Polyol composition, foamed urethane resin composition, and polyurethane foam

Abstract

The objective is to provide a polyol composition that exhibits both good storage stability and ease of application. [Solution] A polyol composition for obtaining a polyurethane foam by reacting with a polyisocyanate compound, wherein the polyol composition comprises a polyester polyol, a polyether polyol, a catalyst, a blowing agent, and a solid flame retardant or filler, wherein the polyether polyol includes a polyether polyol synthesized with a nitrogen-containing compound as an initiator, and the content of the polyester polyol is greater than the content of the polyether polyol.

Description

[Technical Field]

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

[0002] Polyurethane foams are used in practical applications for insulation and condensation prevention in various structures such as ceilings, roofs, and walls of buildings, including apartment buildings, detached houses, and commercial buildings, due to their excellent thermal insulation properties. Polyurethane foams are formed, for example, by spraying a urethane resin composition obtained by mixing a polyol-containing composition and polyisocyanate onto the surface of each structure, followed by foaming and curing. Polyol-containing compositions are known to contain polyols, blowing agents, flame retardants, and catalysts, and in recent years, the use of hydrofluoroolefins as blowing agents has been considered from the viewpoint of environmental protection (see, for example, Patent Document 1). Furthermore, the use of solid flame retardants such as red phosphorus is also being considered to improve flame retardancy. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2022-030312 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] However, when hydrofluoroolefins are used as blowing agents, the catalyst contained in the polyol-containing composition becomes inactivated by reacting with the hydrofluoroolefin, which leads to a problem of reduced storage stability of the composition. To address these problems, it is conceivable to use a catalyst that can maintain good storage stability of polyol-containing compositions. However, in that case, the workability of the composition may deteriorate, such as the formation of gaps between the surface of each structure and the polyurethane foam during spray application. In other words, there is a trade-off between storage stability and workability.

[0005] Therefore, the object of the present invention is to provide a polyol composition that has improved flame retardancy while also having good storage stability and workability. [Means for solving the problem]

[0006] As a result of diligent research, the inventors have found that the above problems can be solved by including a highly active polyol, initiated by an amine compound, in the polyol composition. In other words, the present invention provides the following [1] to

[10] .

[0007] [1] A polyol composition for obtaining a polyurethane foam by reacting with a polyisocyanate compound, wherein the polyol composition comprises a polyester polyol, a polyether polyol, a catalyst, a blowing agent, and a solid flame retardant or filler, wherein the polyether polyol includes a polyether polyol synthesized with a nitrogen-containing compound as an initiator, and the content of the polyester polyol is greater than the content of the polyether polyol. [2] The polyol composition according to [1], wherein the initiator of the polyether polyol synthesized with the nitrogen-containing compound as an initiator is at least one selected from the group consisting of ethylenediamine, toluenediamine, triethanolamine, and Mannich condensates. [3] The polyol composition according to [1] or [2], wherein the content of the polyether polyol is 30 parts by mass or less per 100 parts by mass of the polyol compound. [4] A polyol composition according to any one of [1] to [3], further comprising a liquid flame retardant. [5] The polyol composition according to any one of [1] to [4], comprising a phosphorus compound as the solid flame retardant. [6] A polyol composition according to any one of [1] to [5], comprising an organic acid bismuth salt. [7] A polyol composition according to any one of [1] to [6], comprising a heterocyclic compound having a nitrogen atom. A foamable urethane resin composition obtained by mixing a polyol composition described in any one of items [8][1] to [7] with a polyisocyanate compound. [9] The foaming urethane resin composition according to [8], wherein the isocyanate index is 250 or higher. A polyurethane foam formed by spray foaming the foamed urethane resin composition described in

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

[0008] According to the present invention, it is possible to provide a polyol composition that has improved flame retardancy while also having good storage stability and workability. [Modes for carrying out the invention]

[0009] [Polyol composition] The polyol composition of the present invention is for obtaining a polyurethane foam by reacting it with a polyisocyanate compound, and comprises a polyol compound, a catalyst, a blowing agent, and a solid flame retardant or filler. Among these, the polyol compound includes polyester polyols and polyether polyols.

[0010] In addition, the polyol composition of the present invention is characterized in that the content of the polyester polyol is larger than the content of the polyether polyol. By the content of the polyester polyol being larger than the content of the polyether polyol, excellent flame retardancy can be imparted to the polyurethane foam. Specifically, in the polyol composition, the content ratio of the polyether polyol to the polyester polyol (polyether polyol / polyester polyol) is preferably 45 / 55 or less, more preferably 30 / 70 or less, still more preferably 25 / 75 or less, and even more preferably 15 / 85 or less, based on mass. Also, from the viewpoint of making it easier to contain a polyether polyol synthesized using a nitrogen-containing compound as an initiator, the polyether polyol / polyester polyol is preferably 2 / 98 or more, more preferably 5 / 95 or more, and still more preferably 8 / 92 or more.

[0011] (Polyol compound) (Polyether polyol) The polyether polyol used in the present invention includes a polyether polyol synthesized using a nitrogen-containing compound as an initiator. Generally, when a catalyst having excellent storage stability such as a resinification catalyst described later is blended into the polyol composition, when the composition is reacted with a polyisocyanate compound and sprayed onto a spraying target to obtain a polyurethane foam, there is a problem that the workability deteriorates due to the generation of a gap between the foam and the spraying target. In the present invention, by including a polyether polyol synthesized using a nitrogen-containing compound as an initiator as the polyether polyol, both the workability and the storage stability can be made excellent. The reason is not clear, but a polyether polyol synthesized using a nitrogen-containing compound as an initiator typically has a tertiary amino group, and the rate of the curing reaction between the polyol compound and the polyisocyanate compound is gently promoted, and the curing reaction proceeds moderately while adapting to the spraying target, so it is presumed that the workability becomes good.

[0012] As the polyether polyol using a nitrogen-containing compound as an initiator, for example, a polyoxyalkylene polyol synthesized by subjecting a nitrogen-containing compound to ring-opening addition polymerization of an alkylene oxide can be used. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and the like. The nitrogen-containing compound used as an initiator preferably has two or more active hydrogen atoms and is preferably an amine compound. The amine compound preferably has active hydrogen atoms directly bonded to two or more nitrogen atoms. As the initiator, it is preferably at least one selected from the group consisting of aromatic diamines such as toluenediamine, ethylenediamine, triethanolamine, diethylenetriamine, and Mannich condensates. Among them, it is more preferably at least one selected from the group consisting of ethylenediamine, toluenediamine, triethanolamine, and Mannich condensates. By using these initiators, it becomes easier to improve the workability of the polyol composition.

[0013] When a Mannich condensate is used as an initiator, it is preferably a Mannich polyether polyol. A Mannich polyether polyol is obtained by utilizing a Mannich reaction and is a Mannich condensate having two or more hydroxyl groups in the molecule or a polyether polyol obtained by adding an alkylene oxide to such a Mannich condensate. More specifically, it is a polyether polyol obtained by subjecting at least one of phenol and its alkyl-substituted derivatives, a Mannich condensate obtained by the Mannich reaction of formaldehyde and an alkanolamine, or this compound to ring-opening addition polymerization of at least one alkylene oxide such as ethylene oxide or propylene oxide.

[0014] The polyol composition of the present invention may contain, to the extent that it does not hinder the objective of the present invention, a polyether polyol synthesized using a nitrogen-free compound as an initiator (hereinafter also referred to as "other initiator") (hereinafter also referred to as "other polyether polyol"). Examples of other 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, cyclohexanedimethanol, triols such as trimethylolpropane and glycerin, tetrafunctional alcohols such as pentaerythritol, sucroses, sorbitols, etc.).

[0015] In the polyether polyol contained in the polyol composition, the proportion of polyether polyol initiated by a nitrogen-containing compound is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 90 to 100% by mass, and even more preferably 100% by mass. By keeping the proportion of polyether polyol initiated by a nitrogen-containing compound within the above range, it becomes easier to achieve excellent workability and storage stability.

[0016] In the polyol composition, the polyether polyol content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, per 100 parts by mass of the polyol compound. By keeping the polyether polyol content below the above upper limit, it becomes easier to impart excellent flame retardancy to the polyurethane foam. Furthermore, from the viewpoint of easily including a certain amount of polyether polyol synthesized with a nitrogen-containing compound as an initiator, the polyether polyol content is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 8 parts by mass or more, per 100 parts by mass of the polyol compound. The polyether polyol content referred to here is the total content of polyether polyols synthesized using nitrogen-containing compounds as initiators, and other polyether polyols.

[0017] The hydroxyl value of the polyether polyol initiated with a nitrogen-containing compound is not particularly limited, but is preferably 100 to 2000 mg KOH / g, more preferably 200 to 1500 mg KOH / g, and even more preferably 300 to 900 mg KOH / g. The hydroxyl value is measured in accordance with JIS K1557-1:2007. The hydroxyl value of polyester polyols, which will be discussed later, is measured in the same manner.

[0018] <Polyester Polyol> The polyol composition of the present invention contains a polyester polyol as described above. The presence of a polyester polyol makes it easier to improve the flame retardancy of the polyol composition. 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 contains 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.

[0019] The hydroxyl value of the polyester polyol is not particularly limited, but is preferably 100 to 1500 mg KOH / g, more preferably 120 to 1000 mg KOH / g, and even more preferably 150 to 500 mg KOH / g.

[0020] The polyol composition of the present invention may also contain polyol compounds other than the polyether polyols and polyester polyols described above (hereinafter also referred to as "other polyol compounds"). Examples of other polyol compounds include polymer polyols and polycarbonate polyols. Examples of polycarbonate polyols include polyols obtained by the de-alcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, etc. Examples of polymer polyols include polymers obtained by graft polymerization of ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate onto aromatic polyols, alicyclic polyols, aliphatic polyols, etc., polybutadiene polyols, or hydrogenated versions thereof. The content of other polyol compounds is preferably less than the content of polyether polyols and polyester polyols. Specifically, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 0 parts by mass, per 100 parts by mass of the polyol compound.

[0021] (catalyst) The catalyst is not particularly limited, but examples include resin catalysts and trimerization catalysts.

[0022] <Resin-based catalyst> The catalyst used in this invention preferably includes a metal catalyst as a resinification catalyst. This metal catalyst is generally called a resinification metal catalyst. In this invention, including the above resinification metal catalyst promotes the reaction between the polyol compound and the polyisocyanate compound, and in particular, the initial reaction rate can be increased. Furthermore, including the resinification metal catalyst makes it easier to appropriately control the reaction rate between the polyol compound and the polyisocyanate compound. From the viewpoint of foaming properties, the above resinification metal catalyst is preferably a bismuth compound containing bismuth or a tin compound containing tin, and a bismuth compound is more preferable. Bismuth compounds have low reactivity to HFO and high storage stability. In addition, they improve initial activity without reducing the flame retardancy of the polyurethane foam, making it easier to improve workability.

[0023] The resin-based metal catalyst containing bismuth or tin is preferably an organic acid metal salt, and more preferably an organic acid bismuth salt. Specifically, examples of organic acid metal salts include metal salts of carboxylic acids. Examples of metal salts of carboxylic acids include bismuth salts and tin salts of carboxylic acids, with bismuth salts of carboxylic acids being more preferred. Of the bismuth salts of carboxylic acids, bismuth salts of carboxylic acids having 5 or more carbon atoms are even more preferred. By including a specific metal salt in this way, it is possible to prevent problems such as dripping from occurring when the polyol compound and the polyisocyanate compound react. The carboxylic acid has five or more carbon atoms, which improves its stability against blowing agents, particularly 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 branched, but it is preferable to have a branched structure.

[0024] Specific examples of carboxylic acids include octic acid, lauric acid, versatic acid, pentanoic acid, and acetic acid, with octic acid being preferred among these. That is, the resin-based metal catalyst is preferably a metal salt of octic acid, and more preferably a bismuth salt of octic acid. These carboxylic acids may be linear as described above, but may also have a branched structure. An example of octic acid having a branched structure is 2-ethylhexanoic acid.

[0025] The metal salt of the carboxylic acid may also be a carboxylate salt of an alkyl metal. For example, the tin carboxylate 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.

[0026] The polyol composition of the present invention may also preferably contain a heterocyclic compound having a nitrogen atom (hereinafter also referred to as "nitrogen-containing heterocyclic compound") as a resinification catalyst. Including a nitrogen-containing heterocyclic compound as a resinification catalyst improves stability with respect to hydrofluoroolefins, thereby preventing the decomposition of hydrofluoroolefins and resulting in good foaming properties. Furthermore, it is possible to maintain a reaction rate above a certain level, improving the workability when spraying the foaming urethane resin composition. Specifically, it is possible to prevent problems such as dripping that occur when the polyol compound and the polyisocyanate compound react. Among nitrogen-containing heterocyclic compounds, it is more preferable to include an imidazole derivative. As described above, imidazole derivatives are less affected by hydrofluoroolefins and facilitate the reaction between polyol compounds and polyisocyanate compounds while increasing the stability of the polyol composition. Therefore, by containing imidazole derivatives, the reactivity between the polyol compound and the polyisocyanate compound is enhanced, resulting in even better foaming properties. The imidazole derivative is preferably imidazole substituted at the 1-position and 2-position independently with an alkyl group having 8 or fewer carbon atoms, and the alkyl group preferably has 6 or fewer carbon atoms, more preferably 4 or fewer carbon atoms. Preferred specific examples of the imidazole derivative are represented by the following general formula (1).

[0027] [Chemical formula] (In general formula (1), R 4 and R 5 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.)

[0028] R 4 and R 5 in general formula (1) each independently represent an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. The alkyl group and the alkenyl group may each be linear or may have a branched structure. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, isopentyl group, sec-pentyl group, hexyl group, heptyl group, octyl group, etc. Specific examples of the alkenyl group include vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, etc. R 4 and R 5 When the number of carbon atoms of the alkyl group or alkenyl group of is at least the lower limit value, the steric hindrance becomes large and it is less likely to be affected by a blowing agent such as hydrofluoroolefin, which is preferable. On the other hand, when the number of carbon atoms of the alkyl group of is at most the upper limit value, the steric hindrance does not become extremely large, so that the reaction between the polyol and the polyisocyanate can proceed rapidly and the foaming property also becomes good. 4 and R 5 From these viewpoints, R 4 and R 5 ​Each of these groups is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group.

[0029] Examples of imidazole derivatives represented by general formula (1) include 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. Among these, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferred from the viewpoint of improving the catalytic activity in the presence of hydrofluoroolefins and allowing the reaction to proceed rapidly. Furthermore, 1,2-dimethylimidazole is even more preferred from the viewpoint of further enhancing stability.

[0030] The content of the resinified metal catalyst in the polyol composition is not particularly limited, but is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, even more preferably 1 to 5 parts by mass, and even more preferably 1.5 to 4 parts by mass, per 100 parts by mass of the polyol compound. If the resinified metal catalyst is above the lower limit, the reaction rate between the polyol compound and the polyisocyanate compound is increased, making it easier to form a high-quality polyurethane foam. If the resinified metal catalyst is below the upper limit, the reaction rate between the polyol compound and the polyisocyanate compound can be appropriately controlled.

[0031] The content of nitrogen-containing heterocyclic compounds in the polyol composition is not particularly limited, but is preferably 0.3 to 15 parts by mass, more preferably 1 to 10 parts by mass, even more preferably 2 to 7 parts by mass, and still more preferably 2 to 3.5 parts by mass, per 100 parts by mass of the polyol compound. If the content of nitrogen-containing heterocyclic compounds is above the lower limit, urethane bond formation is more likely to occur, the reaction proceeds rapidly, and foaming properties are good. On the other hand, if the content of nitrogen-containing heterocyclic compounds is below the upper limit, the reaction rate is easier to control, which is preferable.

[0032] The total content of the resinification catalyst in the polyol composition is not particularly limited, but is preferably 0.3 to 25 parts by mass, more preferably 1 to 18 parts by mass, even more preferably 3 to 12 parts by mass, and still more preferably 3.5 to 8 parts by mass, per 100 parts by mass of the polyol compound. The resinified metal catalyst preferably contains at least one of the resinified metal catalyst and a nitrogen-containing heterocyclic compound, but it is more preferable that it contains both the resinified metal catalyst and the nitrogen-containing heterocyclic compound.

[0033] (trimerization catalyst) A trimerizing catalyst is a catalyst that promotes trimerization, which involves the formation of isocyanurate bonds, in a foamed urethane resin composition. This promotion of trimerization improves the flame retardancy and resistance to flame spread of the polyurethane foam. The trimerizing catalyst preferably contains at least one selected from quaternary ammonium salts and potassium salts, and more preferably contains both quaternary ammonium salts and potassium salts.

[0034] Quaternary ammonium salts Examples of quaternary ammonium salts include quaternary ammonium carboxylates. The carboxylic acid in the quaternary ammonium carboxylate may have one or more carbon atoms, but it is preferable that it has two or more carbon atoms. The carboxylic acid is preferably an aliphatic carboxylic acid, and more preferably a saturated aliphatic carboxylic acid. The number of carbon atoms in the carboxylic acid is, for example, 20 or less, but is preferably 12 or less, and more preferably 8 or less. The carboxylic acid may be linear or have a branched structure, but it is preferable that it has a branched structure. Having a branched structure tends to reduce reactivity with blowing agents such as hydrofluoroolefins due to steric hindrance, thus improving the stability of the polyol composition.

[0035] Suitable specific examples of carboxylic acids in quaternary ammonium carboxylates include 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. Among these, at least one selected from acetic acid and 2,2-dimethylpropanoic acid is preferred, and 2,2-dimethylpropanoic acid is more preferred.

[0036] In quaternary ammonium carboxylates, the quaternary ammonium ion is preferably a tetraalkylammonium ion or a hydroxyalkyltrialkylammonium ion, and more preferably a tetraalkylammonium ion.

[0037] Each alkyl group in the tetraalkylammonium ion is, for example, an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms, and more preferably a methyl group. Specific examples of tetraalkylammonium ions include tetramethylammonium ions and triethylmethylammonium ions.

[0038] Each alkyl group in the hydroxyalkyltrialkylammonium ion is, for example, an alkyl group having 1 to 4 carbon atoms, preferably a methyl group, an ethyl group, or a butyl group. A hydroxyalkyl group is a group in which one of the hydrogen atoms in the alkyl group is substituted with a hydroxyl group, for example, having 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms, and more preferably 3 or 4 carbon atoms. Examples of hydroxyalkyl groups include hydroxyethyl group, hydroxypropyl group, and hydroxybutyl group. Specific examples of hydroxyalkyltrialkylammonium ions include, for example, hydroxybutyltrimethylammonium ions, hydroxypropyltrimethylammonium ions, and hydroxyethyltrimethylammonium ions.

[0039] The ammonium ion in the quaternary ammonium carboxylate is preferably at least one selected from the group consisting of triethylmethylammonium ion, tetramethylammonium ion, hydroxybutyltrimethylammonium ion, and hydroxypropyltrimethylammonium ion, more preferably at least one selected from the group consisting of triethylmethylammonium ion, tetramethylammonium ion, and hydroxybutyltrimethylammonium ion, and even more preferably tetramethylammonium ion.

[0040] Furthermore, suitable specific examples of quaternary ammonium carboxylates include tetramethylammonium acetate, tetramethylammonium 2,2-dimethylpropanoate, triethylmethylammonium 2-ethylhexanoate, and hydroxybutyltrimethylammonium 2-ethylhexanoate. Among these, at least one selected from tetramethylammonium acetate and tetramethylammonium 2,2-dimethylpropanoate is preferred, and tetramethylammonium 2,2-dimethylpropanoate is more preferred, from the viewpoint of facilitating the formation of isocyanurate bonds by the trimer of polyisocyanate and facilitating the imparting of excellent flame retardancy to polyurethane foam. In this invention, quaternary ammonium carboxylates may be used alone or in combination of two or more types.

[0041] Potassium salts Examples of potassium salts include potassium carboxylate salts. The carboxylic acid in the potassium carboxylate salt may have one or more carbon atoms, but it is preferable that it has five or more carbon atoms. The carboxylic acid is preferably an aliphatic carboxylic acid, and more preferably a saturated aliphatic carboxylic acid. The number of carbon atoms in the carboxylic acid is, for example, 20 or less, but is preferably 12 or less, and more preferably 8 or less. The carboxylic acid may be linear or have a branched structure, but it is preferable that it has a branched structure. Having a branched structure tends to reduce reactivity with blowing agents such as hydrofluoroolefins due to steric hindrance, thus improving the stability of the polyol composition.

[0042] Potassium carboxylate salts are preferably those represented by the following general formula (2). Potassium carboxylate salts represented by the following general formula (2) have appropriate steric hindrance, which can suppress the reaction that decomposes the foaming agent and also prevent a decrease in catalytic activity.

[0043] [ka] (In general formula (2), R 1 and R 2 Each of these independently represents an alkyl group, and R 3 represents a hydrogen atom or an alkyl group. Also, K + (This represents potassium ions.)

[0044] R in general formula (2) 1 and R 2 Each of these independently represents an alkyl group, specifically, alkyl groups having 1 to 6 carbon atoms are preferred, alkyl groups having 1 to 4 carbon atoms are more preferred, and alkyl groups having 1 to 2 carbon atoms are even more preferred. The alkyl group may be linear or have a branched structure. R 1 , R 2 If the number of carbon atoms is greater than or equal to the lower limit, steric hindrance increases, which can suppress the reaction that decomposes hydrofluoroolefins. On the other hand, R 1 , and R2 If the number of carbon atoms is below the aforementioned upper limit, steric hindrance does not become too large, thus preventing the reaction from becoming slow. Also, R 3 R represents a hydrogen atom or an alkyl group, with a hydrogen atom being preferred. 3 If the alkyl group is an alkyl group, it is preferably one to six carbon atoms, more preferably one to four carbon atoms, and even more preferably one to two carbon atoms.

[0045] Preferred specific examples of carboxylic acids in potassium carboxylic acid salts include at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. Furthermore, carboxylic acids as shown in the above general formula (2) are preferred, and among these, 2,2-dimethylpropanoic acid and 2-ethylhexanoic acid are more preferred. In this invention, potassium carboxylate salts may be used alone or in combination of two or more types.

[0046] The content of the trimerizing catalyst in the polyol composition is preferably 2 to 20 parts by mass, more preferably 2.5 to 15 parts by mass, even more preferably 3 to 12 parts by mass, and still more preferably 3 to 8 parts by mass, per 100 parts by mass of the polyol compound. If the content of the trimerizing catalyst is above the lower limit, trimerization of the polyisocyanate is more likely to occur, and the flame retardancy of the resulting polyurethane foam is improved. On the other hand, if the content of the trimerizing catalyst is below the upper limit, the reaction is easier to control. Furthermore, the trimerizing catalyst contained in the polyol composition of the present invention may be used alone or in combination of two or more types.

[0047] Furthermore, the quaternary ammonium salt and potassium salt described above may contain only one of them, but it is also preferable to contain both. The content of the quaternary ammonium salt is preferably 1 to 10 parts by mass, more preferably 1.2 to 8 parts by mass, even more preferably 1.5 to 7 parts by mass, and still more preferably 1.5 to 5 parts by mass, per 100 parts by mass of the polyol compound. The potassium salt content is preferably 1 to 10 parts by mass, more preferably 1.2 to 8 parts by mass, even more preferably 1.3 to 5 parts by mass, and still more preferably 1.3 to 3 parts by mass, per 100 parts by mass of the polyol compound.

[0048] The polyol composition of the present invention preferably substantially does not contain nitrogen-containing compounds other than imidazole derivatives such as triethylenediamine, N,N-dimethylcyclohexylamine, diazabicycloundecene, tetramethylethylenediamine, tetramethylhexamethylenediamine, and hexamethyltriethylenetetramine as catalysts, and more preferably does not contain triethylenediamine. By substantially excluding nitrogen-containing compounds other than imidazole derivatives, particularly triethylenediamine, as catalysts, the storage stability of the polyol composition can be more easily improved. Furthermore, "substantially absent" means that the amount is such that it does not adversely affect storage stability, and the content may be, for example, less than 0.3 parts by mass per 100 parts by mass of the polyol compound, preferably 0.1 parts by mass or less, more preferably 0.05 parts by mass or less, and even more preferably 0 parts by mass.

[0049] (Foaming agent) The blowing agent promotes the foaming of the foamable urethane resin composition. Examples of blowing agents include organic physical blowing agents such as water, low-boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane; chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride; ether compounds such as hydrofluoroolefins (hereinafter sometimes referred to as "HFO") and diisopropyl ether; or mixtures of these compounds; and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Of these, it is preferable to include hydrofluoroolefin (HFO), which has high stability as a blowing agent, does not easily reduce catalytic activity, has a low environmental impact, and does not easily affect the flame retardancy of polyurethane foam.

[0050] 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), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,1,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), and trans-1,2,3,3,3-pene. Examples include tafluoropropene (HFO-1225ye(E)), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1,1,2,3,3-pentafluoropropene (HFO-1225yc), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)), and 1,1,1,4,4,4-hexafluorobuto-2-ene (HFO-1336mzz). Among these, HFO-1233zd(E) is preferred.

[0051] The content of the blowing agent is not particularly limited, but is preferably 20 to 57 parts by mass, more preferably 25 to 52 parts by mass, and even more preferably 30 to 46 parts by mass, per 100 parts by mass of the polyol compound. 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.

[0052] The above-mentioned foaming agents can be used individually or in combination of two or more. The polyol composition of the present invention preferably uses the above-mentioned HFO in combination with other foaming agents. For example, HFO may be used in combination with water, oxygen gas, or carbon dioxide gas, which have excellent handling properties. Water is particularly preferred from the viewpoint of adjusting the isocyanate index and ease of handling. The HFO content is preferably 20 to 55 parts by mass, more preferably 25 to 50 parts by mass, and even more preferably 30 to 45 parts by mass, per 100 parts by mass of the polyol compound. Keeping the HFO content within the above range allows for good foaming properties and makes it easier to impart excellent flame retardancy to the polyurethane foam. In particular, keeping the HFO content above a certain level allows the required water content to be kept below a certain level, making it easier to improve flame retardancy. The water content is preferably 0.1 to 2 parts by mass, more preferably 0.2 to 1.5 parts by mass, and even more preferably 0.5 to 1 part by mass, per 100 parts by mass of the polyol compound. Keeping the water content within the above range allows for good foaming properties, sufficient nurate bonds to be formed, and makes it easier to impart excellent flame retardancy to the polyurethane foam. In particular, keeping the water content below a certain level makes it easier to improve flame retardancy.

[0053] (Solid flame retardant) Solid flame retardants are flame retardants that become solid at room temperature (25°C) and normal pressure (1 atm). The polyol composition of the present invention exhibits improved flame retardancy by containing a solid flame retardant. Specific examples of solid flame retardants include phosphate-containing flame retardants, phosphorus-based compounds such as red phosphorus-based flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, and metal hydroxides.

[0054] 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 orthophosphate, phosphite, or hypophosphate, 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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 a boron-containing flame retardant containing borax and zinc borate, or one or more solid flame retardants of different classifications may be used, such as a red phosphorus-based flame retardant and a boron-containing flame retardant.

[0063] The amount of solid flame retardant is not particularly limited, but is preferably 10 to 120 parts by mass, more preferably 15 to 100 parts by mass, even more preferably 25 to 80 parts by mass, and even more preferably 30 to 60 parts by mass, per 100 parts by mass of the polyol compound. Increasing the amount of solid flame retardant makes it easier to impart high flame retardancy. On the other hand, decreasing the amount of solid flame retardant prevents the viscosity from increasing and makes it easier to improve the workability of the polyol composition.

[0064] (Filler) Any filler other than the solid flame retardants mentioned above may be used; specifically, inorganic fillers are examples of such fillers. Examples of inorganic fillers include diatomaceous earth, alumina, titanium dioxide, 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.

[0065] The filler content is not particularly limited, but is preferably 15 to 120 parts by mass, more preferably 25 to 110 parts by mass, and even more preferably 30 to 100 parts by mass, per 100 parts by mass of the polyol compound. Increasing the amount of filler makes it easier to impart high flame retardancy. On the other hand, decreasing the amount of filler prevents the viscosity from increasing and makes it easier to improve the workability of the polyol composition.

[0066] The polyol composition of the present invention may contain either a solid flame retardant or a filler, but from the viewpoint of imparting excellent flame retardancy to the polyurethane foam, it is preferable to include a solid flame retardant, more preferably a phosphorus compound, and even more preferably a red phosphorus flame retardant.

[0067] (Liquid flame retardant) The polyol composition of the present invention preferably contains a liquid flame retardant. Including a liquid flame retardant makes it easier to impart excellent flame retardancy to polyurethane foam without excessively increasing the viscosity of the polyol composition. A liquid flame retardant is one that becomes liquid at room temperature (25°C) and normal pressure (1 atm). While there are no particular limitations on the liquid flame retardant, a phosphate ester-based flame retardant is preferred.

[0068] As phosphate ester-based flame retardants, 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.

[0069] 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.

[0070] The phosphate ester flame retardants 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.

[0071] The content of the phosphate ester-based flame retardant in the polyol composition is not particularly limited, but is preferably 15 to 90 parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 30 to 60 parts by mass, per 100 parts by mass of the polyol compound. When the content of the phosphate ester-based flame retardant is above these lower limits, it becomes easier to impart flame retardancy to the polyurethane foam without making the viscosity of the polyol composition too high or the content of the solid flame retardant too high. Furthermore, when the content of the phosphate ester-based flame retardant is below these upper limits, foaming is not inhibited, making it easier to manufacture the polyurethane foam.

[0072] (Foam stabilizer) The polyol composition of the present invention may contain a foam stabilizer. Suitable foam stabilizers include compounds having polar and non-polar portions within their molecule and exhibiting surfactant properties. The foam stabilizer is not particularly limited, but examples include surfactants such as polyoxyalkylene foam stabilizers like polyoxyalkylene alkyl ethers and silicone foam stabilizers like organopolysiloxanes. As a silicone foam stabilizer, a graft copolymer of polyoxyalkylene glycol (a polymer of ethylene oxide or propylene oxide) and polydimethylsiloxane may also be used. Commercially available products can also be used, specifically foam stabilizers such as SH-193 (Toray Dow Corning), S-824-02 (Nippon Unicar), SZ-1704 (Nippon Unicar), F501 (Shin-Etsu Chemical Co., Ltd.), and SF-2937F (Dow Toray). The amount of foam stabilizer is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of the polyol compound.

[0073] (Other ingredients) In addition to the above, the polyol composition of the present invention may contain, as necessary and within the limits that do not impair its purpose, one or more additives selected from the following: anti-settling agents, antioxidants such as phenolic, amine, and sulfur-based agents, heat stabilizers, metal damage inhibitors (metal deactivators), antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, plasticizers, pigments, tackifying resins, polybutene, petroleum resins, and other tackifying agents.

[0074] [Foamed urethane resin composition] The present invention also provides a foamable urethane resin composition. The foamable urethane resin composition of the present invention can be obtained by mixing the above-mentioned polyol composition with a polyisocyanate compound. Furthermore, the foamed urethane resin composition may contain foam stabilizers, other components, etc., as needed. The details of each component in the foamed urethane resin composition, excluding the polyisocyanate compound, are as described above, and therefore, further explanation is omitted. The present invention also provides a polyurethane foam. The polyurethane foam of the present invention is formed by spray foaming a foamable urethane resin composition.

[0075] (Polyisocyanate compounds) Examples of polyisocyanate compounds include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates. Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate (also called polymeric MDI or crude MDI).

[0076] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0077] Examples of aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0078] Among these, aromatic polyisocyanates are preferred from the viewpoint of ease of use and availability, diphenylmethane diisocyanate, polymeric MDI, or mixtures thereof are more preferred, with diphenylmethane diisocyanate being even more preferred, and 4,4'-diphenylmethane diisocyanate being particularly preferred. Polyisocyanates may be used individually or as a mixture of two or more. Furthermore, before mixing the polyisocyanate compound with the polyol composition, known additives that are incorporated into polyisocyanate compounds may be added as appropriate.

[0079] Furthermore, it is preferable that the volume of the polyol composition and the polyisocyanate compound mixed with the polyol composition are substantially the same. Specifically, the volume ratio of the polyisocyanate compound to the polyol composition is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05.

[0080] (Isocyanate Index) In the foamable urethane resin composition of the present invention, the isocyanate index is preferably 250 or higher. When the isocyanate index is above this lower limit, the amount of polyisocyanate compound relative to the polyol compound becomes excessive, making it easier to form isocyanurate bonds by the trimer of the polyisocyanate compound, resulting in improved flame retardancy of the polyurethane foam. It also becomes possible to impart flame retardancy. Furthermore, when the index is above the lower limit, in combination with the various catalysts described above, it becomes easier to produce a polyurethane foam with sufficient isocyanurate bonds, that is, a polyurethane foam that combines flame retardancy and heat insulation at a high level. From these viewpoints, an isocyanate index of 270 or higher is more preferable, and 300 or higher is even more preferable. Furthermore, the isocyanate index is preferably 1,000 or less, more preferably 600 or less, and even more preferably 400 or less. When the isocyanate index is below the above upper limit, flame retardancy that is sufficiently commensurate with the manufacturing cost can be obtained.

[0081] The isocyanate index can be calculated using the following method. Isocyanate Index = Equivalents of polyisocyanate compound ÷ (Equivalents of polyol compound + Equivalents of water) × 100 Here, each equivalent number can be calculated as follows: • Equivalent weight of polyisocyanate compound = Amount of polyisocyanate compound used (g) × NCO content (mass%) / Molecular weight of NCO (moles) × 100 • Equivalent weight of polyol compound = OHV × Amount of polyol compound used (g) ÷ Molecular weight of KOH (millimoles) OHV is the hydroxyl value (mgKOH / g) of a polyol compound. • Equivalent amount of water = Amount of water used (g) / Molecular weight of water (moles) × Number of OH groups in water In the above formulas, the molecular weight of NCO is 42 moles, the molecular weight of KOH is 56,100 millimoles, the molecular weight of water is 18 moles, and the number of OH groups in water is 2.

[0082] (Method for manufacturing polyurethane foam) There are no particular restrictions on the method for producing polyurethane foam, but it is preferable to produce polyurethane foam by mixing a polyol composition with a polyisocyanate compound in a foaming machine or the like, and then spray foaming the resulting mixture (foamable urethane resin composition). As the foaming machine, a spray device equipped with a spray gun or the like is preferable. The polyol composition is supplied to a foaming machine and mixed with a polyisocyanate compound supplied from another container inside the foaming machine. The resulting mixture (foamable urethane resin composition) is then discharged from a nozzle such as a spray gun, and a polyurethane foam is formed from the discharged foamable urethane resin composition.

[0083] This manufacturing method is preferably applicable to spray applications. Therefore, the mixed liquid discharged from the foaming machine is sprayed onto the surface to be treated at a constant discharge pressure and foamed to form a polyurethane foam on the surface to be treated.

[0084] (Application) The uses of the foamable 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 spray 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 a polyol composition and a polyisocyanate compound in separate containers within the spraying device, causing them to collide and mix at the tip of the spray gun, and then 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]

[0085] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these examples.

[0086] [Materials used] (Polyisocyanate compounds) • 4,4'-Diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Manka Chemical Japan Co., Ltd., product name: PM200)

[0087] (Polyol composition) <Polyol compounds> • p-phthalate polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g) • Polyether polyol 1 (manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd., product name: Actcol GR-08, initiator: ethylenediamine, hydroxyl value = 820 mg KOH / g) • Polyether polyol 2 (manufactured by AGC, product name: EXCENOL 750ED, initiator: ethylenediamine, hydroxyl value = 760 mg KOH / g) • Polyether polyol 3 (manufactured by Mitsui Chemicals, product name: Actcol GR-40A, initiator: toluenediamine, hydroxyl value = 400 mg KOH / g) • Polyether polyol 4 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: DK Polyol 3776S, initiator: Mannich condensate, hydroxyl value = 350 mg KOH / g)

[0088] <Flame retardant> • Phosphate ester: Tris(β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP) • Red phosphorus (manufactured by Phosphorus Chemical Industry Co., Ltd., product name: Nova Excel 140)

[0089] <Foaming agent> ·water • Hydrofluoroolefin (HFO), trans-1-chloro-3,3,3-trifluoropropene (manufactured by Honeywell Japan, product name: Soltis LBA)

[0090] <Catalyst> • Resin-forming catalyst 1: Amine catalyst, triethylenediamine (manufactured by Tosoh Corporation, product name: TEDA-L33), concentration 33% by mass • Trimerization catalyst 1: Quaternary ammonium salt, tetramethylammonium 2,2-dimethylpropanoate (manufactured by Air Products, product name: DABCO(registered trademark) TMR7), concentration 45-55% by mass • Trimerization catalyst 2: Metal catalyst, potassium 2-ethylhexanoate (Air Products, Inc., product name: DABCO(registered trademark) K-15), concentration 70-80% by mass • Resin-based catalyst 2: Metal catalyst, bismastrioctate (manufactured by Nitto Chemical Co., Ltd., product name: Neostan U-600), concentration 55-58% by mass • Resin-forming catalyst 3: Amine catalyst, 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT(registered trademark)-DM70), concentration 65-75% by mass

[0091] [Measurement and evaluation methods for each physical property] (Workability) The workability of the polyol composition was evaluated according to the following procedures (1) to (3). (1) The polyol compositions and polyisocyanate compounds prepared in each example and comparative example were all heated to 38°C. (2) A polyol composition and a polyisocyanate compound, both heated to 38°C, were mixed in a spray gun at 20°C to obtain a foamable urethane resin composition. This composition was then spray-foamed onto a flexible board having dimensions of 600 mm × 300 mm × 9 mm, so that the foamed thickness was 20 mm or more, to obtain a polyurethane foam. (3) The workability of the polyol composition was evaluated based on the following evaluation criteria. <Evaluation Criteria> ○: No gaps were created between the flexible board and the polyurethane foam. ×: A gap formed between the flexible board and the polyurethane foam.

[0092] (Storage stability) The change in curing time was measured after curing the polyol compositions prepared in each example and comparative example at 55°C for 5 days. In this measurement, the polyol composition was sprayed onto a flexible board, and the time from the start of spraying until the surface hardened was defined as the curing time. Furthermore, the storage stability of the polyol composition was evaluated based on the following evaluation criteria. <Evaluation Criteria> ○: The curing time after curing was less than twice the curing time before curing. ×: The curing time after curing was more than twice the curing time before curing.

[0093] (Flame retardant) A polyurethane foam was obtained by spray-foaming a foamable urethane resin composition onto gypsum board using the same method as used for evaluating workability. The foam was then cut into pieces measuring 10 cm vertically, 10 cm horizontally, and 3.25 cm thick (with 12.5 mm of gypsum board thickness) to prepare samples for cone calorimeter testing. The cone calorimeter test samples were then measured for a radiant heat intensity of 50 kW / m² in accordance with the ISO-5660 test method. 2 The total heat generated when heated for 10 minutes was measured. Furthermore, the flame retardancy of the polyurethane foam was evaluated based on the following evaluation criteria. <Evaluation Criteria> 〇: Total heat output over 10 minutes is 8 MJ / m³ 2 The results were as follows: ×: Total heat output over 10 minutes is 8 MJ / m³ 2 It was incredible.

[0094] (judgement) Various physical properties were comprehensively evaluated based on the following evaluation criteria. <Evaluation Criteria> ○: All evaluation results for workability, storage stability, and flame retardancy were ○. ×: At least one of the evaluation results for workability, storage stability, and flame retardancy was ×.

[0095] [Examples 1-6, Comparative Examples 1-3] A polyol composition was prepared by mixing each component according to the formulations shown in Table 1. A polyurethane foam was manufactured using the polyol composition and a polyisocyanate compound, and various physical properties were evaluated. The results are shown in Table 1. The mixing ratio of the polyol composition to the polyisocyanate compound was 1:1 by volume.

[0096] [Table 1]

[0097] As is clear from the above results, the polyol composition prepared in the examples contained a polyether polyol synthesized with a nitrogen-containing compound as an initiator, and the polyester polyol content was higher than the polyether polyol content, resulting in excellent workability and storage stability. Furthermore, excellent flame retardancy was imparted to the polyurethane foam formed from this composition. In contrast, the polyol composition prepared in Comparative Example 3 did not contain a polyether polyol synthesized using a nitrogen-containing compound as an initiator, resulting in insufficient workability. Furthermore, since the polyol composition prepared in Comparative Example 1 did not contain a polyether polyol synthesized using a nitrogen-containing compound as an initiator, when highly reactive triethylenediamine was used as a catalyst to improve workability, the storage stability was insufficient. Furthermore, the polyol composition prepared in Comparative Example 2 did not contain a polyether polyol synthesized using a nitrogen-containing compound as an initiator. Therefore, hydrofluoroolefin was not included to prevent catalyst deactivation, but the flame retardancy was not good.

Claims

1. A polyol composition for obtaining a polyurethane foam by reacting with a polyisocyanate compound, The polyol composition comprises a polyester polyol, a polyether polyol, a catalyst, a blowing agent, and a solid flame retardant or filler. The polyether polyol includes a polyether polyol synthesized using a nitrogen-containing compound as an initiator. A polyol composition in which the content of the polyester polyol is greater than the content of the polyether polyol.

2. The polyol composition according to claim 1, wherein the initiator of the polyether polyol synthesized with the nitrogen-containing compound as an initiator is at least one selected from the group consisting of ethylenediamine, toluenediamine, triethanolamine, and Mannich condensates.

3. The polyol composition according to claim 1 or 2, wherein the content of the polyether polyol is 30 parts by mass or less per 100 parts by mass of the polyol compound.

4. The polyol composition according to claim 1 or 2, further comprising a liquid flame retardant.

5. The polyol composition according to claim 1 or 2, wherein the solid flame retardant comprises a phosphorus-based compound.

6. A polyol composition according to claim 1 or 2, comprising an organic acid bismuth salt.

7. A polyol composition according to claim 1 or 2, comprising a heterocyclic compound having a nitrogen atom.

8. A foamable urethane resin composition obtained by mixing the polyol composition according to claim 1 or 2 with a polyisocyanate compound.

9. The foamable urethane resin composition according to claim 8, wherein the isocyanate index is 250 or higher.

10. A polyurethane foam formed by spray foaming the foaming urethane resin composition described in claim 9.

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