterproof coatings, adhesives, urethane paints, elastomer materials, and surfactants. [Examples]

[0105] The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. The raw materials and evaluation methods used in the following examples and comparative examples are as shown below. (raw materials) <Polyol> The properties of the polyols used in the examples or comparative examples are shown in Tables 1 and 2.

[0106] [Table 1]

[0107] [Table 2]

[0108] Polyols (A1)~(A4): A 40% isopropanol solution with an imino group-containing phosphazenium salt (IPZ) catalyst was added to a bifunctional polyoxypropylene glycol with a molecular weight of 200, and dehydration and solvent removal were carried out under reduced pressure at 110°C for 3 hours. Furthermore, a toluene solution of triisopropoxyaluminum was added, and dehydration and solvent removal were carried out under reduced pressure at 110°C for 3 hours.

[0109] Propylene oxide, which was then treated with a zeolite-based drying agent for more than one day and dried, was polymerized at 105°C and less than 0.3 MPa to remove monomers. Subsequently, ethylene oxide was block copolymerized at 110°C to remove monomers, thereby obtaining polyol (A3).

[0110] The catalyst was removed from polyol (A3) by a conventional method to obtain polyol (A2). The Al content and P component in polyol (A2) were both less than 0.1 ppm.

[0111] Polyol (A3) was subjected to catalyst adsorption treatment by reducing the solid acid content to 1 wt%, and polyol (A1) was obtained by pressure filtration using 0.7 wt% of a filter aid. Polyol (A1) was transparent and contained 8 ppm (Al content 1.1 ppm) of a soluble Al compound that acted as a thickening agent.

[0112] Polyol (A4) was obtained by hydrolysis treatment with water added to polyol (A3) to remove the water. The remaining Al residue in polyol (A4) precipitated in particulate form, and no thickening effect was observed.

[0113] Polyol (A5): A polyalkylene oxide produced by adding propylene oxide and ethylene oxide using a potassium hydroxide catalyst by a conventional method.

[0114] Polyol (A6): A polyalkylene oxide produced by adding propylene oxide and ethylene oxide using only an iminophosphozenium salt catalyst by a conventional method.

[0115] Polyols (A7) and (A8): Polyalkylene oxides produced by the same method as polyol (A2), except that the ratio of propylene oxide to ethylene oxide was changed in a bifunctional polyoxypropylene glycol with a molecular weight of 200. The Al content and P component in polyols (A7) and (A8) were both less than 0.1 ppm.

[0116] Polyol (A9): A polyalkylene oxide produced by the same method as polyol (A3), except that the ratio of propylene oxide and ethylene oxide, and the amount of catalyst, were changed in relation to a bifunctional polyoxypropylene glycol with a molecular weight of 200.

[0117] Polyol (A10): Commercially available polytetramethylene glycol (PTMG-3000, manufactured by Mitsubishi Chemical Corporation).

[0118] Polyol (A11): A polyalkylene oxide produced using the same method as polyol (A2), except that ethylene oxide was not used and the amount of propylene oxide was increased. The Al content and P component in polyol (A11) were both less than 0.1 ppm.

[0119] The polyols mentioned above were heated and vacuum-dehydrated before use.

[0120] Polyols (A1) to (A4) had significantly lower degrees of unsaturation and narrower molecular weight distributions than polyols (A5) and (A6). Polyols (A7) to (A9) also had low degrees of unsaturation and narrower molecular weight distributions.

[0121] <Polyisocyanate> A modified isocyanate obtained by adding PTMG to a partially carbodiimide-modified polyisocyanate (C1):4,4'-diphenylmethane diisocyanate (Millionate MTL, manufactured by Tosoh Corporation) to a concentration of 20 wt%.

[0122] These were used as is, without any purification.

[0123] <Additives> Urethane catalyst: Commercially available tertiary amine catalyst mixture (manufactured by Tosoh Corporation) 1,4-BD:1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) Si foam stabilizer: Commercially available silicone foam stabilizer (manufactured by Toray Dow Corning Co., Ltd.) Rheology control agent: BYK-410 (manufactured by BYK Chemie Co., Ltd.) The above commercially available product was used as is. Deionized water was used as the effervescent agent.

[0124] <Phosphorus compounds>

[0125] [ka]

[0126] [In the above general formula, R1 and R2 are Me groups. X - [is a hydroxyanion] The above iminophosphazene base was neutralized with phosphoric acid before use.

[0127] <Organometallic compound (B)> Commercially available Al(OiPr)3, Fe (OAc) 2. Zr(OBu)4 and Ti(OIPr)3 were dispersed in a solvent and added, then dehydrated and desolvent-removed under reduced pressure to form an alkoxide. (Method for evaluating polyols) <Hydroxyl value, molecular weight> The hydroxyl value (OHV) of the polyol was measured according to the method of JIS-K1557-1. The number-average molecular weight of the polyol was calculated using the above formula (4) based on the hydroxyl value of the polyol.

[0128] <Unsaturation degree> The measurements were performed according to the method described in the Journal of Polymer Science, 1993, 50, 2, 121-126, using nuclear magnetic resonance (NMR) spectroscopy, and confirmed by the method in JIS K1557 6.7. For NMR measurements, deuterated chloroform was used, and the measurement device was a JEOL 400MHz NMR ECZS.

[0129] <Molecular weight distribution (Mw / Mn)> 10 mg of polyol and 10 ml of THF were added to a sample bottle, dissolved by standing overnight, and the sample was obtained by filtering with a PTFE cartridge filter (0.5 μm). As a detector, an RI detector RI8020 was used. As measurement columns, a total of 4 columns, two Tosoh Tskgel SuperH4000 columns filled with a packing material with a particle size of 3 μm and two Tosoh Tskgel SuperH3000 columns, were connected in series. On the reference side, five resistance tubes were connected. Special grade tetrahydrofuran containing a BHT stabilizer manufactured by Wako Pure Chemical Industries, Ltd. was used as the developing solvent. Analysis was performed under the conditions of a flow rate of 0.6 ml / min on the separation column side, a flow rate of 0.15 ml / min on the reference side, and a column temperature of 40°C. Using a third-order approximation curve of eight standard polystyrenes manufactured by Tosoh with known molecular weights as a calibration curve, the molecular weight distribution (Mw / Mn) was analyzed. The measurement device used was a Tosoh HLC-8320GPC, and the analysis used a Tosoh HLC-8320GPC-ECOSEC-WorkStation.

[0130] <EO content (wt%)> Using a nuclear magnetic resonance apparatus (NMR), 1H NMR was measured using deuterated chloroform containing tetramethylsilane as a heavy solvent. The ethylene oxide content in the polyol was calculated from the integral values in the range of 0.8 to 1.5 ppm (propylene oxide chain) and the integral values in the range of 3.2 to 3.9 ppm (propylene oxide chain and ethylene oxide chain).

[0131] <Primary ratio of OH groups> Using a nuclear magnetic resonance apparatus (NMR), 1H NMR of a sample treated with trifluoroacetic anhydride was measured using deuterated chloroform containing tetramethylsilane as a heavy solvent. The primary ratio of the polyol OH groups was calculated from the integral value near 4.3 ppm (methylene to which an ester derived from a primary OH group is bonded) and the integral value near 5.2 ppm (methine to which an ester derived from a secondary OH group is bonded) of the sample treated with trifluoroacetic anhydride.

[0132] <Properties of polyol composition> The properties of the polyol composition were evaluated according to the following criteria.

[0133] ○ (Pass): Haze is less than 5% at a thickness of 100 μm. × (Failure): Haze of 5% or more at a thickness of 100 μm (e.g., cloudy liquid or white solid) (Evaluation of polyol composition foams) <Formability> A polyol premix containing a polyol composition with auxiliary materials other than isocyanate added, and isocyanate were mixed using a disperser at 7000 rpm for 5 seconds. The liquid flowability was then evaluated according to the following criteria when the mixture was poured into the center of a 1.5 m square acrylic box heated to 55°C for 5 seconds.

[0134] ◎ (Pass): The mixed solution is contained within a 0.5m square area, and the maximum height of the foam is 20cm or more. ○ (Pass): The mixed solution is contained within a 1m square area, and the maximum height of the foam is 20cm or more. × (Fail): Anything other than passing (large liquid drip) The liquids marked with ◎ and ○ have good viscosity and do not flow easily, and foam well without flowing during slab foaming, etc., so their foam moldability is judged as ○ (pass). The liquids marked with × have too low viscosity and flow easily, so molding defects such as leakage from gaps and shrinkage are likely to occur during mold foaming, so their foam moldability is judged as × (fail).

[0135] <Foam stability> A polyol premix containing a polyol composition with auxiliary materials other than isocyanate was mixed with isocyanate using a disperser at 7000 rpm for 5 seconds, and the foaming behavior was evaluated according to the following criteria when the mixture was placed in the center of an acrylic box heated to 55°C for 5 seconds.

[0136] ◎ (Pass): The average diameter of the cells at the bottom of the foam is 70-130 μm and the bubbles are visually uniform. ○ (Pass): The average diameter of the cells at the bottom of the foam is 50-70 μm and the bubbles are visually uniform. × (Failure): The average diameter of the cells at the bottom of the form is less than 50 μm or greater than 130 μm, The bubbles in the foam appear uneven to the naked eye. ◎ and ○ indicate that the cell diameter is not refined and the cell structure is uniform, resulting in a thicker rib skeleton of the urethane foam and easier manifestation of mechanical properties. Therefore, the foam structure was judged as ○ (pass). × indicates that the foam is uneven or the cells tend to be fine, making it difficult to manifest mechanical properties and increasing the specific surface area, which makes flame retardancy unpredictable. Therefore, the foam structure was judged as × (fail). (Evaluation of polyol compositions for non-foaming applications) <Moldability> The polyol composition, isocyanate (C1), and 500 ppm of the amine catalyst triethylenediamine were added, mixed, and degassed. The mixture was then applied to a release PET sheet at a coating speed of 2 m / min with a gap of 500 μm using a Baker-type applicator, and the liquid flowability after curing was evaluated using the following indicators.

[0137] ◎ (Pass): Coating thickness exceeds 90% (thickness after curing exceeds 450 μm) ○ (Pass): Coating thickness is 80% to 90% (thickness after curing: 400 to 450 μm) × (Failure): Coating thickness is less than 80% (thickness after curing is less than 400 μm) ◎ and ○ indicate that the coating liquid does not run, making it easy to obtain a cured product of the desired thickness and thus easy to mold, and are therefore judged to have moldability of ○ (pass). × indicates that the coating liquid runs, resulting in large variations in thickness and making it difficult to mold, and are therefore judged to have moldability of × (fail).

[0138] <Defoaming property> The polyol composition, isocyanate (C1), and 500 ppm of triethylenediamine amine catalyst were added, mixed, and degassed. The mixture was then applied to a release PET sheet at a coating speed of 2 m / min with a thickness of 500 μm in the gap of a Baker-type applicator, and the appearance of the cured coating was evaluated using the following indicators.

[0139] ◎ (Pass): No air bubbles are visible in the coating. ○ (Pass): Only a few air bubbles are visible to the naked eye in the coating. × (Failure): The paint film has visible microscopic air bubbles throughout. ◎ indicates that the foam-regulating properties are good because the bubbles generated during application, such as those from moisture in the air, tend to grow larger and disappear easily, resulting in excellent defoaming properties. × indicates that the foam-regulating properties are poor because the generated bubbles remain fine and stable, tending to remain on the paint film. (Evaluation of polyurethane foam properties) The cell structure of the foam was observed using an optical microscope, and the average bubble diameter was calculated.

[0140] <Polyol composition> Polyol compositions were prepared with the compositions shown in Tables 3, 4, and 5. Polyurethane foam was prepared by foaming the polyol compositions with the compositions shown in Tables 3 and 4, along with water, isocyanate (C1), a Si foam stabilizer, and a urethane catalyst. The foam's moldability was evaluated as liquid flowability, and its foaming properties as cell diameter and cell structure.

[0141] [Table 3]

[0142] [Table 4]

[0143] [Table 5]

[0144] Example 1 The viscosity of polyol (A1), i.e., polyol (A1) composition with a small amount of residual Al compound, was measured at 25°C. The properties were evaluated by measuring the haze of the polyol (A1) composition when it was spread to a thickness of 100 μm. The haze of the polyol composition was less than 5%, no cloudy components or solid matter were observed, and it showed a remarkable thickening effect of 8.6% compared to polyol (A2), from which the Al compound had been removed to less than 0.1 ppm.

[0145] A polyol premix was prepared by adding 100 parts of polyol (A1) composition, 1 part of a commercially available silicone foam stabilizer (manufactured by Toray Dow Corning), 1.7 parts of water as a foaming agent, and 0.8 parts of a tertiary amine catalyst mixture as a urethane catalyst, and mixing them at 2000 rpm for 10 minutes using a tabletop disperser.

[0146] Isocyanate (C1), heated to 45°C, was mixed and stirred with a polyol premix at a tabletop mixer at a rotation speed of 7000 rpm to achieve an NCO index of 90. After applying a release agent, the mixture was placed in a dried acrylic box and allowed to foam freely.

[0147] The mixed liquid that was added remained within a 1m square area, foamed to a good height of 20cm or more, and exhibited good foam moldability. The resulting urethane foam had a bubble diameter of 50μm or more, and showed good foam structure without becoming extremely fine.

[0148] Example 2 The polyol (A1) composition was prepared using the same method as in Example 1, except that an Al(OiPr)3 / hexane solution and an isopropanol solution of an iminophosphazene base phosphate were separately added to the polyol (A1) composition to obtain the composition shown in Table 3, and then dehydrated and desolvated under heating and reduced pressure to obtain the polyol composition. Its properties, foam moldability, and foam stability were then evaluated.

[0149] The polyol composition of Example 2 thickened even more effectively than polyol (A1), and the resulting mixture foamed to a good height of over 20 cm without dripping, demonstrating excellent foam moldability. Furthermore, the resulting urethane foam had a bubble diameter of 70 μm or more, showing good foam-stable properties without becoming fine, which was a better result than in Example 1.

[0150] Example 3 The preparation was carried out using the same method as in Example 2, except that polyol (A2) was used and an isopropanol solution of iminophosphazene base phosphate was not added. The properties, foam moldability, and foam stability were then evaluated.

[0151] The mixture obtained using the polyol composition of Example 3 did not drip and foamed to a good height of 20 cm or more, showing good foam moldability. The resulting urethane foam also had a bubble diameter of 50 μm or more, showing good foaming properties without becoming extremely fine. However, because it did not contain phosphorus compounds, the bubble diameter was finer than that of Example 2.

[0152] Examples 4-5 The preparation was carried out in the same manner as in Example 3, except that an isopropanol solution of iminophosphazene base phosphate was added, and its properties, foam moldability, and foam-forming properties were evaluated. The mixture obtained using the polyol composition of Example 4 did not drip and foamed to a good height of 20 cm or more, showing good foam moldability. The resulting urethane foam also had a bubble diameter of 50 μm or more, and was not nearly fine, showing good foam-stable properties. Example 6 The preparation was carried out in the same manner as in Examples 4 and 5, except that the amounts of Al(OiPr)3 / hexane solution and isopropanol solution of iminophosphazene base phosphate were both increased, and the properties, foam moldability, and foam stability were evaluated.

[0153] The polyol composition was transparent and liquid, and its viscosity increased, although a slight gel-like substance was observed.

[0154] The mixed liquid that was added remained within a 1m square area, foamed to a good height of 20cm or more, and exhibited good foam moldability. The resulting urethane foam had a bubble diameter of 50μm or more, and showed good foam structure without becoming extremely fine.

[0155] Comparative Example 1 The preparation was carried out in the same manner as in Examples 4-5, except that a polyol (A2) that does not contain the reaction product of Al(OiPr)3 and polyol, and a polyol (A2) that does not contain an iminophosphazenium salt structure as the Al compound, and neither an Al(OiPr)3 / hexane solution nor an isopropanol solution of an iminophosphazene base phosphate was added. The properties, foam moldability, and foam stability were then evaluated.

[0156] Polyol (A2) does not contain organometallic compounds and has low viscosity, so it could not be expected to suppress foam molding properties or the refinement of bubbles by suppressing liquid flow.

[0157] The mixed liquid that was added was prone to flowing and had poor moldability. The air bubbles were also very small, less than 50 μm in size, and therefore could not be expected to exhibit desirable physical properties such as flame retardancy or mechanical properties (mainly tensile strength).

[0158] Comparative Example 2 The preparation was carried out using the same method as in Comparative Example 1, except that an Al(OiPr)3 / hexane solution was added as an organometallic compound to an Al(OiPr)3 content of 1200 ppm, followed by dehydration and desolvation under reduced pressure. The properties, foam moldability, and foam-stable properties were then evaluated.

[0159] The resulting polyol composition had such a high viscosity that it was difficult to measure, likely due to gelation caused by excessive crosslinking of the polyol termini in the Al component.

[0160] Furthermore, the polyol premix and isocyanate components did not mix uniformly, making it difficult to pour into the acrylic box and resulting in poor foam molding properties.

[0161] Furthermore, the resulting urethane foam had an uneven cellular structure with bubbles exceeding 130 μm, making it difficult to suppress the refinement of the bubbles and resulting in poor foam structure. Therefore, it could not be expected to have good mechanical properties.

[0162] Comparative Example 3 The following polyols were prepared using the same method as in Example 1, except that instead of polyol (A1), a polyol (A3) composition was used, which contained a large amount of Al(OiPr)3 and a polyol (or its reaction product) as the Al compound without removing the catalyst at all, and a large amount of an iminophosphozenium salt structure as the phosphorus compound. The properties, foam moldability, and foam stability were then evaluated.

[0163] The resulting polyol composition had such a high viscosity that it was difficult to measure, likely due to gelation caused by excessive crosslinking of the polyol termini in the Al component.

[0164] Furthermore, the polyol premix and isocyanate components did not mix uniformly, making it difficult to pour into the acrylic box and resulting in poor foam molding properties.

[0165] Furthermore, the resulting urethane foam had an uneven cellular structure with bubbles exceeding 200 μm, making it difficult to suppress the refinement of the bubbles and resulting in poor foam structure. Therefore, it could not be expected to have good mechanical properties.

[0166] Comparative Example 4 Polyol (A4) was obtained by hydrolysis treatment with water added to polyol (A3) and removing the water. The Al residue precipitated in particulate form and no thickening effect was observed. Except for using polyol (A4), the preparation was carried out in the same manner as in Comparative Example 1, and its properties, foam moldability, and foam-forming properties were evaluated.

[0167] Because the Al component precipitated in particulate form, gelation did not occur, but no thickening effect was observed, resulting in low viscosity. Therefore, it could not be expected to suppress liquid flow, thus improving foam moldability or inhibiting the miniaturization of air bubbles.

[0168] Furthermore, due to its low viscosity, the liquid flows during foam molding, resulting in an uneven bubble structure, making it unsuitable for achieving desirable mechanical properties.

[0169] Comparative Example 5 Except for changing the polyol from (A2) to a polyol with a higher degree of unsaturation (A5), a polyol composition free of Al compounds and phosphorus compounds was prepared using the same method as in Comparative Example 1, and its properties, foam moldability, and foam-stable properties were evaluated.

[0170] Polyol (A5) has low viscosity, and therefore cannot be expected to suppress foam molding or the miniaturization of air bubbles by suppressing liquid flow.

[0171] The mixed liquid that was added had low viscosity, causing it to flow and resulting in poor moldability. Furthermore, the air bubbles were very small, less than 50 μm in size, making it unsuitable for flame retardancy or mechanical properties (mainly tensile strength).

[0172] Comparative Example 6 The preparation was carried out in the same manner as in Example 4, except that the polyol used was a polyol with a high degree of unsaturation (A5) from (A2), and its properties, foam moldability, and foam-stable properties were evaluated.

[0173] Although its viscosity was slightly higher than that of Comparative Example 5, it was still low viscosity, and therefore could not be expected to suppress foam molding properties or the miniaturization of air bubbles by suppressing liquid flow.

[0174] The mixed liquid that was added was prone to flowing and had poor moldability. The air bubbles were also very small, less than 50 μm in size, and therefore could not be expected to have flame retardancy or mechanical properties (mainly tensile strength).

[0175] Comparative Examples 7-8 Except for using polyol (A6) with a reduced degree of unsaturation to 0.032 instead of polyol (A2) to obtain the composition shown in Table 3, the preparation was carried out in the same manner as in Examples 3, 4, and 5, and its properties, foam moldability, and foam-stable properties were evaluated.

[0176] The polyol still had a high degree of unsaturation and low viscosity, making it impossible to expect improved foam moldability or reduced bubble density by suppressing liquid flow.

[0177] The mixed liquid that was added was prone to flowing and had poor moldability. The air bubbles were also very small, less than 50 μm in size, and therefore could not be expected to have flame retardancy or mechanical properties (mainly tensile strength).

[0178] Examples 7-9 A polyol (A7) with a remarkably low degree of unsaturation and a molecular weight of 3000 was used as the polyol, and the composition was adjusted to match that shown in Table 4. The preparation was carried out in the same manner as in Example 2, and its properties, foam moldability, and foam-stable properties were evaluated.

[0179] The polyol compositions of Examples 7, 8, and 9 thickened well compared to polyol (A7), and the mixtures using them foamed to a good height of 20 cm or more without dripping, showing good foam moldability. Furthermore, the bubble diameter of the resulting urethane foam was 70 μm or more in Example 7 and 50 μm or more in Examples 8 and 9, showing good foam-stable properties without becoming finely divided.

[0180] Examples 10-12 A polyol (A8) with a remarkably low degree of unsaturation and a molecular weight of 7000 was used as the polyol, and the composition was adjusted to match that shown in Table 4. The preparation was carried out in the same manner as in Example 7, and its properties, foam moldability, and foam-stable properties were evaluated.

[0181] The polyol compositions of Examples 10, 11, and 12 thickened well compared to polyol (A8), and the mixtures using them foamed to a good height of 20 cm or more without dripping, showing good foam moldability. Furthermore, the resulting urethane foam had a bubble diameter of 70 μm or more, showing good foam-stable properties without becoming finely divided.

[0182] Comparative Example 9 The preparation was carried out in the same manner as in Examples 7-9, except that a polyol (A7) was used as the Al compound, which does not contain the reaction product of Al(OiPr)3 and polyol, and a polyol (A7) that does not contain an iminophosphazenium salt structure as the phosphorus compound, and neither an Al(OiPr)3 / hexane solution nor an isopropanol solution of an iminophosphazene base phosphate was added. The properties, foam moldability, and foam stability were then evaluated.

[0183] Polyol (A7) has low viscosity, and therefore cannot be expected to suppress foam molding properties or the miniaturization of air bubbles by suppressing liquid flow.

[0184] The mixed liquid that was added was prone to flowing and had poor moldability. The air bubbles were also very small, less than 50 μm in size, and therefore could not be expected to have flame retardancy or mechanical properties (mainly tensile strength).

[0185] Comparative Example 10 The preparation was carried out in the same manner as in Example 10, except that an Al(OiPr)3 / hexane solution was added as an organometallic compound to an Al(OiPr)3 content of 1100 ppm, followed by dehydration and solvent removal under reduced pressure to form an alkoxide. The properties, foam moldability, and foam-stable properties were then evaluated.

[0186] The resulting polyol composition had such a high viscosity that it was difficult to measure, likely due to gelation caused by excessive crosslinking of the polyol termini in the Al component.

[0187] Furthermore, the polyol premix and isocyanate components did not mix uniformly, making it difficult to pour into the acrylic box and resulting in poor foam molding properties.

[0188] Furthermore, the resulting urethane foam had an uneven cellular structure with bubbles exceeding 130 μm, making it difficult to suppress the refinement of the bubbles and resulting in poor foam structure. Therefore, it could not be expected to have good mechanical properties.

[0189] Comparative Example 11 A polyol (A8) was used as the Al compound, which does not contain the reaction product of Al(OiPr)3 and polyol, and as the phosphorus compound, it does not contain an iminophosphazenium salt structure. The preparation was carried out in the same manner as in Example 10, except that neither an Al(OiPr)3 / hexane solution nor an isopropanol solution of an iminophosphazene base phosphate was added. The properties, foam moldability, and foam-stable properties were evaluated.

[0190] Polyol (A8) had a lower viscosity compared to Examples 10 and 11, and therefore could not be expected to suppress foam molding properties or the refinement of air bubbles by suppressing liquid flow.

[0191] The mixed liquid that was added was prone to flowing and had poor moldability. The air bubbles were also very small, less than 50 μm in size, and therefore could not be expected to have flame retardancy or mechanical properties (mainly tensile strength).

[0192] Comparative Example 12 The preparation was carried out in the same manner as in Comparative Example 3, except that the catalyst was not removed and a polyol (A9) composition containing more than 1000 ppm each of the reaction products of Al(OiPr)3 and polyol as Al compounds, and an iminophosphozenium salt structure as the phosphorus compound was used. The properties, foam moldability, and foam stability were then evaluated.

[0193] The resulting polyol composition had such a high viscosity that it was difficult to measure, likely due to gelation caused by excessive crosslinking of the polyol termini in the Al component.

[0194] Furthermore, the polyol premix and isocyanate components did not mix uniformly, making it difficult to pour into the acrylic box and resulting in poor foam molding properties.

[0195] Furthermore, the resulting urethane foam had an uneven cellular structure with bubbles exceeding 200 μm, making it difficult to suppress the refinement of the bubbles and resulting in poor foam structure. Therefore, it could not be expected to have good mechanical properties.

[0196] Reference example 1 The composition was prepared in the same manner as in Example 1, except that commercially available polytetramethylene glycol was used. The composition showed good viscosity of 2840 mPa·s at 40°C, did not flow, had good foam moldability, and no micronization of bubbles was observed. However, polytetramethylene glycol is a white, waxy solid at room temperature, and the composition has significantly poor handling properties at room temperature, making it difficult to use at room temperature and thus difficult to use depending on the application.

[0197] Examples 13-15 The polyol composition was prepared in the same manner as in Example 2, except that Zr, Ti, and Fe compounds were used as organometallic compounds to obtain the composition shown in Table 5, and an isopropanol solution of iminophosphazene base phosphate was separately added to polyol (A2), followed by dehydration and desolvation under reduced pressure and alkoxide formation. The properties, foam moldability, and foam stability were then evaluated.

[0198] The polyol compositions of Examples 13-15 thickened well compared to polyol (A2), and the mixtures using them foamed to a good height of 20 cm or more without dripping, showing good foam moldability. Furthermore, the resulting urethane foam had a bubble diameter of 70 μm or more, showing good foam-stable properties without becoming fine, which was a better result than Comparative Example 1.

[0199] Comparative Example 13 The same method as in Example 14 was used to prepare the product, except that a Ti compound was added as an organometallic compound to a concentration of 3200 ppm. The properties, foam moldability, and foam-stable properties were then evaluated.

[0200] The resulting polyol composition had such a high viscosity due to gelation that it was difficult to measure.

[0201] Furthermore, the polyol premix and isocyanate components did not mix uniformly, making it difficult to pour into the acrylic box and resulting in poor foam molding properties.

[0202] Furthermore, the resulting urethane foam had an uneven cellular structure with bubbles exceeding 130 μm, making it difficult to suppress the refinement of the bubbles and resulting in poor foam structure. Therefore, it could not be expected to have good mechanical properties.

[0203] Comparative Example 14 The preparation was carried out in the same manner as in Example 13, except that solid iron powder was added as a metal component, and its properties, foam moldability, and foam stability were evaluated.

[0204] Because the metal components precipitated in particulate form, no thickening effect was observed, resulting in low viscosity. Consequently, it could not be expected to suppress liquid flow, thus improving foam moldability or inhibiting the miniaturization of air bubbles.

[0205] Furthermore, due to its low viscosity, the liquid flows during foam molding, resulting in an uneven bubble structure, making it unsuitable for achieving desirable mechanical properties.

[0206] Comparative Example 15 The preparation was carried out in the same manner as in Example 2, except that BYK-410 (manufactured by BYC Chemie), a urea derivative-based nonmetallic rheology control agent, was added as a thickening agent instead of an organometallic compound. The properties, foam moldability, and foam stability were then evaluated.

[0207] At a thickening agent concentration of 100 ppm, no thickening effect was observed, resulting in low viscosity. Therefore, it could not be expected to improve foam moldability by suppressing liquid flow or inhibit the miniaturization of air bubbles.

[0208] Furthermore, due to its low viscosity, the liquid flowed during foam molding, and the resulting bubbles were very small, making it unsuitable for mechanical properties. Additionally, because this rheology control agent is an organic compound, it could not be expected to exhibit flame retardancy.

[0209] Non-foaming urethane cured products were prepared using polyol compositions and isocyanate (C1) with the compositions shown in Table 6, and their moldability (liquid dripping) and foaming / defoaming properties (surface appearance) were evaluated.

[0210] [Table 6]

[0211] Example 16 A polyol composition was obtained by separately adding Al(OiPr)3 / hexane solution and an isopropanol solution of iminophosphazene base phosphate to polyol (A7) to achieve the composition shown in Table 6, followed by dehydration and desolvation under reduced pressure, and subsequent alkoxide formation.

[0212] A polyol composition, isocyanate (C1), and 500 ppm of triethylenediamine amine catalyst were added, mixed, and degassed. The mixture was then applied to a release PET sheet with a thickness of 500 μm in the gap of a Baker-type applicator at a coating speed of 2 m / min. After curing, the moldability (thickness) and film appearance (foaming and defoaming properties) were evaluated.

[0213] The polyol composition of Example 16 had high viscosity, and the urethane cured product obtained using it had a thickness of 450 μm or more, showed no shrinkage, exhibited excellent moldability, had a good coating appearance, and had excellent defoaming properties.

[0214] Example 17 A polyol composition was obtained by using polyol (A11), adding Al(OiPr)3 / hexane solution and an isopropanol solution of iminophosphazene base phosphate separately to obtain the composition shown in Table 6, and then performing vacuum dehydration and solvent removal to alkoxide formation, except that the method was the same as in Example 16. The properties, moldability, foaming and defoaming properties were then evaluated.

[0215] The polyol composition of Example 17 had high viscosity, and the urethane cured product using it had a thickness of 450 μm or more, showed no shrinkage, exhibited excellent moldability, had a good coating appearance, and had excellent defoaming properties.

[0216] Example 18 The polyol composition prepared in Example 17 and polyol (A10) were mixed and heated to dissolve in a weight ratio of 90:10 to prepare a polyol composition, and its properties, moldability, and foaming and defoaming properties were evaluated. The polyol composition of Example 18 was liquid and had high viscosity, and the urethane cured product using it was 450 μm or more in thickness, showed no shrinkage, had excellent moldability, had a good coating appearance, and exhibited excellent defoaming properties.

[0217] Comparative Example 1 6 A polyol (A7) that does not contain Al compounds or phosphorus compounds was used, and the same method as in Example 16 was used, except that Al(OiPr)3 / hexane solution and iminophosphozenium salt were not added as Al compounds and phosphorus compounds. The properties, moldability, and foaming and defoaming properties were then evaluated.

[0218] Comparative Example 1 6 The polyol composition had low viscosity, and the urethane cured product using it was less than 400 μm thick, exhibiting shrinkage and poor moldability. The coating also had a poor appearance with many fine bubbles and poor foaming and defoaming properties.

[0219] Comparative Example 1 7 A polyol (A11) that does not contain Al compounds or phosphorus compounds was used, and the same method as in Example 17 was used, except that Al(OiPr)3 / hexane solution and iminophosphozenium salt were not added as Al compounds and phosphorus compounds. The properties, moldability, and foam-stable / defoam-defoam-resistance were then evaluated.

[0220] Comparative Example 1 7 The polyol composition had low viscosity, and the urethane cured product using it was less than 400 μm thick, exhibiting shrinkage and poor moldability. The coating also had a poor appearance with many fine bubbles and poor foaming and defoaming properties.

Claims

1. A polyol containing a polyalkylene oxide (A) having a three-membered ring alkylene oxide residue with three or more carbon atoms, a number-average molecular weight of 800 or more calculated from the hydroxyl value, and a degree of unsaturation in the range of 0.001 to 0.004 meq / g, and one or more organometallic compounds (B) selected from the group consisting of alkoxyaluminum, alkoxyzirconium, alkoxytitanium, and iron acetate, wherein the content of organometallic compound (B) is in the range of 0.5 to 50 ppm. It contains phosphorus compounds in the range of 0.1 to 1000 ppm. A polyol composition in which the weight ratio of oxyethylene groups to oxypropylene groups in polyalkylene oxide (A) is in the range of 1:99 to 49:51, the primary proportion of hydroxyl groups is 40 to 99%, and it is liquid at room temperature.

2. The polyol composition according to claim 1, wherein the organometallic compound (B) is alkoxyaluminum.

3. The polyol composition according to claim 1 or 2, wherein the haze at a thickness of 100 μm is less than 5%.

4. A polyol composition according to any one of claims 1 to 3, wherein the Gardner color number is in the range of 1 to 3.

5. A polyol composition according to any one of claims 1 to 4, wherein the number average molecular weight calculated from the hydroxyl value of polyalkylene oxide (A) is in the range of 1,500 to 100,000.

6. A polyurethane comprising a reaction product of a polyol composition according to any one of claims 1 to 5 and an isocyanate compound.

7. A polyurethane foam made of the polyurethane described in claim 6.

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