Polyol-containing composition, foamable polyurethane composition, and polyurethane foam

Abstract

To provide a polyol-containing composition that can produce a polyurethane foam with no liquid separation and with high flame retardancy and high designability.SOLUTION: A polyol-containing composition is reacted with polyisocyanate to give a polyurethane foam, the polyol-containing composition containing a polyol, a foamer, a catalyst, a flame retardant, and a dye, the flame retardant containing a solid flame retardant.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyol-containing composition, a foaming polyurethane composition, and a polyurethane foam.

Background Art

[0002] Due to its excellent heat insulation and adhesiveness, polyurethane foam is used, for example, as a heat insulating material for buildings such as apartment houses, detached houses, various facilities in schools, and commercial buildings. Polyurethane foam is obtained by mixing a polyol composition and a polyisocyanate and foaming them, and spraying them onto objects such as ceilings, walls, and roofs 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 fire from spreading to the entire building by spreading to the polyurethane foam in the event of a fire. Therefore, solid flame retardants such as red phosphorus with a high flame retardant effect may be incorporated into the polyurethane foam.

[0003] In recent years, such polyurethane foams have been increasingly adopted in conspicuous places with the expansion of their applications, so the design of the surface has become more important. Along with this, the demand for colored polyurethane foams is also increasing. As a coloring means for polyurethane foam, for example, as described in Patent Document 1, a method of containing a pigment in a composition for producing a polyurethane foam containing a polyol can be mentioned.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, when using pigments in this way, the pigments are not sufficiently dispersed in the composition for producing polyurethane foam, and the pigments precipitate, resulting in liquid separation of the composition, uneven coloring of the polyurethane foam, and deterioration of the design quality.

[0006] Therefore, an object of the present invention is to provide a polyol-containing composition capable of producing a polyurethane foam that does not cause liquid separation and has high flame retardancy and design quality.

Means for Solving the Problems

[0007] As a result of intensive studies, the present inventor has found that a polyol-containing composition for obtaining a polyurethane foam by reacting with a polyisocyanate, which contains a polyol, a foaming agent, a catalyst, a flame retardant, and a dye, and the flame retardant contains a solid flame retardant, can solve the above problems, and has completed the present invention.

[0008] The present invention has the following gist of [1] to

[13] . [1] A polyol-containing composition for obtaining a polyurethane foam by reacting with a polyisocyanate, wherein the polyol-containing composition contains a polyol, a foaming agent, a catalyst, a flame retardant, and a dye, and the flame retardant contains a solid flame retardant. [2] The polyol-containing composition according to [1], wherein the solid flame retardant contains a red phosphorus-based flame retardant. [3] The polyol-containing composition according to [1] or [2], wherein the catalyst contains a trimerization catalyst. [4] The polyol-containing composition according to [3], wherein the trimerization catalyst contains a quaternary ammonium salt. [5] The polyol-containing composition according to any one of [1] to [4], wherein the catalyst contains an imidazole derivative. [6] The polyol-containing composition according to any one of [1] to [5], wherein the catalyst contains a metal catalyst selected from at least one of bismuth and tin. [7] The polyol-containing composition according to any one of [1] to [6], which does not cause liquid separation when stored in an environment of 40 ° C for 3 days. [8] A foaming polyurethane composition containing the polyol-containing composition according to any one of [1] to [7] and a polyisocyanate. [9] A foaming polyurethane composition containing a polyol, a polyisocyanate, a foaming agent, a catalyst, a flame retardant, and a dye, wherein the flame retardant contains a solid flame retardant.

[10] The foaming polyurethane composition according to [8] or [9], wherein the isocyanate index is 200 or more.

[11] The foaming polyurethane composition according to any one of [8] to

[10] , which is used for spraying applications.

[12] A polyurethane foam obtained by foaming the foaming polyurethane composition according to any one of [8] to

[11] .

[13] A method for producing a polyurethane foam, which comprises preparing a polyol-containing composition by blending at least a polyol, a foaming agent, a catalyst, and a flame retardant containing a solid flame retardant, mixing the polyol-containing composition with a polyisocyanate, and foaming to produce a polyurethane foam, wherein the dye is added in advance to the polyol-containing composition or the polyisocyanate, or added when the polyol-containing composition and the polyisocyanate are mixed. [Advantages of the Invention]

[0009] According to the present invention, it is possible to provide a polyol-containing composition capable of producing a polyurethane foam that does not cause liquid separation and has high flame retardancy and design properties. [Embodiments for Carrying Out the Invention]

[0010] [Polyol-Containing Composition] The polyol-containing composition of the present invention contains a polyol, a foaming agent, a catalyst, a flame retardant, and a dye.

[0011] [Dye] The colorant contained in the polyol-containing composition of the present invention is a dye. Dyes are generally dissolved in the polyol-containing composition and are sufficiently dispersed in the polyol-containing composition. Therefore, by using a dye instead of a pigment, liquid separation of the polyol-containing composition can be prevented, and the polyurethane foam can be uniformly colored. The dye can be a solvent dye, a disperse dye, or the like. The dye contained in the polyol-containing composition of the present invention is preferably at least one selected from the group consisting of black dyes and blue dyes. When the dye is a black dye, the color of the polyurethane foam becomes black or a gray color close to black, so that even if the polyurethane foam is colored red or pink by adding a flame retardant described later, the red color can be effectively masked to improve the design. Furthermore, if the dye is a blue dye, the dye exerts a complementary color effect, and red colors are more effectively masked, so that the color of the polyurethane foam becomes gray or close to gray, thereby improving the design. The term "blue dye" used in the present invention may refer not only to blue dyes but also to dyes of colors similar to blue, specifically purple dyes, light blue dyes, and the like.

[0012] The black dye or blue dye used in the present invention may be one that expresses a black or blue color by using only one type of compound, or may be one that expresses a black or blue color by using a combination of two or more types of compounds. Below, some specific examples of black dyes and blue dyes are listed in more detail as dyes, but the dyes used in the present invention are not limited to these, and dyes other than those listed below may be used as long as they can suppress liquid separation of the composition when contained in a polyol-containing composition.

[0013] As the black dye, nigrosine dye, azo dye, azine dye, etc. can be used, and various solvent blacks, reactive blacks, and disperse blacks described in the Color Index can be used. As the black dye, commercially available products may be used. For example, Reactint Black X95AB, Reactint Black 1852, Reactint Black 2256, Reactint Black X77, Reactint Black 454SS (all manufactured by Milliken&Company) etc. can be used. In addition, when using the black dye in the present invention, one kind may be used alone, or two or more kinds may be used in combination.

[0014] The blue-based dye may be a blue dye or a purple dye. Also, the blue dye may be a light blue dye. As the blue dye, various solvent blues, reactive blues, disperse blues etc. described in the Color Index can be used. Also, as the purple dye, various solvent violets, reactive violets, disperse violets etc. described in the Color Index can be used. As the blue-based dye, commercially available products may be used. For example, as the blue dye, Reactint Blue X17AB, Reactint Blue X77 (both manufactured by Milliken&Company) etc. can be mentioned. Also, as the blue dye, Cold Dye Navy Blue (manufactured by Keiya Fine Goods) etc. may be used, or light blue dyes such as Cold Dye Sky Blue (manufactured by Keiya Fine Goods) etc. may be used. Also, as the purple dye, for example, Reactint Violet X80LT (manufactured by Milliken&Company) etc. can be mentioned. In addition, when using the blue-based dye in the present invention, similar to the black dye, one kind may be used alone, or two or more kinds may be used in combination.

[0015] In the present invention, further, as long as the effects of the present invention are not impaired, dyes having a third color such as red, yellow, orange, etc., other than the black dye and the blue-based dye (hereinafter referred to as the third dye) may be used in combination with the black dye or the blue-based dye. Note that commercially available dyes can also be used as the third dye. Examples of commercially available products include Reactint Red X64, Reactint Orange X94, Reactint Yellow X15, Reactint Yellow X36 (all manufactured by Milliken&Company).

[0016] As the dye contained in the polyol-containing composition of the present invention, a blue-based dye is more preferable, and a blue dye is even more preferable. The blue-based dye can suppress the red color of the flame retardant more effectively than the black dye. By using the blue-based dye, the design property of the polyurethane foam can be further enhanced, and the content can be less than that when using the black dye, so that an effect commensurate with the production cost can be obtained.

[0017] The content of the dye is not particularly limited, but is preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the polyol. When the content of the dye is 0.2 parts by mass or more, the effect of using the dye can be obtained and the colorability of the polyurethane foam becomes good. Also, when it is 10 parts by mass or less, an effect commensurate with the blending amount can be obtained, and problems such as deterioration of the performance of the polyurethane foam due to the blending of the dye are less likely to occur. From these viewpoints, the content of the dye is, for example, more preferably 2 to 10 parts by mass and even more preferably 2 to 8 parts by mass in the case of a black dye. In the case of a blue-based dye, it is more preferably 0.1 to 8 parts by mass and even more preferably 0.2 to 6 parts by mass.

[0018] <Liquid separation> The polyol-containing composition of the present invention preferably does not cause color separation of the liquid component even when stored at 40°C for 3 days. By not causing color separation of the liquid component, variations in the shade of the colored polyurethane foam are suppressed, and the designability of the polyurethane foam is improved. Note that not causing color separation of the liquid component means a state where there is no separation of the color of the liquid component and no color unevenness is observed visually.

[0019] <Polyol> The polyol is not particularly limited, and examples thereof include polyether polyol, polyester polyol, etc. From the viewpoint of improving the flame retardancy of the polyurethane foam, the polyol preferably contains polyester polyol. Also, from the viewpoint of improving the flame retardancy, the use of halogen-containing polyol, phosphorus-containing polyol, etc. is also preferable. From such a viewpoint, among 100 parts by mass of the polyol, it is preferable that the polyester polyol is 20 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 80 parts by mass or more, and particularly preferably 100 parts by mass.

[0020] From the viewpoint of improving the flame retardancy of the polyurethane foam, the average hydroxyl value of the polyol used in the present invention is preferably 100 to 500 mgKOH / g, more preferably 150 to 450 mgKOH / g, and still more preferably 200 to 400 mgKOH / g.

[0021] Note that the average hydroxyl value means the hydroxyl value of the polyol when there is one type of polyol. Also, when using two or more types of polyols, the average hydroxyl value is the weighted average value of the hydroxyl groups according to the blending ratio of the two or more types of polyol compounds as the hydroxyl value of the polyol. For example, when using two types of polyols, polyol (d1) and polyol (d2), as the polyol, if the hydroxyl value of polyol (d1) is X1, the blending ratio is m1, the hydroxyl value of polyol (d2) is X2, and the blending ratio is m2, the average hydroxyl value is represented by the following formula. Note that the blending ratio is based on mass. 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.

[0022] (Polyester polyol) The polyester polyol may be an aromatic ring-containing polyester polyol or an aliphatic polyester polyol. However, considering the flame retardancy of the resulting polyurethane foam, it is preferable to use an aromatic ring-containing polyester polyol. The aromatic ring-containing polyester polyol 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), naphthalenedicarboxylic acid, and glycol. Among them, from the viewpoint of enhancing the flame retardancy of the polyurethane foam, the polyol compound preferably contains a phthalic acid-based polyester polyol that is a condensate of phthalic acid and glycol, and more preferably contains a p-phthalic acid-based polyester polyol that is a condensate of p-phthalic acid and glycol. The glycol is not particularly limited, but it is preferable to use a low-molecular-weight aliphatic glycol known as a constituent of polyester polyols such as ethylene glycol, propylene glycol, and diethylene glycol.

[0023] The hydroxyl value of the polyester polyol is preferably 100 to 500 mgKOH / g, more preferably 150 to 450 mgKOH / g, and even more preferably 200 to 400 mgKOH / g.

[0024] (Polyether polyol) A polyether polyol is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of an alkylene oxide to an initiator having two or more active hydrogen atoms. Specific examples of the initiator include aliphatic polyhydric alcohols (such as glycols like ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, cyclohexanedimethanol, etc., triols like trimethylolpropane, glycerin, etc., tetrafunctional alcohols like pentaerythritol, highly functional compounds like sucrose and sorbitol), aliphatic amines (such as alkylene diamines like ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, etc., alkanolamines like monoethanolamine, diethanolamine), aromatic amines (such as aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, Mannich condensates, etc.). The polyether polyol preferably has an aromatic ring. Among the above, a polyether polyol produced using an initiator having an aromatic ring is a polyether polyol having an aromatic ring. For example, a polyether polyol produced using an aromatic amine as an initiator is a polyether polyol having an aromatic ring. Among the polyether polyols having an aromatic ring, tolylenediamine-based polyether polyols, Mannich-based polyether polyols, etc. can be preferably used.

[0025] A tolylenediamine-based polyether polyol is a tolylenediamine-based polyether polyol produced using tolylenediamine as an initiator. The above-mentioned Mannich polyether polyol is obtained by using the 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 ring-opening addition polymerization of at least one of phenol and its alkyl-substituted derivatives, a Mannich condensate obtained by the Mannich reaction of formaldehyde and alkanolamine, or this compound with at least one of ethylene oxide and propylene oxide.

[0026] The hydroxyl value of the polyether polyol is preferably 200 to 2000 mgKOH / g, and more preferably 300 to 1000 mgKOH / g.

[0027] <Catalyst> (Metal catalyst (resinified metal catalyst)) The polyol-containing composition of the present invention contains a catalyst. The catalyst may contain, for example, one or both of a resinification catalyst and a trimerization catalyst, and it is preferable to contain both. The resinification catalyst preferably contains a metal catalyst. This metal catalyst is generally called a resinified metal catalyst. In the present invention, by containing the above resinified metal catalyst, the reaction between the polyol and the polyisocyanate is promoted, and in particular, the initial reaction rate can be increased. Also, when a certain amount or more of a filler such as a red phosphorus-based flame retardant described later is contained, the reactivity of the polyurethane foam is inhibited and the foamability is likely to decrease. However, by containing a resinified metal catalyst, it becomes easier to maintain good foamability of the polyurethane foam. From the viewpoint of foamability and the like, the above metal catalyst preferably contains bismuth or tin, and more preferably contains bismuth.

[0028] The above resinified metal catalyst preferably contains a metal salt selected from bismuth salts and tin salts, and more preferably a bismuth salt. The metal salt is preferably an organic acid metal salt, and more preferably a metal salt of a carboxylic acid having 5 or more carbon atoms. By having 5 or more carbon atoms, the carboxylic acid has good stability against foaming agents, particularly hydrofluoroolefins. Also, from the perspective of catalyst activity and the like, the number of carbon atoms of 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 may have a branched structure, but preferably has a branched structure. Specific examples of the carboxylic acid include octylic acid, lauric acid, versatic acid, pentanoic acid, acetic acid, etc., and among these, octylic acid is preferred. That is, the transition metal salt is preferably a metal salt of octylic acid. These carboxylic acids may be linear as described above, but may also have a branched structure. Note that as octylic acid having a branched structure, 2-ethylhexanoic acid can be mentioned. As the metal salt of the carboxylic acid, a bismuth salt of the carboxylic acid and a tin salt of the carboxylic acid are preferred, and among them, a bismuth salt of octylic acid is preferred. Also, the metal salt of the carboxylic acid may be a carboxylate of an alkyl metal. For example, the tin carboxylate may be a dialkyltin carboxylate or the like, and is preferably a dioctyltin carboxylate or the like. Specific examples of the metal salt of the carboxylic acid include bismuth trioctoate, dioctyltin versatate, dibutyltin dilaurate, dioctyltin dilaurate, tin dioctoate, etc., and preferably bismuth trioctoate, dioctyltin versatate, and more preferably bismuth trioctoate.

[0029] The content of the above resinified metal catalyst in the polyol-containing composition is not particularly limited, but is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass, still more preferably 1.5 to 8 parts by mass, and even more preferably 2 to 5 parts by mass with respect to 100 parts by mass of the polyol.

[0030] (Imidazole derivative) The catalyst used in the polyol-containing composition of the present invention preferably contains a resinifying amine catalyst as a resinifying catalyst, and more preferably contains an imidazole derivative as the resinifying amine catalyst. The imidazole derivative is hardly affected by hydrofluoroolefins, and facilitates the reaction between the polyol and the polyisocyanate while enhancing the stability of the polyol-containing composition. Therefore, in addition to the above-mentioned metal catalyst, the polyol-containing composition contains an imidazole derivative, so that the reactivity between the polyol and the polyisocyanate is enhanced and the foaming property becomes even better. The imidazole derivative is preferably an imidazole in which the 1-position and the 2-position are each independently substituted with an alkyl group having 8 or less carbon atoms, and the alkyl group preferably has 6 or less carbon atoms, more preferably 4 or less carbon atoms. Preferable specific examples of the imidazole derivative are represented by the following general formula (1).

[0031] [Chemical formula] (In the general formula (1), R 1 and R 2 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.)

[0032] R 1 and R 2 in the 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. Specific examples of the alkenyl group include a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group. R 1 and R 2 When the number of carbon atoms in the alkyl group or alkenyl group in R is equal to or greater than the lower limit, steric hindrance increases and the copolymer is less susceptible to the effects of blowing agents such as hydrofluoroolefins, which is preferable. 1 and R 2 When the number of carbon atoms in the alkyl group is equal to or less than the upper limit, the steric hindrance is not extremely large, so that the reaction between the polyol and the polyisocyanate can proceed quickly, and the foaming properties are also good. From these perspectives, R 1 and R 2 are each independently preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group.

[0033] The imidazole derivative represented by general formula (1) includes 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole, among which, from the viewpoint of improving the activity of the catalyst in the presence of hydrofluoroolefin and from the viewpoint of rapidly proceeding the reaction, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferred.Moreover, from the viewpoint of further increasing stability, 1,2-dimethylimidazole is even more preferred.

[0034] The content of the imidazole derivative in the polyol-containing composition is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, further preferably 2 to 15 parts by mass, and particularly preferably 3 to 10 parts by mass, relative to 100 parts by mass of the polyol. When the content of the imidazole derivative is equal to or more than the lower limit, the formation of a urethane bond is easily generated, the reaction proceeds quickly, and the foamability is good. On the other hand, when the content of the imidazole derivative is equal to or less than the upper limit, the reaction rate is easily controlled, which is preferable.

[0035] (Trimerization catalyst) The polyol-containing composition of the present invention preferably further contains a trimerization catalyst. The trimerization catalyst is a catalyst that reacts with the isocyanate groups contained in the polyisocyanate to trimerize and promotes the formation of an isocyanurate ring. By containing the trimerization catalyst, there is an advantage that a good polyurethane foam can be obtained by completing the reaction of unreacted isocyanate groups. Examples of the trimerization catalyst include metal catalysts and ammonium salts. Examples of the metal catalyst (trimerization metal catalyst) used as the trimerization catalyst include potassium organic acids, preferably potassium octylate such as potassium 2-ethylhexanoate, potassium acetate, potassium propionate, potassium butyrate, potassium benzoate, etc., which are potassium carboxylates having 2 to 8 carbon atoms. As the ammonium salt, tertiary ammonium salts such as triethylammonium salt and triphenylammonium salt, quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, and tetraphenylammonium salt can be used. Among these, quaternary ammonium salts are preferred. The ammonium salt is, for example, an ammonium salt of a carboxylic acid. Examples of the carboxylic acid in the ammonium salt include saturated fatty acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms. The saturated fatty acid may have a straight-chain hydrocarbon group or a branch, but preferably has a branch. Specific examples of the carboxylic acid include 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. Among these, 2,2-dimethylpropanoic acid is preferred. It may be used alone or in combination of two or more. The trimerization catalyst preferably contains at least a quaternary ammonium salt. It is more preferable to use a quaternary ammonium salt and a metal catalyst in combination.

[0036] The content of the trimerization catalyst in the polyol-containing composition is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, still more preferably 2 to 20 parts by mass, and even more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the polyol. When the content of the trimerization catalyst is at least the above lower limit value, there is no significant difference in the activities of resinification and trimerization, and the foaming can be suppressed from becoming two-stage, resulting in good foamability. On the other hand, when the content of the trimerization catalyst is at most the above upper limit value, the resinification reaction proceeds actively, and the heat of the resinification reaction can assist the activity of trimerization, resulting in good foamability and enabling the formation of a good polyurethane foam.

[0037] From the above viewpoints, for example, when an ammonium salt is contained as the trimerization catalyst, the content of the ammonium salt is preferably 0.3 to 23 parts by mass, more preferably 0.7 to 19 parts by mass, still more preferably 1.5 to 15 parts by mass, and even more preferably 3 to 11 parts by mass with respect to 100 parts by mass of the polyol. Further, when a metal catalyst is contained as the trimerization catalyst, the content of the metal catalyst is preferably 0.2 to 7 parts by mass, more preferably 0.3 to 6 parts by mass, still more preferably 0.5 to 5 parts by mass, and even more preferably 2 to 4 parts by mass with respect to 100 parts by mass of the polyol.

[0038] <Solid flame retardant> The polyol-containing composition of the present invention contains a solid flame retardant as a filler. Here, the solid flame retardant is a flame retardant that is solid at normal temperature (23°C) and normal pressure (1 atm), and is generally a component present in the form of granules or powder in the polyol-containing composition. By containing the solid flame retardant in the polyol-containing composition of the present invention, the flame retardancy of the polyurethane foam can be improved.

[0039] The solid flame retardant may be any component that is solid at normal temperature (23°C) and normal pressure (1 atm) and does not dissolve in the polyol-containing composition. From the viewpoint of reducing the water absorption rate of the polyurethane foam, the solid flame retardant preferably has no hygroscopicity and deliquescence. It should be noted that the above-mentioned catalysts are not included in the solid flame retardant. As the solid flame retardant in the present invention, specifically, red phosphorus-based flame retardants, metal phosphinates, phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, chlorine-containing flame retardants, metal hydroxides, etc. can be mentioned. These solid flame retardants may be used alone or in combination of two or more.

[0040] (Red phosphorus-based flame retardant) The red phosphorus-based flame retardant may consist of elemental red phosphorus, or may be red phosphorus coated with a resin, metal hydroxide, metal oxide, etc., or may be a mixture of red phosphorus with a resin, metal hydroxide, metal oxide, etc. The resin for coating or mixing with red phosphorus is not particularly limited, but examples include thermosetting resins such as phenol resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. From the viewpoint of flame retardancy, metal hydroxides are preferable as the compound for coating or mixing. As the metal hydroxide, those described later may be appropriately selected and used.

[0041] (Metal phosphinate) The metal phosphinate is a metal salt of an organic phosphinic acid. Specific examples of the metal phosphinate include, for example, aluminum tris(diethylphosphinate), aluminum tris(methylethylphosphinate), aluminum tris(diphenylphosphinate), zinc bis(diethylphosphinate), zinc bis(methylethylphosphinate), zinc bis(diphenylphosphinate), titanyl bis(diethylphosphinate), titanium tetrakis(diethylphosphinate), titanyl bis(methylethylphosphinate), titanium tetrakis(methylethylphosphinate), titanyl bis(diphenylphosphinate), titanium tetrakis(diphenylphosphinate), etc.

[0042] (Phosphate-containing flame retardant) Examples of the phosphate-containing flame retardant include phosphates composed of salts of various phosphoric acids and at least one metal or compound selected from metals in Groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. The term "various phosphoric acids" is a concept that includes not only phosphoric acid but also phosphorous acid, hypophosphorous acid, and the like. Examples of the metals in Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron(II), iron(III), aluminum, and the like. Examples of the aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, and the like. Examples of the aromatic amines include aniline, o-toluidine, 2,4,6-trimethylaniline, anisidine, 3-(trifluoromethyl)aniline, and the like. Examples of the heterocyclic compounds containing nitrogen in the ring include pyridine, triazine, melamine, and the like.

[0043] Specific examples of the phosphate-containing flame retardant include, for example, monophosphates, polyphosphates, and the like. The monophosphates are not particularly limited, and examples thereof include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; sodium salts such as sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium phosphite, disodium phosphite, and sodium hypophosphite; potassium salts such as potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium phosphite, dipotassium phosphite, and potassium hypophosphite; lithium salts such as lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, lithium phosphite, dilithium phosphite, and lithium hypophosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, barium phosphate, and barium hypophosphite; magnesium salts such as magnesium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite. Here, the polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, aluminum polyphosphate, and the like. The phosphate-containing flame retardant may be used alone or in combination of two or more thereof selected from the above.

[0044] (Bromine-containing flame retardant) The bromine-containing flame retardant is not particularly limited as long as it is a compound containing bromine in its molecular structure and is solid at normal temperature (23 °C) and normal pressure (1 atm), and examples thereof include aromatic compounds containing brominated aromatic rings. Examples of the aromatic compound containing a brominated aromatic ring 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.

[0045] The aromatic compound containing a brominated aromatic ring may also be a bromine compound polymer. Specifically, brominated polycarbonates such as polycarbonate oligomers produced from brominated bisphenol A, copolymers of this polycarbonate oligomer and bisphenol A, diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin, and the like can be mentioned. Furthermore, brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, condensates of brominated phenols of brominated polyphenylene ether, brominated bisphenol A, and cyanuric chloride, uncrosslinked or crosslinked brominated polystyrene, and the like can be mentioned. Compounds other than aromatic compounds containing brominated aromatic rings such as hexabromocyclododecane may also be used. These bromine-containing flame retardants may be used alone or in combination of two or more thereof.

[0046] (Boron-containing flame retardant) Examples of the boron-containing flame retardant used in the present invention include borax, boron oxide, boric acid, borate, etc. Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, tetraboron pentoxide, etc. Examples of borates include borates of alkali metals, alkaline earth metals, Group 4, Group 12, and Group 13 elements of the periodic table, and ammonium. Specifically, alkali metal borates such as lithium borate, sodium borate, potassium borate, cesium borate, etc., alkaline earth metal borates such as magnesium borate, calcium borate, barium borate, etc., zirconium borate, zinc borate, aluminum borate, ammonium borate, etc. The boron-containing flame retardant may be used alone or in combination of two or more. The boron-containing flame retardant used in the present invention is preferably a borate, and more preferably zinc borate.

[0047] (Antimony-containing flame retardant) Examples of the antimony-containing flame retardant include antimony oxide, antimonate, pyroantimonate, etc. Examples of antimony oxide include antimony trioxide, antimony pentoxide, etc. Examples of antimonate include sodium antimonate, potassium antimonate, etc. Examples of pyroantimonate include sodium pyroantimonate, potassium pyroantimonate, etc. The antimony-containing flame retardant may be used alone or in combination of two or more. The antimony-containing flame retardant used in the present invention is preferably antimony oxide.

[0048] (Chlorine-containing flame retardant) Examples of the chlorine-containing flame retardant include those commonly used in polyurethane foam, such as polychlorinated naphthalene, chlorendic acid, dodecachlorododecahydrodimethanodibenzocyclooctene sold under the trade name "Dechlorane Plus", etc.

[0049] (Metal hydroxide) Examples of the metal hydroxide 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, tin hydroxide, etc. The metal hydroxide may be used alone or in combination of two or more. As the metal hydroxide, aluminum hydroxide is preferable.

[0050] As the solid flame retardant contained in the polyol-containing composition of the present invention, from the viewpoint of imparting good flame retardancy to the polyurethane foam, at least one selected from the group consisting of red phosphorus-based flame retardants and metal phosphinates is preferable, and it is more preferable to contain at least a red phosphorus-based flame retardant.

[0051] The content of the solid flame retardant in the polyol-containing composition is preferably 20 to 150 parts by mass, more preferably 25 to 130 parts by mass, and still more preferably 30 to 120 parts by mass with respect to 100 parts by mass of the polyol. When a red phosphorus-based flame retardant is contained as the solid flame retardant, the content of the red phosphorus-based flame retardant is preferably 10 to 60 parts by mass, more preferably 15 to 50 parts by mass, and still more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the polyol. Further, when a metal phosphinate is contained as the solid flame retardant, the content of the metal phosphinate is preferably 35 to 120 parts by mass, more preferably 50 to 100 parts by mass, and still more preferably 60 to 90 parts by mass. When the content of these solid flame retardants is not less than the above lower limit value, it becomes possible to impart good flame retardancy and good mechanical properties to the polyurethane foam. On the other hand, when the content of these solid flame retardants is not more than the above upper limit value, the handleability and foamability when mixing the polyol-containing composition with the polyisocyanate become good.

[0052] <Liquid flame retardant> The polyol-containing composition of the present invention may contain a liquid flame retardant that is liquid at normal temperature (23°C) and normal pressure (1 atm). Specific examples of the liquid flame retardant include phosphate esters. By using a phosphate ester, the fluidity of the polyol-containing composition can be maintained, and the formation of polyurethane foam becomes easier.

[0053] As the phosphate ester, monophosphate esters, condensed phosphate esters, etc. can be used. A monophosphate ester is a phosphate ester having one phosphorus atom in the molecule. Examples of monophosphate esters include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, 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, diphenyl(2-ethylhexyl) phosphate; and acidic phosphate esters such as monoisodecyl phosphate, diisodecyl phosphate, etc.

[0054] Examples of condensed phosphate esters include aromatic condensed phosphate esters such as trialkyl polyphosphates, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, bisphenol A polyphenyl phosphate. Commercially available products of condensed phosphate esters include, for example, "CR-733S", "CR-741", "CR747" manufactured by Daihachi Chemical Industry Co., Ltd., "ADEKA STAB PFR", "FP-600" manufactured by ADEKA Corporation, etc.

[0055] The phosphate ester may be used alone or in combination of two or more thereof among those described above. Among these, from the viewpoint of facilitating appropriate adjustment of the viscosity of the polyol-containing composition and improving the flame retardancy of the polyurethane foam, monophosphate ester is preferable, and halogen-containing phosphate esters such as tris(β-chloropropyl) phosphate are more preferable. The content of the phosphate ester in the polyol-containing composition is preferably 5 to 100 parts by mass, more preferably 12 to 90 parts by mass, still more preferably 20 to 75 parts by mass, and even more preferably 30 to 60 parts by mass with respect to 100 parts by mass of the polyol.

[0056] <Inorganic filler> As the filler contained in the polyol-containing composition of the present invention, an inorganic filler other than the above-described solid flame retardant may be used. Examples of such inorganic fillers include acicular fillers, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, mica, montmorillonite, bentonite, activated clay, imogolite, sericite, glass beads, aluminum nitride, boron nitride, silicon nitride, various metal powders, magnesium sulfate, lead zirconate titanate, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash, etc., which can be appropriately used. These inorganic fillers may be used alone or in combination of two or more. The inorganic filler used in the present invention is not particularly limited, but from the viewpoint of imparting good mechanical properties to the polyurethane foam, etc., among those described above, it is preferable to contain an acicular filler. Further, it is more preferable that the polyol-containing composition contains at least one selected from the group consisting of a red phosphorus-based flame retardant and a metal phosphinate, and an acicular filler.

[0057] (Acicular filler) Examples of the acicular filler include potassium titanate whisker, aluminum borate whisker, magnesium-containing whisker, silicon-containing whisker, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fiber, carbon fiber, graphite fiber, metal fiber, slag fiber, gypsum fiber, silica fiber, alumina fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, stainless steel fiber, and the like. One or more of these acicular fillers can be used. The aspect ratio (length / diameter) of the acicular filler used in the present invention preferably ranges from 5 to 50, more preferably from 10 to 40. The aspect ratio can be determined by observing the acicular filler with a scanning electron microscope and measuring its length and width.

[0058] The content of the inorganic filler in the polyol-containing composition is not particularly limited, but is preferably 20 to 120 parts by mass, more preferably 30 to 100 parts by mass, and still more preferably 40 to 80 parts by mass with respect to 100 parts by mass of the polyol. When the content of the inorganic filler is at least the above lower limit value, it becomes possible to impart good mechanical properties to the polyurethane foam. On the other hand, when the content of the inorganic filler is at most the above upper limit value, the handleability and foamability are improved when the polyol-containing composition is mixed with the polyisocyanate composition. When an acicular filler is used as the inorganic filler, the content of the acicular filler is preferably 20 to 100 parts by mass, more preferably 25 to 95 parts by mass, and still more preferably 30 to 90 parts by mass with respect to 100 parts by mass of the polyol.

[0059] <Foaming agent> The foaming agent promotes the foaming of the foaming polyurethane composition described below. Examples of the foaming agent include low-boiling hydrocarbons such as water, propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, etc., chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, etc., hydrofluoroolefins (hereinafter sometimes referred to as "HFO"), ether compounds such as diisopropyl ether, or organic physical foaming agents such as mixtures of these compounds, and inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas, carbon dioxide gas, etc. Among these, it is preferable to contain hydrofluoroolefin (HFO) which has high stability as a foaming agent, is less likely to have its catalytic activity reduced, and further has a lower environmental load.

[0060] Examples of suitable HFO as the foaming agent include fluoroalkenes having about 3 to 6 carbon atoms. Further, the HFO may be a hydrochlorofluorooletin having a chlorine atom, and thus may be a chlorofluoroalkene having about 3 to 6 carbon atoms. Examples of HFO 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)), trans-1,2,3,3,3-pentafluoropropene (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)), 1,1,1,4,4,4-hexafluorobut-2-ene (HFO-1336mzz), etc. may be mentioned. Among these, HFO-1233zd(E) is preferable.

[0061] The content of the foaming agent is not particularly limited, and 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and still more preferably 35 to 60 parts by mass are preferable with respect to 100 parts by mass of the polyol. When the content of the foaming agent is at least the above lower limit value, foaming is promoted, the foamability becomes good, and the density of the polyurethane foam can be reduced. On the other hand, when the content of the foaming agent is at most the above upper limit value, it is possible to suppress the excessive progress of foaming.

[0062] As described above, one kind or two or more kinds of foaming agents can be used. In the foaming polyurethane composition of the present invention, it is preferable to use 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 are excellent in handleability. In particular, water is preferable from the viewpoints of adjusting the isocyanate index and ease of handling.

[0063] The content of the HFO is not particularly limited, and preferably 19 to 75 parts by mass, more preferably 29 to 67 parts by mass, still more preferably 34 to 58 parts by mass, based on 100 parts by mass of the polyol. When the content of the blowing agent is equal to or higher than the lower limit value, foaming is promoted, the foamability becomes good, and the density of the polyurethane foam can be reduced. On the other hand, when the content of the blowing agent is equal to or lower than the upper limit value, it is possible to suppress the excessive progress of foaming.

[0064] The content of water is not particularly limited, and preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, still more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the polyol. When the content of the blowing agent is equal to or higher than the lower limit value, foaming is promoted, the foamability becomes good, and the density of the polyurethane foam can be reduced. On the other hand, when the content of the blowing agent is equal to or lower than the upper limit value, it is possible to suppress the excessive progress of foaming.

[0065] <Foam stabilizer> The polyol-containing composition of the present invention may contain a foam stabilizer. By containing a foam stabilizer, the foamability of the polyurethane foam can be improved, and for example, when reacting with a polyisocyanate in spray spraying, foaming can be promoted. Specific examples of the foam stabilizer include surfactants, and more specifically, nonionic surfactants, cationic surfactants, anionic surfactants, etc. can be exemplified. Specific examples of the nonionic surfactant include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, and silicone foam stabilizers such as organopolysiloxanes. The foam stabilizer used in the present invention is not particularly limited, but a silicone foam stabilizer is preferred from the viewpoint of foamability. The foam stabilizer may be used alone or in combination of two or more.

[0066] The content of the foam stabilizer in the polyol-containing composition of the present invention is preferably 0.1 to 12 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 2 to 8 parts by mass with respect to 100 parts by mass of the polyol. When the content of the foam stabilizer is not less than the above lower limit value, it becomes easier to foam the mixture of the polyol-containing composition and the polyisocyanate composition, so that a homogeneous polyurethane foam can be obtained. Further, when the content of the foam stabilizer is not more than the above upper limit value, the balance between the production cost and the obtained effect becomes optimal.

[0067] <Other components> The polyol-containing composition may contain, as necessary, one or more selected from antioxidants such as phenolic, amine-based, and sulfur-based antioxidants, heat stabilizers, metal damage inhibitors (metal deactivators), antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, plasticizers, tackifier resins, etc., and tackifiers such as polybutene and petroleum resins, etc., within the range not impairing the object of the present invention.

[0068] [Foamable polyurethane composition, and polyurethane foam] The present invention also provides a foamable polyurethane composition. The foamable polyurethane composition of the present invention contains a polyisocyanate in addition to a polyol, a foaming agent, a catalyst, a flame retardant, and a dye. Further, the foamable polyurethane composition may contain fillers other than the flame retardant, liquid flame retardants such as phosphate esters, etc., or may contain a foam stabilizer, other components, etc. Note that the details of each component contained in the foamable polyurethane composition are as described above, and the description thereof is omitted.

[0069] The foamable polyurethane composition of the present invention preferably contains the above polyol-containing composition and poly isocyanate, and is obtained by mixing these. Before mixing the polyol-containing composition and the polyisocyanate, it is advisable to store them in separate containers. Also, as will be described later, the foaming polyurethane composition may include a polyol-containing composition that does not contain a dye and a polyisocyanate that contains a dye, or it may be obtained by mixing these. Also, the foaming polyurethane composition may be one in which a polyol-containing composition that does not contain a dye, a polyisocyanate that does not contain a dye, and a dye are separately prepared and obtained by mixing these immediately before use.

[0070] <Polyisocyanate> Examples of the polyisocyanate in the present invention include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates. Examples of the aromatic polyisocyanate include phenylenediisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI).

[0071] Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0072] Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0073] Among these, from the viewpoints of ease of use and availability, aromatic polyisocyanates are preferred, diphenylmethane diisocyanate, polymeric MDI, or a mixture thereof is more preferred, and among them, diphenylmethane diisocyanate is even more preferred, and in particular, 4,4'-diphenylmethane diisocyanate is preferred. The polyisocyanate may be used alone or in combination of two or more. Also, before mixing with the polyol-containing composition, known additives to be compounded in the polyisocyanate may be appropriately compounded in the polyisocyanate.

[0074] It should be noted that the polyol-containing composition and the polyisocyanate mixed with the polyol-containing composition preferably have substantially the same volume. Specifically, the volume ratio of the polyisocyanate composition to the polyol-containing composition is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05.

[0075] <Isocyanate index> There is no particular limitation on the isocyanate index in the foaming polyurethane composition of the present invention, but it is preferably 200 or more. When the isocyanate index is at or above the lower limit value, the amount of polyisocyanate relative to the polyol becomes excessive and isocyanurate bonds formed by trimers of polyisocyanate are likely to be generated. As a result, the flame retardancy of the polyurethane foam is improved. Also, it becomes possible to impart flame retardancy. Furthermore, when it is at or above the above lower limit value, in combination with the above-described various catalysts used together, it is easy to produce a polyurethane foam having sufficient isocyanurate bonds, that is, a polyurethane foam having high levels of flame retardancy and heat insulation. From these viewpoints, the isocyanate index is more preferably 250 or more, and even more preferably 300 or more. Also, the isocyanate index is preferably 1,000 or less, more preferably 800 or less, and even more preferably 600 or less. When the isocyanate index is at or below the upper limit value, flame retardancy commensurate with the production cost can be obtained.

[0076] The isocyanate index can be calculated by the following method. Isocyanate index = Number of equivalents of polyisocyanate ÷ (Number of equivalents of polyol + Number of equivalents of water) × 100 Here, each number of equivalents can be calculated as follows. · Number of equivalents of polyisocyanate = Amount of polyisocyanate used (g) × NCO content (mass %) / Molecular weight of NCO (mol) × 100 · Number of equivalents of polyol = OHV × Amount of polyol used (g) ÷ Molecular weight of KOH (mmol) OHV is the hydroxyl value of the polyol (mgKOH / g). · Number of equivalents of water = Amount of water used (g) / Molecular weight of water (mol) × Number of OH groups of water In the above formulas, the molecular weight of NCO is 42 (mol), the molecular weight of KOH is 56,100 (mmol), the molecular weight of water is 18 (mol), and the number of OH groups of water is 2.

[0077] <Total heat release> The polyurethane foam composed of the foaming polyurethane composition of the present invention, in accordance with the test method of ISO-5660, when heated at a radiant heat intensity of 50 kW / m 2 for 10 minutes, the total heat release is preferably 8 MJ / m 2 or less. By having a total heat release of 8 MJ / m 2 or less, the polyurethane foam composed of the foaming polyurethane composition of the present invention has a predetermined flame retardancy. From the viewpoint of further improving the flame retardancy of the foam, the above total heat release is more preferably 7.5 MJ / m 2 or less, and even more preferably 7 MJ / m 2 or less. Also, the polyurethane foam composed of the foaming polyurethane composition of the present invention, even when heated for 20 minutes by the same method as above, the total heat release is more preferably 8 MJ / m 2 or less, and particularly preferably 7.5 MJ / m 2 or less.

[0078] The foaming polyurethane composition of the present invention preferably has a color difference ΔE of 3 or more, more preferably 4 or more, and even more preferably 5 or more, between polyurethane foam A obtained by mixing the above polyol-containing composition and a polyisocyanate, and polyurethane foam B obtained by mixing a polyol-containing composition without a colorant and a polyisocyanate. When the color difference ΔE is equal to or greater than the lower limit value, it can be said that the polyurethane foam is well colored. Note that the polyol-containing composition without a colorant means a polyol-containing composition having the same composition as the polyol-containing composition except that a colorant such as a dye is not blended. The above color difference ΔE can be obtained by preparing polyurethane foams A and B by the method described in the examples using the polyol-containing composition and the polyisocyanate constituting the foaming polyurethane composition, and also using a polyol-containing composition without a colorant and a polyisocyanate, and measuring the color difference with respect to the polyurethane foams A and B.

[0079] <Use> The foaming polyurethane composition of the present invention can preferably be used for spraying applications. Therefore, the foaming polyurethane composition of the present invention and the use of the polyurethane foam may be excellent in flame retardancy and heat insulation, and can be suitably used for buildings such as walls, ceilings, roofs, and floors of buildings. It is preferable to mold the polyurethane foam with walls, ceilings, roofs, floors, etc. as the spraying target surface.

[0080] <Method for producing polyurethane foam> The method for producing a polyurethane foam of the present invention is to prepare a polyol-containing composition by blending at least a flame retardant containing a polyol, a foaming agent, a catalyst, and a solid flame retardant, and then mixing and foaming the polyol-containing composition and a polyisocyanate to produce a polyurethane foam. In the method for producing a polyurethane foam, the dye may be added in advance to either the polyol-containing composition or the polyisocyanate, or may be added when the polyol-containing composition and the polyisocyanate are mixed.

[0081] First, a method of adding the dye in advance to the polyol-containing composition will be described as a first embodiment. The method for producing a polyurethane foam according to the first embodiment of the present invention first prepares a polyol-containing composition by blending at least a polyol, a foaming agent, a catalyst, a flame retardant containing a solid flame retardant, and a dye. Here, there is no particular limitation on the method for preparing the polyol-containing composition. For example, it can be obtained by stirring each component at about 20 to 40 °C for about 30 seconds to 20 minutes using a homodisper or the like. The polyol-containing composition obtained by preparing by this method contains a dye, and the details are as described above. Then, the polyol-containing composition thus prepared and the polyisocyanate are brought to the construction site and mixed on-site to obtain a foaming polyurethane composition, and the foaming polyurethane composition is reacted and foamed to produce a polyurethane foam.

[0082] Next, a method of adding the dye in advance to the polyisocyanate will be described as a second embodiment. The method for producing a polyurethane foam according to the second embodiment of the present invention first prepares a polyol-containing composition by blending at least a polyol, a foaming agent, a catalyst, and a flame retardant containing a solid flame retardant. Here, the method for preparing the polyol-containing composition is as described above. Also, the polyol-containing composition obtained by preparing by this method is the same as the polyol-containing composition described above except that it does not contain a dye. Then, the polyol-containing composition thus prepared and the polyisocyanate added with the dye are brought to the construction site and mixed on-site to obtain a foaming polyurethane composition, and the foaming polyurethane composition is reacted and foamed to produce a polyurethane foam.

[0083] Furthermore, as a third embodiment, a method of adding a dye when mixing a polyol-containing composition and a polyisocyanate will be described. That is, in the third embodiment, a polyol-containing composition is prepared by blending at least a polyol, a blowing agent, a catalyst, and a flame retardant containing a solid flame retardant. At this time, the polyol-containing composition may not contain a dye. Therefore, the polyol-containing composition obtained by preparing by this method is the same as the polyol-containing composition described above except that it does not contain a dye. Then, the polyol-containing composition, the polyisocyanate, and the dye are brought to the construction site, and the dye is added (also referred to as post-addition) when the polyol-containing composition and the polyisocyanate are mixed at the construction site. By adding the dye post-addition, it can be adjusted to a preferred color tone at the site. Here, the phrase "when mixing the polyol-containing composition and the polyisocyanate" does not strictly require the dye to be added simultaneously with the mixing of the polyol-containing composition and the polyisocyanate, and includes a mode of adding the dye to the polyol-containing composition or the polyisocyanate immediately before mixing brought to the construction site. Note that immediately before mixing means, for example, within about one week before mixing, preferably within about three days, more preferably within about one day. In addition, the polyol-containing composition or the polyisocyanate to which the dye has been added once can be used if re-stirred at the time of reuse regardless of the storage period.

[0084] Therefore, the dye may be added to the polyol-containing composition at the construction site, and the polyol-containing composition to which the dye has been added may be further mixed with the polyisocyanate. Also, the dye may be added to the polyisocyanate at the construction site, and the polyisocyanate to which the dye has been added may be mixed with the polyol-containing composition. Further, at the construction site, the dye, the polyol-containing composition, and the polyisocyanate may be mixed together simultaneously. Among these, it is preferable to add the dye to the polyol-containing composition at the construction site and then mix the polyol-containing composition with the added dye further with the polyisocyanate.

[0085] The polyurethane foam is preferably produced, for example, using a foaming machine. For example, it may be produced by mixing the polyol-containing composition with the polyisocyanate in a foaming machine or the like and then foaming the resulting mixed liquid (foamable polyurethane composition). As the foaming machine, a spraying device having a spray gun or the like may be used. At this time, as described above, it is preferable that the dye is incorporated in either the polyol-containing composition or the polyisocyanate, but it is preferably contained in the polyol-containing composition. The polyol-containing composition may be fed into the foaming machine and collided and mixed with the polyisocyanate fed from another container or the like inside the foaming machine. Then, the mixed liquid (foamable polyurethane composition) may be discharged from a discharge port such as a spray gun, and the polyurethane foam may be formed with the discharged foamable polyurethane composition.

[0086] This production method can preferably be applied to spraying applications. Therefore, the mixed liquid discharged from the foaming machine may be sprayed onto the surface to be constructed at a certain discharge pressure and foamed to form the polyurethane foam on the surface to be constructed.

Examples

[0087] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

[0088] [Materials Used] <Polyisocyanate> ·4,4'-Diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Wanhua Chemical Japan Co., Ltd., product name: PM200)

[0089] <Polyol-Containing Composition> (Polyol) p-Phthalic acid polyester polyol (Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g)

[0090] (catalyst) Ammonium salt (trimerization catalyst), tetramethylammonium salt of 2,2-dimethylpropanoic acid (Air Products, product name: DABCO (registered trademark) TMR7) concentration 45 to 55 mass% Metal catalyst (trimerization catalyst), potassium 2-ethylhexanoate (manufactured by Air Products, product name: DABCO (registered trademark) K-15) concentration 70 to 80% by mass Resinized amine catalyst, 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT DM70) concentration 65-75% by mass Resinized metal catalyst, bismuth trioctate (manufactured by Nitto Kasei, product name: Neostan U-600) concentration 55-58% by mass Resinized metal catalyst, dioctyl (2-ethylhexyl) tin versatate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-830), concentration approximately 99% by mass

[0091] (foaming agent) Hydrofluoroolefin (HFO), trans-1-chloro-3,3,3-trifluoropropene (Honeywell, product name: Solstice LBA) ·water

[0092] (Liquid flame retardant) Phosphate ester plasticizer: Tris(β-chloropropyl)phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name: TMCPP)

[0093] (Solid flame retardant) Red phosphorus flame retardant (Rinkagaku Kogyo Co., Ltd., product name: Nova Excel 140) Metal phosphinate (Clariant, product name: EXOLIT OP930)

[0094] (Inorganic filler) Wollastonite (SiO2·CaO) (Kinsei Matec Co., Ltd., product name: SH-1250)

[0095] (Colorant) ·Black colorant: Black dye (manufactured by Milliken & Company, product name: REACTINT BLACK X95AB), black pigment (manufactured by Milliken & Company, product name: DispersiTech Black 2140) ·Blue colorant: Blue pigment (manufactured by Milliken & Company, product name: DispersiTech Blue 2402)

[0096] [Manufacture of polyurethane foam] Each component was mixed according to the formulation described in Table 1 to prepare a polyol-containing composition. Using the polyol-containing composition and polyisocyanate, a polyurethane foam was manufactured under the following conditions. <Manufacturing conditions> ·Spraying machine: Graco spraying device H-25 ·Setting (heater setting) Isocyanate heater: 38 °C Premix heater (for heating polyol-containing composition): 38 °C Hose heater (for preheating before mixing polyisocyanate and polyol-containing composition): 38 °C Pressure: Appropriately adjusted so that the mist forms a wide circular shape ·Substrate temperature (temperature of the spraying surface): 20 °C ± 1 °C

[0097] [Evaluation methods for each physical property] 1. Liquid separation The polyol-containing composition was stored in a mayonnaise bottle at 40 °C for 3 days, and the liquid separation state of the composition was visually confirmed. The evaluation criteria for liquid separation are as follows. 〇: No liquid separation ×: Liquid separation present

[0098] 2. Flame retardancy The polyurethane foam prepared under the above manufacturing conditions was cut into a cube of 10 cm × 10 cm × 5 cm to obtain a test piece. The test piece was in accordance with ISO 5660, and the radiant heat intensity was 50 kW / m 2The total calorific value when heated for 10 to 20 minutes was measured. The evaluation criteria for flame retardancy are as follows. 〇: 8 MJ / m at the 20-minute mark from the start of heating 2 Below △: 8 MJ / m at the 10-minute mark from the start of heating 2 Below ×: More than 8 MJ / m at the 10-minute mark from the start of heating 2 Exceeding

[0099] 3. Colorability A polyurethane foam A formed by reacting a polyol-containing composition containing a dye with a polyisocyanate, and a polyurethane foam B formed by reacting a polyol-containing composition not containing a colorant (a polyol-containing composition not containing a colorant) with a polyisocyanate were each prepared. A color difference meter (manufactured by KONICA MINOLTA, product name: SPECTROPHOTOMETER CM-5) was applied to the respective surfaces of the polyurethane foams A and B, and after obtaining the color difference ΔE between the two polyurethane foams, the colorability of the surface was evaluated based on the color difference ΔE. The evaluation criteria for colorability are as follows. 〇: ΔE = 3 or more, coloring present ×: ΔE < 3, no coloring

[0100] [Examples 1 to 12, Comparative Examples 1 to 6] Each component was mixed according to the formulation described in Table 1 to prepare a polyol-containing composition. A polyurethane foam was produced using the polyol-containing composition and a polyisocyanate, and evaluations based on the above evaluation methods 1 to 3 were performed. The results are shown in Table 1. The mixing ratio of the polyol-containing composition and the polyisocyanate was 1:1 by volume.

[0101]

Table 1

[0102] As is clear from the results of the above Examples and Comparative Examples, the polyol-containing composition of the present invention did not undergo liquid separation, and the polyurethane foam formed from the composition had good flame retardancy and colorability. On the other hand, the polyol-containing compositions of Comparative Examples 1 to 5 contained a pigment as a colorant, and thus liquid separation occurred. In addition to the occurrence of liquid separation, the polyol-containing composition of Comparative Example 5 did not contain a solid flame retardant, so the flame retardancy of the polyurethane foam was impaired. Further, since the polyol-containing composition of Comparative Example 6 did not contain any colorant, the polyurethane foam could not be colored.

Claims

1. A polyol-containing composition for obtaining a polyurethane foam by reacting with a polyisocyanate, wherein the polyol-containing composition contains a polyol, a blowing agent, a catalyst, a flame retardant, and a dye, and the flame retardant contains a solid flame retardant.

2. The polyol-containing composition according to claim 1, wherein the solid flame retardant contains a red phosphorus-based flame retardant.

3. The polyol-containing composition according to claim 1 or 2, wherein the catalyst contains a trimerization catalyst.

4. The polyol-containing composition according to claim 3, wherein the trimerization catalyst contains a quaternary ammonium salt.

5. The polyol-containing composition according to any one of claims 1 to 4, wherein the catalyst contains an imidazole derivative.

6. The polyol-containing composition according to any one of claims 1 to 5, wherein the catalyst contains a metal catalyst selected from at least one of bismuth or tin.

7. The polyol-containing composition according to any one of claims 1 to 6, which does not undergo liquid separation when stored in an environment of 40 °C for 3 days.

8. A foaming polyurethane composition containing the polyol-containing composition according to any one of claims 1 to 7 and a polyisocyanate.

9. A foaming polyurethane composition containing a polyol, a polyisocyanate, a blowing agent, a catalyst, a flame retardant, and a dye, and the flame retardant contains a solid flame retardant.

10. The foaming polyurethane composition according to claim 8 or 9, wherein the isocyanate index is 200 or more.

11. The foaming polyurethane composition according to any one of claims 8 to 10, which is used for spraying applications.

12. A polyurethane foam obtained by foaming the foaming polyurethane composition according to any one of claims 8 to 11.

13. Prepare a polyol-containing composition by blending at least a polyol, a blowing agent, a catalyst, and a flame retardant containing a solid flame retardant, A method for producing a polyurethane foam, comprising mixing the polyol-containing composition with a polyisocyanate and foaming to produce a polyurethane foam, A method for producing a polyurethane foam, wherein a dye is added in advance to the polyol-containing composition or the polyisocyanate, or added when the polyol-containing composition and the polyisocyanate are mixed.

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