Polyol composition, urethane resin composition, and polyurethane foam

Abstract

To provide a polyol composition that prevents explosive boiling even when the polyol composition is stirred in a state where a low-boiling foamer is contained in the polyol composition.SOLUTION: A polyol composition contains a polyol, a foamer, a filler, and alcohol A, the foamer containing a compound with a boiling point of 40°C or lower. The alcohol group A has a carbon number of 5-24 and contains one hydroxy group or two or more hydroxy groups bound to different carbon atoms respectively.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyol composition, a urethane resin composition, and a polyurethane foam.

Background Art

[0002] Polyurethane foam is used as a heat insulating material for buildings such as condominiums, single-family houses, various facilities in schools, and commercial buildings because of its excellent heat insulating property and adhesiveness. Polyurethane foam is obtained by mixing a polyol composition and an isocyanate and foaming them, and spraying them onto an object such as a ceiling, wall, or roof using a spraying device or the like. Since such polyurethane foam is used in buildings, it is required to have flame retardancy in order to prevent the spread of fire in case of a fire.

[0003] As a polyol composition for obtaining such polyurethane foam, for example, as described in Patent Documents 1 and 2, a polyol composition containing a foaming agent, a catalyst, and a flame retardant is known, and such a polyol composition may contain HFO as a foaming agent and a filler as a flame retardant, respectively.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

特許文献2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, these conventional polyol compositions require stirring before foaming because the fillers may precipitate or aggregate during storage. Furthermore, when HFO is used as a foaming agent, its low boiling point can cause the foaming agent to vaporize during stirring, potentially leading to the composition boiling up and degrading its handling properties and performance as a raw material for polyurethane foam.

[0006] Therefore, the object of the present invention is to provide a polyol composition that can suppress bumping even when the polyol composition is stirred while containing a low-boiling-point blowing agent. [Means for solving the problem]

[0007] As a result of diligent research, the inventors have found a solution to the above problem in a polyol composition containing a polyol, a foaming agent, a filler, and alcohol A, wherein the foaming agent contains a compound with a boiling point of 40°C or lower, and alcohol A has 5 to 24 carbon atoms and has one hydroxyl group, or two or more hydroxyl groups on different carbon atoms.

[0008] The present invention is summarized in the following [1] to

[10] . [1] A polyol composition comprising a polyol, a blowing agent, a filler, and alcohol A, wherein the blowing agent comprises a compound with a boiling point of 40°C or less, and alcohol A has 5 to 24 carbon atoms and has one hydroxyl group or two or more hydroxyl groups bonded to different carbon atoms. [2] The polyol composition according to [1], wherein the partition coefficient of alcohol A is -0.8 or greater. [3] The polyol composition according to [1] or [2], wherein the alcohol A has two hydroxyl groups. [4] The polyol composition according to any one of [1] to [3], wherein the alcohol A comprises dipropylene glycol. [5] The polyol composition according to [4], wherein the content of the dipropylene glycol is 0.5% by mass or more on a basis of the total amount of the polyol composition. [6] The polyol composition according to any one of [1] to [5], wherein the polyol composition contains a catalyst, the catalyst contains a metal salt of a carboxylic acid, and the metal component of the metal salt is one selected from the group consisting of bismuth, lead, tin, and zinc. [7] The polyol composition according to any one of [1] to [6], wherein the compound with a boiling point of 40°C or less is a hydrofluoroolefin. A urethane resin composition obtained by mixing a polyol composition described in any one of items [8][1] to [7] with a polyisocyanate. [9] The urethane resin composition described in [8], used for spray application at construction sites of buildings. A polyurethane foam formed from the urethane resin composition described in

[10] [8] or [9]. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a polyol composition that can suppress bumping even when the polyol composition is stirred while containing a low-boiling point blowing agent. [Modes for carrying out the invention]

[0010] [Polyol composition] The polyol composition of the present invention contains a polyol, a foaming agent, a filler, and alcohol A.

[0011] <Alcohol A> The polyol composition of the present invention contains alcohol A. Alcohol A has 5 to 24 carbon atoms and has one hydroxyl group or two or more hydroxyl groups bonded to different carbon atoms. Alcohol A, having the specific structure described above, has improved hydrophobicity and functions as a compatibilizer. Therefore, even if the blowing agent has a low boiling point, the compatibility of the blowing agent with the polyol composition is improved, and bumping of the polyol composition during stirring can be suppressed. On the other hand, if the number of carbon atoms in alcohol A is less than 5, the hydrophobicity of alcohol A is not sufficiently improved, and therefore the compatibility of the blowing agent with the polyol composition is not sufficiently improved, which may prevent the suppression of bumping of the polyol composition. Furthermore, if the number of carbon atoms in compound A exceeds 24, alcohol A becomes a long chain, which impairs the foaming performance (reactivity between the polyol and polyisocyanate). Considering these points, it is preferable that the number of carbon atoms in alcohol A is 6 or more. On the other hand, the upper limit of the number of carbon atoms in alcohol A is preferably 16 or less, more preferably 15 or less, and even more preferably 10 or less.

[0012] Examples of alcohol A compounds having one hydroxyl group include polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, 1-pentanol, 2-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, cyclopentanol, 1-hexanol, 2-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, octyl alcohol, decyl alcohol, and stearyl alcohol.

[0013] Furthermore, examples of alcohol A compounds having two hydroxyl groups include dipropylene glycol (DPG), 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, cis-1,2-cyclopentanediol, trans-1,2-cyclopentanediol, 1,2-hexanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,3-butanediol, and 2-methyl-2,4-pentanediol.

[0014] The structure of alcohol A other than the hydroxyl group may consist of a hydrocarbon group, or a combination of a hydrocarbon group and an ether bond. The hydrocarbon group may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group, but it is preferable that it be an aliphatic group. If the hydrocarbon group is an aliphatic group, it may be a saturated aliphatic group or an unsaturated aliphatic group. The structure of these aliphatic groups may be a linear structure, a branched structure, a cyclic structure, or a combination of two or more selected from linear, branched, and cyclic structures. In the present invention, the hydrocarbon group constituting alcohol A is more preferably a saturated aliphatic group, and even more preferably a linear saturated aliphatic group, from the viewpoint of increasing the compatibility of the foaming agent with the polyol composition and effectively suppressing bumping of the polyol composition. Furthermore, the position of the hydroxyl group in alcohol A is not particularly limited, and alcohol A may be a primary, secondary, or tertiary alcohol. However, from the viewpoint of improving hydrophobicity and suppressing bumping of the polyol composition while ensuring the reactivity of the polyol and polyisocyanate, a primary or secondary alcohol is preferred. Generally, the lower the classification of alcohol A, the better the reactivity of the polyol and polyisocyanate can be ensured.

[0015] In the present invention, the alcohol A used preferably has a partition coefficient of -0.8 or higher, and more preferably -0.5 or higher. Generally, the higher the partition coefficient of alcohol A, the higher the hydrophobicity of alcohol A, which in turn increases the compatibility of the foaming agent with the polyol composition, making it easier to suppress bumping of the polyol composition. On the other hand, there is no particular upper limit to the partition coefficient, but it is preferably 4 or less, more preferably 3 or less, and even more preferably 1 or less. The partition coefficient is the octanol / water partition coefficient (logP OWIt means O and can be calculated by, for example, the flask shaking method. Specifically, well-purified water and octanol are mixed for 24 hours or more to saturate each, taken into a flask together with a well-purified measurement target substance, and shaken well while maintaining the temperature. Then, it is centrifuged to completely separate the phases, and the sample amounts contained in each phase are quantified by instrumental analysis suitable for the substance. For quantification, methods such as spectroscopic methods such as ultraviolet, visible, and near-infrared spectroscopy, gas chromatography, high-performance liquid chromatography, and especially for samples containing metal elements, methods such as measuring the dose using radioisotopes are used. The concentration C W in octanol and the concentration C OW in water are each determined, and the concentration ratio P O = C W / C OW or its common logarithm logP is taken as the partition coefficient.

[0016] From the perspective of suppressing the bumping of the polyol composition while reducing the water solubility and ensuring the reactivity between the polyol and the polyisocyanate, it is preferable for alcohol A used in the present invention to have two hydroxyl groups. When the number of hydroxyl groups is two, alcohol A does not inhibit the polymerization reaction between the polyol and the polyisocyanate. Also, it moderately improves the hydrophobicity of alcohol A and makes it easier to suppress the bumping of the polyol composition.

[0017] Based on the above points, as alcohol A used in the present invention, those having 5 to 10 carbon atoms are preferable, DPG and octyl alcohol are more preferable, and DPG is even more preferable. By containing DPG, the compatibility of the foaming agent can be appropriately obtained, and the occurrence of bumping of the polyol composition can be effectively suppressed. Note that DPG is generally 4-oxa-2,5-heptanediol, but its structural isomers, 4-oxa-2,6-heptanediol, 2-(2-hydroxy-propoxy)-propan-1-ol, and 2-(2-hydroxy-1-methyl-ethoxy)-propan-1-ol are also included in DPG. When the polyol composition contains DPG as alcohol A, the content of DPG is, for example, 0.3% by mass or more based on the total amount of the polyol composition, preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and even more preferably 1.0% by mass or more. When the content of DPG is at least the above lower limit, the occurrence of bumping in the polyol composition can be effectively prevented. On the other hand, the content of DPG is preferably 4.5% by mass or less, more preferably 4.0% by mass or less, and even more preferably 3.7% by mass or less based on the total amount of the polyol composition. When the content of DPG is at most the above upper limit, the reactivity between the polyol and the polyisocyanate can be ensured.

[0018] The polyol composition may contain short-chain alcohols other than the above-described alcohol A, and examples of such compounds include ethylene glycol and diethylene glycol. Here, the short-chain alcohol means an alcohol having less than 5 carbon atoms. When the polyol composition contains a short-chain alcohol, from the viewpoint of ensuring the reactivity between the polyol and the polyisocyanate, the ratio of the content of alcohol A to the total content of alcohol A and the short-chain alcohol (hereinafter sometimes referred to as the "total content") (content of alcohol A / total content) is preferably 0.9 or less, more preferably 0.7 or less, and even more preferably 0.45 or less. When the content ratio is at most the above upper limit, there is an advantage that a sufficient amount of the short-chain alcohol can be ensured and the reactivity between the polyol and the polyisocyanate can be ensured. Generally, short-chain alcohols with less steric hindrance are known to be rich in reactivity with isocyanate groups. On the other hand, from the viewpoint of effectively suppressing the bumping of the polyol composition, the content of alcohol A / total content is preferably 0.15 or more, and more preferably 0.2 or more.

[0019] From the viewpoint of achieving both the prevention of bumping of the polyol composition and the assurance of the reactivity of the polyol and polyisocyanate, the content of alcohol A is preferably 0.1 to 10% by mass, more preferably 0.3 to 7% by mass, and even more preferably 0.4 to 4% by mass, based on the total amount of the polyol composition. Because alcohol A has the structure described above, it is possible to suppress bumping of the polyol composition even in relatively small amounts. Therefore, by including a certain amount of alcohol A, it is possible to achieve both the prevention of bumping and the assurance of reactivity as described above.

[0020] The total content of alcohol A and other short-chain alcohols is not particularly limited, as long as it is within a range that can both prevent bumping of the polyol composition and ensure the reactivity of the polyol and polyisocyanate. However, based on the total amount of the polyol composition, it is preferably 2 to 15% by mass, more preferably 3 to 10% by mass, and even more preferably 3.5 to 8% by mass. The individual content of alcohol A, short-chain alcohols, and the total content can be measured quantitatively using a gas chromatography-mass spectrometry (GC-MS) instrument.

[0021] <Polyol> The polyol is not particularly limited, but examples include polyether polyols and polyester polyols. Note that the polyol is a polyol other than alcohol A and short-chain alcohols mentioned above. From the viewpoint of improving the flame retardancy of polyurethane foam, it is preferable that the polyol contains polyester polyol. Furthermore, from the viewpoint of improving flame retardancy, the use of halogen-containing polyols or phosphorus-containing polyols is also preferable. From this viewpoint, it is preferable that of 100 parts by mass of polyol, polyester polyol be 20 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 80 parts by mass or more, and particularly preferably 100 parts by mass.

[0022] The average hydroxyl value of the polyol used in the present invention is preferably 100 to 500 mg KOH / g, more preferably 150 to 450 mg KOH / g, and even more preferably 200 to 400 mg KOH / g, from the viewpoint of improving the flame retardancy of the polyurethane foam.

[0023] The average hydroxyl value refers to the hydroxyl value of a single polyol if only one type of polyol is used. If two or more types of polyols are used, the average hydroxyl value of the polyols is the weighted average value of the hydroxyl groups according to the blending ratio of the two or more polyols. For example, when using two types of polyols, polyol(d1) and polyol(d2), if the hydroxyl value of polyol(d1) is X1 and the mixing ratio is m1, and the hydroxyl value of polyol(d2) is X2 and the mixing ratio is m2, the average hydroxyl value is expressed by the following formula. Note that the mixing ratio is on a mass basis. Average hydroxyl value (mgKOH / g)=X1×(m1 / (m1+m2))+X2×(m2 / (m1+m2)) The hydroxyl value is a value measured in accordance with JIS K1557-1:2007.

[0024] (Polyester polyol) The polyester polyol may be a polyester polyol having an aromatic ring or an aliphatic polyester polyol, but when considering the flame retardancy of the resulting polyurethane foam, it is preferable to use a polyester polyol having an aromatic ring. The polyester polyol having an aromatic ring is preferably a condensate of an aromatic dicarboxylic acid such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), or naphthalenedicarboxylic acid with a glycol. In particular, from the viewpoint of improving the flame retardancy of the polyurethane foam, it is preferable that the polyol includes a phthalic acid-based polyester polyol, which is a condensate of phthalic acid and glycol, and more preferably a p-phthalic acid-based polyester polyol, which is a condensate of p-phthalic acid and glycol. While the glycol is not particularly limited, it is preferable to use a low molecular weight aliphatic glycol known as a component of polyester polyols, such as ethylene glycol, propylene glycol, or diethylene glycol.

[0025] The hydroxyl value of the polyester polyol is preferably 100-500 mgKOH / g, more preferably 150-450 mgKOH / g, and even more preferably 200-400 mgKOH / g.

[0026] (Polyether polyol) Polyether polyols are polyoxyalkylene polyols obtained by ring-opening addition polymerization of alkylene oxide to an initiator having two or more active hydrogen atoms. Examples of initiators include aliphatic polyhydric alcohols (e.g., glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, and cyclohexanedimethanol; triols such as trimethylolpropane and glycerin; tetrafunctional alcohols such as pentaerythritol; highly functional alcohols such as sucrose and sorbitol); aliphatic amines (e.g., alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine; alkanolamines such as monoethanolamine and diethanolamine); and aromatic amines (e.g., aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, Mannich condensates, etc.). Polyether polyols preferably have an aromatic ring. Among the above, polyether polyols produced using an initiator having an aromatic ring are polyether polyols having an aromatic ring. For example, polyether polyols produced using an aromatic amine as an initiator are polyether polyols having an aromatic ring. Among polyether polyols having an aromatic ring, tolylenediamine-based polyether polyols and Mannich-based polyether polyols can be suitably used.

[0027] Tolylenediamine-based polyether polyols are tolylenediamine-based polyether polyols manufactured using tolylenediamine as an initiator. The above-mentioned Mannich-type polyether polyols are obtained using the Mannich reaction and are Mannich condensates having two or more hydroxyl groups in the molecule, or polyether polyols obtained by adding alkylene oxide to such Mannich condensates. More specifically, they are Mannich condensates obtained by the Mannich reaction of at least one of phenol and its alkyl-substituted derivatives, formaldehyde and alkanolamines, or polyether polyols obtained by ring-opening addition polymerization of these compounds with at least one of ethylene oxide and propylene oxide.

[0028] The hydroxyl value of the polyether polyol is preferably 200 to 2000 mg KOH / g, and more preferably 300 to 1000 mg KOH / g.

[0029] <Foaming agent> The blowing agent used in the present invention includes a compound with a boiling point of 40°C or lower, from the viewpoint of foaming properties. The blowing agent promotes foaming when the polyol composition of the present invention is mixed with polyisocyanate to produce polyurethane foam. Examples of compounds with a boiling point of 40°C or lower that can be used as a blowing agent include low-boiling-point hydrocarbons such as propane, butane, pentane, cyclopropane, and cyclobutane; chlorinated aliphatic hydrocarbon compounds such as propyl chloride and isopropyl chloride; hydrofluoroolefins (hereinafter sometimes referred to as "HFO"); and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. The foaming agent contained in the polyol composition of the present invention is preferably HFO, which has high stability as a foaming agent, does not easily decrease catalytic activity, and also has a low environmental impact.

[0030] Suitable HFOs as blowing agents include fluoroalkenes with approximately 3 to 6 carbon atoms. Alternatively, the HFO may be a hydrochlorofluoroolefin containing a chlorine atom, and therefore may also be a chlorofluoroalkene with approximately 3 to 6 carbon atoms. Examples of HFOs include trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorodifluoropropene, chlorotrifluoropropene such as HFO-1233, and chlorotetrafluoropropene. More specifically, 3,3,3-trifluoropropene (HFO-1243zf, boiling point: -18℃), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E), boiling point: -19℃), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z), boiling point: 10℃), 2,3,3,3-tetrafluoropropene (HFO-1234yf, boiling point: -29℃), 1,1,3,3-tetrafluoropropene (boiling point: 4℃), trans-1,2,3,3,3-pentafluoropropene (HFO-1225ye(E), boiling point: -10℃), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z) Examples include 1,1,3,3,3-pentafluoropropene (HFO-1225zc, boiling point: -21℃), 1,1,2,3,3-pentafluoropropene (HFO-1225yc, boiling point: 2℃), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E), boiling point: 19℃), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z), boiling point: 39℃), 1,1,1,4,4,4-hexafluorobuto-2-ene (HFO-1336mzz, boiling point: 33℃), and 1-chloro-2,3,3,3-tetrafluoropropene(Z) (HFO-1224yd(Z), boiling point: 14℃). Among these, HFO-1233zd(E) is preferred. These HFOs may be used individually or in combination of two or more types.

[0031] The HFO content is not particularly limited, but is preferably 19 to 75 parts by mass, more preferably 29 to 67 parts by mass, and even more preferably 34 to 58 parts by mass, per 100 parts by mass of polyol. If the foaming agent content is above the lower limit, foaming is promoted, resulting in good foamability and a reduction in the density of the polyurethane foam. On the other hand, if the foaming agent content is below the upper limit, excessive foaming can be suppressed.

[0032] The blowing agent used in this invention may contain water along with HFO. Water is easy to handle, and its inclusion makes it easier to adjust the isocyanate index. When water is included along with HFO as a blowing agent, the amount of water is not particularly limited, but is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and even more preferably 0.3 to 2 parts by mass per 100 parts by mass of polyol. If the amount of blowing agent is above the lower limit, foaming is promoted, resulting in good foamability and a reduction in the density of the polyurethane foam. On the other hand, if the amount of blowing agent is below the upper limit, excessive foaming can be suppressed.

[0033] The content of the blowing agent is not particularly limited, but is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 35 to 60 parts by mass, per 100 parts by mass of polyol. If the content of the blowing agent is above the lower limit, foaming is promoted, resulting in good foamability and a reduction in the density of the polyurethane foam. On the other hand, if the content of the blowing agent is below the upper limit, excessive foaming can be suppressed.

[0034] <Catalyst> The polyol composition in the present invention preferably contains a catalyst. The catalyst is preferably a resinification catalyst, from the viewpoint of activating the reaction between the polyol and polyisocyanate and obtaining a high-quality polyurethane foam.

[0035] (Resin-based catalyst) The resinification catalyst used in the polyol composition of the present invention preferably contains a metal catalyst. This metal catalyst is generally called a resinification metal catalyst. In the present invention, by containing the above metal catalyst, the polyol composition is composed The gel time of the urethane resin composition can be adjusted to a desired range. Furthermore, by including a metal catalyst, it becomes easier to maintain good foaming properties of the polyurethane foam, and in addition, good workability is achieved. The metal component of the above metal catalyst is preferably at least one selected from the group consisting of typical metals and transition metals, more preferably one selected from the group consisting of bismuth, lead, tin, and zinc, and even more preferably bismuth, from the viewpoint of foaming properties and workability. Such metal catalysts are preferably metal salts of organic acids, more preferably metal salts of carboxylic acids, and even more preferably metal salts of carboxylic acids having 5 or more carbon atoms. Having 5 or more carbon atoms in the carboxylic acid provides good stability against foaming agents, especially hydrofluoroolefins. Furthermore, from the viewpoint of catalytic activity, the number of carbon atoms in the carboxylic acid is preferably 18 or less, and more preferably 12 or less. The carboxylic acid is preferably an aliphatic carboxylic acid, and more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may be linear or have a branched structure, but it is preferable to have a branched structure.

[0036] Specific examples of carboxylic acids include octyl acid, lauryl acid, versatic acid, pentanoic acid, and acetic acid, with octyl acid being preferred among these. In other words, the transition metal salt is preferably a metal salt of octyl acid. These carboxylic acids may be linear as described above, but they may also have a branched structure. An example of octyl acid having a branched structure is 2-ethylhexanoic acid. The metal salt of the carboxylic acid is preferably at least one metal component selected from the group consisting of typical metals and transition metals, and more preferably one selected from the group consisting of bismuth, lead, tin, and zinc. Among such metal salts of carboxylic acids, bismuth salt of octyl acid is preferred. The metal salt of the carboxylic acid may also be a carboxylic acid salt of an alkyl metal. For example, the tin carboxylic acid salt may be a dialkyltin carboxylate, and preferably a dioctyltin carboxylate. Specific examples of metal salts of carboxylic acids include bismastrioctate, dioctyltin versatate, dibutyltin dilaurate, dioctyltin dilaurate, and tin dioctylate, with bismastrioctate and dioctyltin versatate being preferred, and bismastrioctate being more preferred.

[0037] In the resinification catalyst, the content of the metal catalyst is preferably 0.05 to 18 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 1 to 13 parts by mass, per 100 parts by mass of polyol. When the content of the metal catalyst is above the lower limit, the initial activity of the urethane resin composition is good, and consequently, the foaming properties of the composition are also good. On the other hand, when the content of the metal catalyst is below the upper limit, the polyol and polyisocyanate can be reacted at an appropriate reaction rate.

[0038] In addition to the metal catalysts mentioned above, the resinification catalyst for the polyol composition of the present invention may also contain amino compounds, acetylacetone metal salts, etc., but amino compounds are preferred among them. Examples of amino compounds include imidazole compounds such as 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group. Among the imidazole compounds, 1,2-dimethylimidazole is preferred.

[0039] When an amino compound is included as the resinification catalyst, the content of the amino compound is preferably 2 to 14 parts by mass, more preferably 3 to 10 parts by mass, and even more preferably 3.5 to 9 parts by mass, per 100 parts by mass of polyol.

[0040] Examples of acetylacetone metal salts include aluminum acetylacetone, iron acetylacetone, copper acetylacetone, zinc acetylacetone, beryllium acetylacetone, chromium acetylacetone, indium acetylacetone, manganese acetylacetone, molybdenum acetylacetone, titanium acetylacetone, cobalt acetylacetone, vanadium acetylacetone, and zirconium acetylacetone.

[0041] The resinification catalyst contained in the polyol composition of the present invention may be used alone or in combination of two or more types. When a metal catalyst is included as the resinification catalyst, it is preferable to include the bismuth compound described above, from the viewpoint of improving foaming properties when forming polyurethane foam by spraying the urethane resin composition. Furthermore, when a resinification catalyst other than a metal catalyst is included in addition to the above metal catalyst, it is preferable to use a combination of a bismuth compound and an amino compound as the resinification catalyst, and more preferable to use a combination of a bismuth compound and an imidazole compound.

[0042] The resinification catalyst content in the polyol composition of the present invention is preferably 2 parts by mass or more, and more preferably 3 parts by mass or more, per 100 parts by mass of polyol. By setting the content above the lower limit, the reaction between the polyol and polyisocyanate can be promoted at an appropriate reaction rate while maintaining good foaming properties. Furthermore, in order to improve the reaction rate and make it suitable for spray applications, the resinification catalyst content is more preferably 4 parts by mass or more, and even more preferably 5 parts by mass or more. In addition, from the viewpoint of obtaining foaming properties and reactivity commensurate with the catalyst content, the resinification catalyst content is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and even more preferably 15 parts by mass or less.

[0043] (trimerization catalyst) The polyol composition of the present invention may further contain a trimerizing catalyst. The trimerizing catalyst is a catalyst that reacts with the isocyanate groups contained in the isocyanate to trimerize them and promote the formation of an isocyanurate ring. The advantage of containing a trimerizing catalyst is that it completes the reaction of unreacted isocyanate groups, thereby yielding a good polyurethane foam. Examples of trimerizing catalysts include metal catalysts and ammonium salts. Examples of metal catalysts used as trimerization catalysts (trimerization metal catalysts) include potassium organic acids, preferably potassium octoates such as potassium 2-ethylhexanoate, potassium acetate, potassium propionate, potassium butanoate, potassium benzoate, and other potassium carboxylates having 2 to 8 carbon atoms. As the ammonium salt, tertiary ammonium salts such as triethylammonium salt and triphenylammonium salt, and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, and tetraphenylammonium salt can be used, but among these, quaternary ammonium salts are preferred. The ammonium salt is, for example, an ammonium salt of a carboxylic acid. Examples of carboxylic acids in the ammonium salt include saturated fatty acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms. The hydrocarbon group of the saturated fatty acid may be linear or branched, but branching is preferred. Specific examples of carboxylic acids include 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid, but among these, 2,2-dimethylpropanoic acid is preferred. The trimerization catalyst may be used alone or in combination of two or more types. When using two or more types in combination, it is preferable to use a quaternary ammonium salt and a metal catalyst in combination.

[0044] The content of the trimerizing catalyst in the polyol composition is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, even more preferably 2 to 20 parts by mass, and even more preferably 3 to 10 parts by mass, per 100 parts by mass of polyol. If the content of the trimerizing catalyst is above the lower limit, there will be no significant difference in the activity between resinification and trimerization, preventing foaming from occurring in two stages and resulting in good foamability. On the other hand, if the content of the trimerizing catalyst is below the upper limit, the resinification reaction will proceed actively, and the heat of the resinification reaction will assist the activity of trimerization, resulting in good foamability and the formation of a good polyurethane foam.

[0045] <Filler> The polyol composition according to the present invention contains a filler. Including a filler makes it easier to improve various properties of the polyurethane foam, such as flame retardancy. Furthermore, because the polyol composition contains a filler, it may be stirred before foaming, but as mentioned above, even if the polyol composition is stirred, bumping can be prevented because it contains alcohol A. The filler preferably contains a flame retardant. By using a flame retardant as a filler, high flame retardancy can be imparted to the polyurethane foam. The flame retardant used as a filler is a solid flame retardant. In the present invention, flame retardancy can be more effectively enhanced by using a solid flame retardant. A solid flame retardant is a flame retardant that becomes solid at room temperature (23°C) and normal pressure (1 atm). As the solid flame retardant used in the present invention, at least one selected from the group consisting of phosphate-containing flame retardants, red phosphorus-based flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, metal hydroxides, and needle-shaped fillers is preferred.

[0046] Examples of phosphate-containing flame retardants include phosphates comprising salts of various phosphoric acids with at least one metal or compound selected from metals of groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. The phosphoric acid is not particularly limited, but may be monophosphates such as phosphorous acid and hypophosphorous acid, or it may be pyrophosphate, polyphosphate, etc. Examples of metals in groups IA through IVB of the periodic table include lithium, sodium, calcium, barium, iron(II), iron(III), and aluminum. Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and piperazine. Examples of aromatic amines include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, and 3-(trifluoromethyl)aniline. Examples of heterocyclic compounds containing nitrogen in the ring include pyridine, triazine, and melamine.

[0047] Specific examples of phosphate-containing flame retardants include monophosphates such as aluminum phosphite and trialuminum phosphate, pyrophosphates, and polyphosphates. Here, the polyphosphates are not particularly limited, but examples include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, and aluminum polyphosphate. One or more of the above-mentioned phosphate-containing flame retardants can be used. In the present invention, trialuminum phosphate is preferred.

[0048] Red phosphorus-based flame retardants may consist of pure red phosphorus, but they may also be red phosphorus coated with a resin, metal hydroxide, metal oxide, etc., or a mixture of red phosphorus and a resin, metal hydroxide, metal oxide, etc. The resin used to coat or mix with red phosphorus is not particularly limited, but examples include thermosetting resins such as phenolic resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, aniline resins, and silicone resins. From the viewpoint of flame retardancy, metal hydroxides are preferred as the compound used for coating or mixing. The metal hydroxides described later may be appropriately selected and used.

[0049] Bromine-containing flame retardants are not particularly limited as long as they contain bromine in their molecular structure and are solid at room temperature and pressure, but examples include aromatic compounds containing brominated aromatic rings. Examples of brominated aromatic ring-containing aromatic compounds include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

[0050] Furthermore, the brominated aromatic ring-containing aromatic compound may also be a brominated polymer. Specifically, examples include polycarbonate oligomers produced using brominated bisphenol A as a raw material, brominated polycarbonates such as copolymers of this polycarbonate oligomer and bisphenol A, and diexo compounds produced by the reaction of brominated bisphenol A and epichlorohydrin. In addition, examples include brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, poly(brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A and cyanuryl chloride condensates, brominated polystyrene such as brominated (polystyrene), poly(brominated styrene), and crosslinked brominated polystyrene, and crosslinked or non-crosslinked brominated poly(methylstyrene). Furthermore, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may also be used. These bromine-containing flame retardants may be used individually or in combination of two or more. Among the above, brominated aromatic ring-containing aromatic compounds are preferred, and among these, monomer-based organic bromine compounds such as hexabromobenzene are preferred.

[0051] Examples of boron-containing flame retardants used in the present invention include borax, boron oxide, boric acid, and borates. Examples of boron oxides include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide. Examples of borates include alkali metals, alkaline earth metals, elements from groups 4, 12, and 13 of the periodic table, and ammonium borates. Specifically, examples include alkali metal borates such as lithium borate, sodium borate, potassium borate, and cesium borate; alkaline earth metal borates such as magnesium borate, calcium borate, and barium borate; zirconium borate, zinc borate, aluminum borate, and ammonium borate. Boron-containing flame retardants may be used alone or in combination of two or more types. The boron-containing flame retardant used in the present invention is preferably a borate, and more preferably zinc borate.

[0052] Examples of antimony-containing flame retardants include antimony oxide, antimonate salts, and pyroantimonate salts. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimonate salts include sodium antimonate and potassium antimonate. Examples of pyroantimonate salts include sodium pyroantimonate and potassium pyroantimonate. Antimony-containing flame retardants may be used alone or in combination of two or more types. The preferred antimony-containing flame retardant used in this invention is antimony trioxide.

[0053] Examples of metal hydroxides used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, and tin hydroxide. A single metal hydroxide may be used, or two or more may be used in combination. A preferred metal hydroxide used in the present invention is aluminum hydroxide.

[0054] Examples of needle-shaped fillers include potassium titanate whiskers, aluminum borate whiskers, magnesium-containing whiskers, silicon-containing whiskers, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fibers, carbon fibers, graphite fibers, metal fibers, slag fibers, gypsum fibers, silica fibers, alumina fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, stainless steel fibers, and the like. These needle-shaped fillers may be used individually or in combination of two or more types.

[0055] The aspect ratio (length / diameter) of the needle-shaped filler used in the present invention is preferably in the range of 5 to 50, and more preferably in the range of 10 to 40. This aspect ratio can be determined by observing the needle-shaped filler with a scanning electron microscope and measuring its length and width.

[0056] The solid flame retardants used in the present invention may be used individually or in combination of two or more types. When using two or more types in combination, for example, two or more solid flame retardants of the same classification may be used, such as containing potassium titanate whiskers and aluminum borate whiskers as needle-shaped fillers, or one or more solid flame retardants of different classifications may be used, such as containing a red phosphorus-based flame retardant and needle-shaped fillers. In the present invention, among the solid flame retardants used, it is preferable to use a red phosphorus-based flame retardant from the viewpoint of fully exhibiting the flame retardant effect. Furthermore, the content of the solid flame retardant is not particularly limited, but is, for example, 10 to 130 parts by mass, preferably 20 to 120 parts by mass, more preferably 30 to 110 parts by mass, and even more preferably 40 to 100 parts by mass, per 100 parts by mass of polyol. By keeping the content of the solid flame retardant within the above range, it is possible to prevent the sedimentation of the solid flame retardant and improve its dispersibility without unnecessarily increasing the solid content.

[0057] As fillers, inorganic fillers other than the solid flame retardants mentioned above may be used. Examples of inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass beads, silica balloons, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon balloons, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash, silica alumina fibers, and zirconia fibers. These inorganic fillers may be used individually or in combination of two or more types.

[0058] When the polyol composition according to the present invention contains a filler, the amount is not particularly limited, but is preferably 10 to 150 parts by mass, more preferably 21 to 135 parts by mass, even more preferably 31 to 120 parts by mass, and still more preferably 42 to 110 parts by mass per 100 parts by mass of polyol. A filler content above the lower limit makes it easier to improve the flame retardancy of the polyurethane foam formed from the polyol composition. Furthermore, a filler content below the upper limit allows the viscosity of the polyol composition to be kept below a certain level, resulting in good handling.

[0059] <Phosphate esters> The polyol-containing composition of the present invention may contain flame retardants other than the solid flame retardant described above. Examples of such flame retardants include liquid flame retardants that are liquid at room temperature (23°C) and atmospheric pressure (1 atm), and specifically, phosphate esters. Using phosphate esters makes it easier to improve the flame retardancy of polyurethane foam without reducing the fluidity of the polyol-containing composition.

[0060] As phosphate esters, monophosphate esters, condensed phosphate esters, etc., can be used. A monophosphate ester is a phosphate ester that has one phosphorus atom in its molecule. Examples of monophosphate esters include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tri(2-ethylhexyl) phosphate; halogen-containing phosphate esters such as tris(β-chloropropyl) phosphate; trialkoxy phosphates such as tributoxyethyl phosphate; aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, cresyldiphenyl phosphate, and diphenyl(2-ethylhexyl) phosphate; and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate.

[0061] Examples of condensed phosphate esters include aromatic condensed phosphate esters such as trialkyl polyphosphates, resorcinol polyphenyl phosphates, bisphenol A polycresyl phosphates, and bisphenol A polyphenyl phosphates. Examples of commercially available condensed phosphate esters include "CR-733S," "CR-741," and "CR747" from Daihachi Chemical Industry Co., Ltd., and "ADEKA Stab PFR" and "FP-600" from ADEKA Corporation.

[0062] The phosphate esters may be used individually from the above-mentioned types, or two or more may be used in combination. Among these, monophosphate esters are preferred from the viewpoint of making it easier to adjust the viscosity of the polyol composition and improving the flame retardancy of the polyurethane foam, and halogen-containing phosphate esters such as tris(β-chloropropyl)phosphate are more preferred. The content of phosphate ester in the polyol composition is preferably 5 to 100 parts by mass, more preferably 12 to 90 parts by mass, even more preferably 20 to 75 parts by mass, and still more preferably 30 to 60 parts by mass, per 100 parts by mass of polyol.

[0063] <Foam stabilizer> The polyol composition of the present invention may contain a foam stabilizer. Examples of foam stabilizers include silicone foam stabilizers such as organopolysiloxanes, but even without a silicone component, a surfactant effect can be obtained as long as the structure has polar and nonpolar parts within the molecule, so the invention is not limited to the above types. Furthermore, the silicone foam stabilizer may include a graft copolymer of polydimethylsiloxane and polyethylene glycol. The foam stabilizer content is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of polyol. The foam stabilizer may be used alone or two or more types may be used.

[0064] <Other ingredients> The polyol composition may contain other additives, such as phenolic, amine, or sulfur-based antioxidants, heat stabilizers, light stabilizers, metal damage inhibitors, antistatic agents, crosslinking agents, lubricants, softeners, pigments, dyes, and tackifying resins, to the extent that they do not interfere with the effects of the present invention.

[0065] <Manufacturing method> There are no particular limitations on the method for producing the polyol composition of the present invention. For example, it can be produced by stirring each component at room temperature using a homodisperser or the like for about 30 seconds to 20 minutes. In the present invention, since the polyol composition does not contain red phosphorus, it is easy to handle during production.

[0066] [Urethane resin composition, polyurethane foam] The urethane resin composition of the present invention comprises the above-mentioned polyol composition and polyisocyanate. More specifically, the urethane resin composition is obtained by mixing at least the above-mentioned polyol composition and polyisocyanate.

[0067] <Polyisocyanate> As the polyisocyanate contained in the urethane resin composition of the present invention, various polyisocyanates such as aromatic, alicyclic, and aliphatic polyisocyanates having two or more isocyanate groups can be used.

[0068] Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI).

[0069] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate. Examples of aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0070] Among these, aromatic polyisocyanates are preferred due to their ease of handling, rapid reaction, excellent physical properties of the resulting polyurethane foam, and low cost, and liquid diphenylmethane diisocyanate (MDI) is preferred. Examples of liquid MDI include crude MDI (also called polymeric MDI). Specific commercially available liquid MDIs include "44V-10" and "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.) and "Millionate MR-200" (Nippon Polyurethane Industry Co., Ltd.). Alternatively, uretonimine-containing MDI (for example, "Millionate MTL" is a commercially available product manufactured by Nippon Polyurethane Industry Co., Ltd.) may also be used. Furthermore, a polyisocyanate may be treated by reacting some of the isocyanate active groups within it with a hydroxyl group-containing compound to increase its affinity with polyols. In addition to liquid MDI, other polyisocyanates may be used in combination, and any polyisocyanates known in the field of polyurethanes can be used without limitation.

[0071] The isocyanate index of the urethane resin composition of the present invention is preferably 600 or less, more preferably 550 or less, and even more preferably 500 or less. When the isocyanate index is below these upper limits, two-stage foaming during polyurethane foam formation is more easily suppressed. Furthermore, from the viewpoint of properly forming polyurethane foam, the isocyanate index of the urethane resin composition is preferably 100 or higher, more preferably 150 or higher, and even more preferably 200 or higher. The isocyanate index (INDEX) is calculated using the following method.

[0072] INDEX = Equivalents of polyisocyanate ÷ (Equivalents of polyol + Equivalents of water) × 100 Here, Equivalent weight of polyisocyanate = Number of parts of polyisocyanate used × NCO content (%) × 100 / Molecular weight of NCO The equivalent weight of the polyol = OHV × the amount of polyol used ÷ the molecular weight of KOH, where OHV is the hydroxyl value of the polyol (mgKOH / g). Equivalent amount of water = Number of parts of water used × Number of OH groups in water / Molecular weight of water In the above formula, the unit of the number of parts used is weight (g), the molecular weight of the NCO group is 42, the NCO content is the proportion of NCO groups in the polyisocyanate expressed as mass%, and for the sake of unit conversion in the above formula, the molecular weight of KOH is assumed to be 56100, the molecular weight of water is assumed to be 18, and the number of OH groups in water is assumed to be 2.

[0073] <Geltime> The urethane resin composition of the present invention provides a good balance between the urethane resin formation rate and the foaming force, and from the viewpoint of forming cells that are effective in obtaining excellent heat insulation properties in polyurethane foam, a formation time of 25 seconds or less is preferred, more preferably 23 seconds or less, and even more preferably 20 seconds or less. The gel time can be adjusted to a desired value by controlling the type and amount of catalyst contained in the polyol composition. The gel time is a value measured by the cup foaming method and serves as an indicator of the activity of the reaction between the polyol and the polyisocyanate. The specific measurement method is described in the examples below.

[0074] <Application> The uses of the urethane resin composition of the present invention and the polyurethane foam formed from the composition are not particularly limited, but they can be used to fill cavities in structures such as buildings, furniture, automobiles, trains, and ships, or to be sprayed onto such structures. In particular, they are preferably used for spraying onto structures, i.e., for spraying, and more preferably for spraying at construction sites of buildings. Spraying can be carried out using a spraying device (e.g., GRACO A-25) and a spray gun (e.g., Gasmar D-gun). Spraying is performed by temperature-controlled mixing of the polyol composition and polyisocyanate in separate containers within the spraying device, then causing them to collide and mix at the tip of the spray gun, and finally atomizing the mixture using air pressure. The spraying device and spray gun are well-known and commercially available. Furthermore, the stock solution temperature settings and pressures can be the same as those for spraying polyurethane foam. [Examples]

[0075] The present invention will be described more specifically below with reference to examples, but the present invention is not limited to these examples.

[0076] [Materials used] <Polyol composition> (Polyol) • p-phthalate polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g)

[0077] (Foam stabilizer) • Silicone-based foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193)

[0078] (catalyst) (1) Resin-based catalyst • Amine-based catalyst: 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT DM70), 1,2-dimethylimidazole concentration 65-75% by mass, ethylene glycol (partition coefficient -1.36), concentration 25-35% by mass. • Bismuth compound: Bismuth 2-ethylhexanoate (manufactured by Nitto Chemical Co., Ltd., product name: Bi28), concentration 81-90% by mass (2) Trimerization catalyst • Quaternary ammonium salt: 2,2-tetramethylammonium dimethylpropanoate (Evonik, product name: DABCO TMR7) 2,2-tetramethylammonium dimethylpropanoate concentration 45-55% by mass, ethylene glycol concentration 45-55% by mass

[0079] (Foaming agent) ·water • HFO-1233zd <Hydrofluoroolefin> (Honeywell, product name: Solstice LBA)

[0080] (Liquid flame retardant) • Phosphate ester-based flame retardant: Tris(β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)

[0081] (Solid flame retardant (filler)) • Red phosphorus-based flame retardant (manufactured by Phosphorus Chemical Industry Co., Ltd., product name: Nova Excel 140)

[0082] (Alcohol A) • Dipropylene glycol (DPG) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name: Dipropylene glycol (isomer mixture)), partition coefficient -0.46 Octyl alcohol (manufactured by Kao Corporation, product name: Calcol 0898), partition coefficient 3.5 The distribution coefficients were all obtained from the safety data sheet issued by Merck.

[0083] (Short-chain alcohols) Butanediol (Merck, product name: 1,4-butanediol), partition coefficient -0.88

[0084] <Polyisocyanate> • Diphenylmethane diisocyanate (manufactured by Sumika Covestro Urethane Co., Ltd., product name: Sumijoule 44V20L)

[0085] Measurement and evaluation were performed using the following methods.

[0086] [Content of alcohol A and short-chain alcohols] Approximately 1-2 μL of the polyol composition solution was taken and placed in a gas chromatography-mass spectrometer (GC-MS) to separate and detect alcohol A, butanediol, and ethylene glycol and diethylene glycol (which are included as diluents in the catalyst) from multiple components in the solution. The content of each alcohol was then measured by quantitative analysis. Based on the content obtained from the above measurement, the content of alcohol A and the total content of alcohol A and short-chain alcohols were determined.

[0087] [Boiling test] Each component was kneaded in a predetermined amount to produce a liquid polyol composition, which was then placed in a centrifuge and subjected to defoaming treatment. (Centrifugal separation conditions: Centrifugation time: 270 seconds, Orbital speed: 300 rpm, Rotational speed: 700 rpm) 60 g of the polyol composition after the degassing treatment described above is poured into a 100 ml vial (model number: 1030-13113, manufactured by Kyoto Rikagaku Kikai Co., Ltd.), and a stirring bar is inserted. To ensure airtightness, an aluminum seal vial is used, and an aluminum cap is placed over the septum and tightened. After that, the vial containing the polyol composition is stored in a 33°C warm bath for at least one hour to adjust the temperature of the polyol composition to 33°C. Then the vial is opened, and the stirring bar is rotated at 1,500 rpm using a magnetic stirrer to stir the liquid. The boiling of the liquid surface during stirring is observed, the height at which the liquid surface reaches its highest point is recorded, and the difference between this value and the liquid surface height before stirring is calculated as the boiling height. The evaluation criteria for the boiling test are as follows. ○: Boiling height less than 30mm △: Boiling height is 30mm or more but less than 35mm ×: Boiling height is 35mm or more

[0088] [Cup foaming method] The gel time of the urethane resin composition was measured using the cup foaming method as shown in the following procedure. (1) A liquid polyol composition was prepared by kneading the components of the polyol composition according to the formulations shown in Table 1. The polyol composition was diluted with TMCPP at a ratio of 3 parts by mass of TMCPP per 1 part by mass of the polyol composition. (2) One part by mass of the polyisocyanate listed in Table 1 was diluted with one part by mass of TMCPP to obtain a polyisocyanate composition. (3) The liquid temperatures of the polyol composition obtained in (1) and the polyisocyanate composition obtained in (2) were each adjusted to 15°C, and 120g of each was mixed in a mass ratio of 1:1. The mixture was then stirred for 5 seconds at a rotation speed of 6000 rpm using a stirring device (manufactured by IKA, product name: EUROSTAR 20 high speed digital). (4) The time from the start of stirring to the time from the start of stirring was set to 0 seconds, and the time (in seconds) from when a rod was inserted into the foaming foam until resistance was felt from the foam was measured to obtain the gel time. The gel time obtained using the above procedure was evaluated. The evaluation criteria for gel time are as follows: 〇: 20 seconds or less △: More than 20 seconds and less than 25 seconds ×: More than 25 seconds

[0089] [Table 1] The catalyst content values ​​listed in Table 1 represent the content in the final product.

[0090] Based on the above, the polyol compositions prepared in the examples contained alcohol A, and therefore, even when stirring was performed to prevent the aggregation and precipitation of fillers while HFO was included as a foaming agent, bumping could be suppressed. In contrast, the polyol composition prepared in the comparative example contained alcohol group A, and as a result of stirring to prevent the aggregation and precipitation of the filler, bumping could not be suppressed.

Claims

1. A polyol composition containing a polyol, a foaming agent, a filler, and alcohol A, used for spray application at construction sites of buildings, The aforementioned foaming agent contains a compound with a boiling point of 40°C or lower. The alcohol A is dipropylene glycol, The amount of the foaming agent is 20 to 80 parts by mass per 100 parts by mass of the polyol. A polyol composition in which the content of the dipropylene glycol is 0.7% by mass or more and 10% by mass or less based on the total amount of the polyol composition.

2. The polyol composition contains a catalyst, The catalyst comprises a metal salt of a carboxylic acid, The polyol composition according to claim 1, wherein the metal component of the metal salt is one selected from the group consisting of bismuth, lead, tin, and zinc.

3. The polyol composition according to claim 1 or 2, wherein the compound with a boiling point of 40°C or less is a hydrofluoroolefin.

4. A urethane resin composition obtained by mixing the polyol composition according to any one of claims 1 to 3 with a polyisocyanate.

5. A polyurethane foam formed from the urethane resin composition described in claim 4.

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