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

Abstract

To provide a polyol-containing composition that suppresses decolorization of a colorant even when stored for a long time, and a polyurethane foam having 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 pigment, 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] Polyurethane foam is used as a heat insulating material for buildings such as condominiums, single-family houses, various facilities in schools, and commercial buildings, etc. because of its excellent heat insulating property and adhesiveness. Polyurethane foam is obtained by mixing a polyol composition and a polyisocyanate and foaming them, and spraying them onto an object such as a ceiling, wall, or roof using a spraying device or the like. Since such polyurethane foam is used in buildings, it is required to have flame retardancy in order to prevent the fire from spreading to the polyurethane foam and causing a fire to spread throughout the building even when a fire occurs. Therefore, a solid flame retardant such as red phosphorus, which has a high flame retardant effect, may be blended in the polyurethane foam.

[0003] In recent years, with the expansion of applications, such polyurethane foams have come to be adopted in conspicuous places, and thus the design property of the surface has come to be emphasized. Along with this, the demand for colored polyurethane foams is also increasing. As a coloring means for polyurethane foam, for example, a method of containing a dye in a polyol composition for forming polyurethane foam, as described in Patent Document 1, 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 such a conventional polyol composition contains a dye as a colorant, the dye may dissolve in the polyol composition and react with other components such as a solid flame retardant and a catalyst, particularly an ammonium salt-based catalyst. Therefore, after storing the polyol composition for a long time and then foaming it, there has been a problem that the dye has already been decolorized and the polyurethane foam cannot be colored in a desired color.

[0006] Therefore, an object of the present invention is to provide a polyurethane foam having flame retardancy and high design properties together with a polyol-containing composition in which decolorization of the colorant is suppressed even after long-term storage.

Means for Solving the Problems

[0007] As a result of intensive studies, the present inventors have 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 pigment, and in which the flame retardant contains a solid flame retardant, can solve the above problems, and have completed the present invention.

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

[13] . [1] 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 pigment, and in which 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 the group consisting of bismuth and tin. [7] A foaming polyurethane composition containing the polyol-containing composition according to any one of [1] to [6] and a polyisocyanate. [8] The foaming polyurethane composition according to [7], wherein the color difference between polyurethane foam A obtained by mixing the polyol-containing composition and the polyisocyanate and polyurethane foam B obtained by mixing the polyol-containing composition stored at 55 °C for 3 days and the polyisocyanate is 3 or less. [9] A foaming polyurethane composition containing a polyol, a polyisocyanate, a foaming agent, a catalyst, a flame retardant, and a pigment, and wherein the flame retardant contains a solid flame retardant.

[10] The foaming polyurethane composition according to any one of [7] to [9], wherein the isocyanate index is 200 or more.

[11] The foaming polyurethane composition according to any one of [7] to

[10] , which is used for spraying applications.

[12] A polyurethane foam obtained by foaming the foaming polyurethane composition according to any one of [7] 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 and a polyisocyanate, and reacting and foaming them to produce a polyurethane foam, wherein the pigment is added to the polyol-containing composition or the polyisocyanate in advance, or added when the polyol-containing composition and the polyisocyanate are mixed. [Effect of the Invention]

[0009] According to the present invention, it is possible to provide a polyol-containing composition in which decoloration of the colorant is suppressed even after long-term storage, and a polyurethane foam having flame retardancy and high design quality. [Embodiments for Carrying Out the Invention]

[0010] [Polyol-containing composition] The polyol-containing composition of the present invention contains a polyol, a blowing agent, a catalyst, a flame retardant, and a pigment.

[0011] <Pigments> The polyol-containing composition of the present invention contains a pigment as a colorant. The pigment is a solid at room temperature (23°C) and normal pressure (1 atm), and is generally present as a granular or powdered component in the polyol-containing composition. In addition, since the pigment does not react with other components in the polyol-containing composition, discoloration of the colorant is suppressed by using the pigment instead of the dye that has been publicly used as a colorant, and it becomes possible to color the polyurethane foam to a desired color. The pigment may be either an inorganic pigment or an organic pigment. The pigment contained in the polyol-containing composition of the present invention is preferably at least one selected from the group consisting of black pigments and blue pigments. When the pigment is a black pigment, the color of the polyurethane foam is 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 pigment is a blue pigment, the pigment 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 properties. The term "blue pigment" used in the present invention may refer not only to blue pigments but also to pigments of colors similar to blue, specifically purple pigments, light blue pigments, and the like.

[0012] The black pigment or blue pigment used in the present invention may be one that expresses a black or blue color by using only one type of compound, or one that expresses a black or blue color by using a combination of two or more types of compounds. Hereinafter, specific examples of black pigments and blue pigments will be listed in more detail as pigments. However, the pigments used in the present invention are not limited to these, and pigments other than those listed below may be used as long as decolorization by other components in the polyol-containing composition is effectively suppressed.

[0013] Examples of black pigments include carbon black, graphite, iron black, titanium black, aniline black, cyanine black, etc., and various pigment blacks described in the Color Index can also be used. Among these, carbon black is preferred as the black pigment. As the black pigment, commercially available products may be used. For example, DispersiTech Black2140 (manufactured by Milliken&Company) etc. can be mentioned. In addition, when using a black pigment in the present invention, one kind may be used alone, or two or more kinds may be used in combination.

[0014] The blue pigment may be a blue pigment or a purple pigment. Also, the blue pigment may be a light blue pigment. Examples of blue pigments include ultramarine, azurite, Prussian blue, ultramarine blue, smalt, cobalt blue (cobalt aluminate), cerulean blue (cobalt stannate), cobalt chromium blue, cobalt-aluminum-silicate oxide, cobalt-zinc-silicate oxide, manganese blue, phthalocyanine, etc. In addition, specific examples of purple pigments include, for example, inorganic pigments such as cobalt violet (cobalt arsenate, cobalt phosphate, cobalt-lithium-phosphate oxide, hydrated ammonium cobalt phosphate, cobalt borate, etc.), violet ultramarine, iron oxide purple, manganese violet, mineral violet, etc., and organic pigments such as indigoid, quinacridone, oxazine, anthraquinone, carbonium, xanthene, etc. Also, as the blue pigment, various pigment blues described in the Color Index etc. can be used, and as the purple pigment, various pigment violets etc. can also be used.

[0015] As the cyan pigment, commercially available products may be used. For example, DispersiTech Blue2402 (manufactured by Milliken & Company), Mitsui PS Blue RR, PET Blue 2000 (all manufactured by Mitsui Chemicals Fine Inc.), Mitsui PS Violet RC (manufactured by Mitsui Chemicals Fine Inc.), etc. can be mentioned. In addition, when using the cyan pigment in the present invention, similar to the black pigment, one type may be used alone, or two or more types may be used in combination.

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

[0017] The content of the pigment is not particularly limited, but it is preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the polyol. When the content of the pigment is 0.2 parts by mass or more, the effect of using the pigment 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 pigment are less likely to occur. From these viewpoints, the content of the pigment is, for example, more preferably 1 to 10 parts by mass and even more preferably 2 to 8 parts by mass in the case of the black pigment. Also, in the case of the cyan pigment, it is more preferably 0.1 to 8 parts by mass and even more preferably 0.2 to 6 parts by mass.

[0018] <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, it is preferable that the polyol contains polyester polyol. Also, from the viewpoint of improving the flame retardancy, it is also preferable to use halogen-containing polyol, phosphorus-containing polyol, etc. 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.

[0019] 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.

[0020] 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. 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.

[0021] (Polyester polyol) The polyester polyol may be a polyester polyol having an aromatic ring or an aliphatic polyester polyol, but 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), 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 which is a condensate of phthalic acid and glycol, and more preferably contains a p-phthalic acid-based polyester polyol which is a condensate of p-phthalic acid and glycol. As the glycol, although not particularly limited, it is preferable to use a low molecular weight aliphatic glycol known as a constituent component of polyester polyol such as ethylene glycol, propylene glycol, diethylene glycol.

[0022] The hydroxyl value of the polyester polyol is preferably 100 to 500 mgKOH / g, more preferably 150 to 450 mgKOH / g, and still more preferably 200 to 400 mgKOH / g.

[0023] (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, high-functional alcohols like sucrose, sorbitol, etc.), 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, the polyether polyol produced using an initiator having an aromatic ring is a polyether polyol having an aromatic ring. For example, the 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.

[0024] 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 the Mannich reaction of at least one of phenol and its alkyl-substituted derivatives, formaldehyde and alkanolamine, or by ring-opening addition polymerization of at least one of ethylene oxide and propylene oxide to this compound.

[0025] The hydroxyl value of the polyether polyol is preferably 200 to 2000 mgKOH / g, and more preferably 300 to 1000 mgKOH / g.

[0026] <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 resinifying catalyst and a trimerizing catalyst, and it is preferable to contain both. The resinifying 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 filler such as a solid flame retardant described later is contained in a certain amount or more, the reactivity of the polyurethane foam is inhibited and the foamability is likely to decrease. However, by containing a resinified metal catalyst, the foamability of the polyurethane foam can be easily maintained well. From the viewpoint of foamability and the like, the above metal catalyst is preferably selected from at least one of the group consisting of bismuth and tin, and more preferably contains bismuth.

[0027] The above resinified metal catalyst preferably comprises a metal salt selected from bismuth salts and tin salts, more preferably a bismuth salt. The metal salt is preferably an organic acid metal salt, 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 provides 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, more preferably 12 or less. The carboxylic acid is preferably an aliphatic carboxylic acid, 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., among which 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 the 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 salt of the carboxylic acid may be a dialkyltin carboxylate or the like, 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 dioctylate, etc., preferably bismuth trioctoate, dioctyltin versatate, more preferably bismuth trioctoate.

[0028] 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.

[0029] (Imidazole derivative) The catalyst used in the polyol-containing composition of the present invention preferably contains a resinification amine catalyst as a resinification catalyst, and more preferably contains an imidazole derivative as the resinification amine catalyst. The imidazole derivative is less 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, thereby enhancing the reactivity between the polyol and the polyisocyanate and further improving the foaming property. 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. Preferred specific examples of the imidazole derivative are represented by the following general formula (1).

[0030]

Chemical formula

[0031] R in general formula (1) 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. 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, an octenyl group, and the like. R 1 and R 2 When the number of carbon atoms in the alkyl group or alkenyl group of R and R is equal to or greater than the lower limit value, the steric hindrance increases and it becomes difficult to be affected by a blowing agent such as hydrofluoroolefin, which is preferable. On the other hand, R 1 and R 2 When the number of carbon atoms in the alkyl group of R and R is equal to or less than the upper limit value, the steric hindrance does not extremely increase, so that the reaction between the polyol and the polyisocyanate can proceed rapidly and the foamability is also good. From these viewpoints, 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 still more preferably a methyl group.

[0032] Examples of the imidazole derivative represented by the general formula (1) include 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methylimidazole. Among them, from the viewpoints of improving the activity of the catalyst in the presence of hydrofluoroolefin and allowing the reaction to proceed rapidly, 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole are preferable. Further, from the viewpoint of further enhancing the stability, 1,2-dimethylimidazole is more preferable.

[0033] 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, still more preferably 2 to 15 parts by mass, and particularly preferably 3 to 10 parts by mass with respect to 100 parts by mass of the polyol. When the content of the imidazole derivative is equal to or greater than the lower limit value, the formation of urethane bonds is likely to occur, the reaction proceeds rapidly, 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 value, it is preferable because the reaction rate is easily controlled.

[0034] (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 acid, 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. The trimerization catalyst may be used alone or in combination of two or more. The trimerization catalyst preferably contains a quaternary ammonium salt. In the present invention, since a pigment is used as the colorant, even if a quaternary ammonium salt is used, problems such as decolorization of the colorant are less likely to occur. More preferably, the trimerization catalyst is used in combination with a quaternary ammonium salt and a metal catalyst.

[0035] 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, there is no significant difference in activity between resinification and trimerization, and it is possible to suppress the foaming 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, 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.

[0036] 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.

[0037] <Solid flame retardant> The polyol-containing composition of the present invention contains a solid flame retardant as a flame retardant. 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 a granular or powdery form in the polyol-containing composition. By containing such a solid flame retardant in the polyol-containing composition of the present invention, the flame retardancy of the polyurethane foam can be improved.

[0038] 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 catalyst is 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.

[0039] (Red phosphorus-based flame retardant) The red phosphorus-based flame retardant may be composed of elemental red phosphorus, or may be one in which red phosphorus is coated with a resin, metal hydroxide, metal oxide, etc., or may be one in which red phosphorus is mixed 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 phenolic resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. From the viewpoint of flame retardancy, metal hydroxides are preferred as the compound for coating or mixing. As the metal hydroxide, those described later may be appropriately selected and used.

[0040] (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), and the like.

[0041] (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, etc. Examples of the metals in Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), aluminum, etc. Examples of the aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, etc. Examples of the aromatic amines include aniline, o-toluidine, 2,4,6-trimethylaniline, anisidine, 3-(trifluoromethyl)aniline, etc. Examples of the heterocyclic compounds containing nitrogen in the ring include pyridine, triazine, melamine, etc.

[0042] Specific examples of the phosphate-containing flame retardant include, for example, monophosphates, polyphosphates, etc. The monophosphates are not particularly limited, but examples include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, etc., sodium salts such as sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium phosphite, disodium phosphite, sodium hypophosphite, etc., potassium salts such as potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium phosphite, dipotassium phosphite, potassium hypophosphite, etc., lithium salts such as lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, lithium phosphite, dilithium phosphite, lithium hypophosphite, etc., barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, barium phosphate, barium hypophosphite, etc., magnesium salts such as magnesium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, magnesium hypophosphite, etc., calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite, etc., zinc salts such as zinc phosphate, zinc phosphite, zinc hypophosphite, etc. 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.

[0043] (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, ethylene bis(pentabromophenyl), ethylene bis(tetrabromophthalimide), and tetrabromobisphenol A.

[0044] Further, the aromatic compound containing a brominated aromatic ring may 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. Further, 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. Moreover, compounds other than aromatic compounds containing brominated aromatic rings such as hexabromocyclododecane may be used. These bromine-containing flame retardants may be used alone or in combination of two or more thereof.

[0045] (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, elements of Group 4, Group 12, and Group 13 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.

[0046] (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 antimonates include sodium antimonate, potassium antimonate, etc. Examples of pyroantimonates 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.

[0047] (Chlorine-containing flame retardant) Examples of the chlorine-containing flame retardant include those commonly used in polyurethane foams, such as polychlorinated naphthalene, chlorendic acid, dodecachlorododecahydrodimethanodibenzocyclooctene sold under the trade name "Dechlorane Plus", etc.

[0048] (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 preferred.

[0049] 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.

[0050] 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 equal to or higher 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 equal to or lower than the above upper limit value, the handleability and foamability become good when the polyol-containing composition is mixed with the polyisocyanate.

[0051] <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 it becomes easier to form a polyurethane foam.

[0052] As the phosphate ester, a monophosphate ester, a condensed phosphate ester, etc. can be used. A monophosphate ester is a phosphate ester having one phosphorus atom in the molecule. Examples of the monophosphate ester 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.

[0053] Examples of the condensed phosphate ester include aromatic condensed phosphate esters such as trialkyl polyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate. Examples of commercially available products of the condensed phosphate ester include "CR-733S", "CR-741", "CR747" manufactured by Daihachi Chemical Industry Co., Ltd., and "ADEKA STAB PFR", "FP-600" manufactured by ADEKA Corporation.

[0054] The phosphate ester may be used alone or in combination of two or more thereof from 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 esters are preferred, and halogen-containing phosphate esters such as tris(β-chloropropyl) phosphate are more preferred. 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.

[0055] <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 thereof. 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.

[0056] (Acicular filler) Examples of the acicular filler include potassium titanate whisker, aluminum borate whisker, magnesium-containing whisker, silicon-containing whisker, wollastonite, sepiolite, zonolite, elesta-dite, 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, etc. 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.

[0057] 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. 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.

[0058] <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, 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 reduce the catalytic activity, and further has a lower environmental load.

[0059] 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 therefore, it 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), and the like can be mentioned. Among these, HFO-1233zd(E) is preferable.

[0060] 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 not less than the above lower limit value, foaming is promoted, the foamability is good, and the density of the polyurethane foam can be reduced. On the other hand, when the content of the foaming agent is not more than the above upper limit value, it is possible to suppress the excessive progress of foaming.

[0061] As described above, one or more kinds of foaming agents can be used. In the foamable 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.

[0062] 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 at least 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 at most the upper limit value, it is possible to suppress the excessive progress of foaming.

[0063] 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 at least 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 at most the upper limit value, it is possible to suppress the excessive progress of foaming.

[0064] <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. 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. 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.

[0065] 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 equal to or higher than the lower limit value, it becomes easier to foam the mixture of the polyol-containing composition and the polyisocyanate, so that a homogeneous polyurethane foam can be obtained. Further, when the content of the foam stabilizer is equal to or lower than the upper limit value, the balance between the production cost and the obtained effect becomes optimal.

[0066] <Other components> The polyol-containing composition may contain, as necessary within a range not impairing the object of the present invention, one or more selected from antioxidants such as phenolic, amine-based, and sulfur-based antioxidants, heat stabilizers, metal damage preventives (metal deactivators), antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, plasticizers, tackifier resins, and other additives, and tackifiers such as polybutene and petroleum resins.

[0067] [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 blowing agent, a catalyst, a flame retardant, and a pigment. Further, the foamable polyurethane composition may contain a filler other than the flame retardant, a liquid flame retardant such as a phosphate ester, or may contain a foam stabilizer, other components, and the like. Note that the details of each component contained in the foamable polyurethane composition are as described above, and the description thereof is omitted.

[0068] 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 described later, the foaming polyurethane composition may include a polyol-containing composition that does not contain a pigment and a polyisocyanate that contains a pigment, 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 pigment, a polyisocyanate that does not contain a pigment, and a pigment are prepared separately and mixed immediately before use.

[0069] <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).

[0070] Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0071] Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0072] Among these, from the viewpoints of ease of use and availability, aromatic polyisocyanates are preferred, diphenylmethane diisocyanate, polymeric MDI, or a mixture thereof are 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. Further, before mixing with the polyol-containing composition, known additives incorporated into the polyisocyanate may be appropriately incorporated into the polyisocyanate.

[0073] In addition, the polyol-containing composition and the polyisocyanate to be mixed with the polyol-containing composition preferably have substantially the same volume. Specifically, the volume ratio of the polyisocyanate 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.

[0074] <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 equal to or higher than the lower limit value, the amount of the polyisocyanate relative to the polyol becomes excessive and isocyanurate bonds are easily formed by the trimer of the polyisocyanate. As a result, the flame retardancy of the polyurethane foam is improved. In addition, it becomes possible to impart flame retardancy. Furthermore, when it is equal to or higher than the above lower limit value, in combination with the above-mentioned 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 equal to or lower than the upper limit value, flame retardancy commensurate with the production cost can be obtained.

[0075] Note that 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 (mgKOH / g) of the polyol. · Number of equivalents of water = Amount of water used (g) / Molecular weight of water (mol) × Number of OH groups in 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 in water is 2.

[0076] <Total heat release> The polyurethane foam made of the foaming polyurethane composition of the present invention, in accordance with the test method of ISO-5660, has a total heat release of 8 MJ / m 2 when heated at a radiant heat intensity of 50 kW / m for 10 minutes. 2 It is preferably as follows. When the total heat release is 8 MJ / m 2 or less, the polyurethane foam made 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 made of the foaming polyurethane composition of the present invention has a total heat release of 8 MJ / m 2 or less even when heated for 20 minutes by the same method as above, and more preferably 7.5 MJ / m 2 or less, and particularly preferably 7.5 MJ / m

[0077] In the present invention, it is preferable that the color difference ΔE(1) between polyurethane foam A obtained by mixing a polyol-containing composition containing a pigment and a polyisocyanate, and polyurethane foam B obtained by mixing a polyol-containing composition stored at 55°C for 3 days and a polyisocyanate is 3 or less. When the color difference ΔE(1) is 3 or less, it can be said that the decolorization of the pigment in the polyol-containing composition is suppressed even when the polyol-containing composition containing the pigment is stored for a long period. Considering such points, the color difference ΔE(1) is preferably 2 or less, and more preferably 1 or less. The above color difference ΔE(1) 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 that constitute the foaming polyurethane composition, and measuring the color difference with respect to the polyurethane foams A and B.

[0078] Further, in the foaming polyurethane composition of the present invention, it is preferable that the color difference ΔE(2) between polyurethane foam A obtained by mixing the above polyol-containing composition and a polyisocyanate, and polyurethane foam C obtained by mixing a polyol-containing composition not containing a colorant and a polyisocyanate is 3 or more. The color difference ΔE(2) is more preferably 4 or more, and still more preferably 5 or more. When the color difference ΔE(2) is equal to or greater than the above lower limit value, it can be said that the polyurethane foam can be colored well. Note that the polyol-containing composition not containing a colorant means a polyol-containing composition having the same composition as the polyol-containing composition except that a colorant such as a pigment is not blended. The above color difference ΔE(2) can be obtained by preparing polyurethane foams A and C by the method described in the examples using the polyol-containing composition and the polyisocyanate that constitute the foaming polyurethane composition, and also using a polyol-containing composition not containing a colorant and a polyisocyanate, and measuring the color difference with respect to the polyurethane foams A and C.

[0079] <Use> The foamed polyurethane composition of the present invention can preferably be used for spraying applications. Therefore, the foamed polyurethane composition and the use of the polyurethane foam of the present invention may also 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 advisable to form a polyurethane foam with surfaces such as walls, ceilings, roofs, and floors as the spraying target surfaces.

[0080] <Method for manufacturing polyurethane foam> The method for manufacturing a polyurethane foam of the present invention is to prepare a polyol-containing composition by blending at least a polyol, a foaming agent, a catalyst, and a flame retardant containing a solid flame retardant, and then mix the polyol-containing composition with a polyisocyanate and foam it to produce a polyurethane foam. In the method for manufacturing a polyurethane foam, the pigment 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] Hereinafter, first, a method of adding the pigment to the polyol-containing composition in advance will be described as a first embodiment. The method for manufacturing a polyurethane foam according to the first embodiment of the present invention is to first prepare 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 pigment. 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 prepared by this method contains a pigment, and the details are as described above.

[0082] Then, the polyol-containing composition prepared in this way and the polyisocyanate are brought to the construction site and mixed on-site to obtain a foamed polyurethane composition, and the foamed polyurethane composition is reacted and foamed to produce a polyurethane foam.

[0083] Next, a method of previously adding a pigment to 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. Further, 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 pigment.

[0084] Then, the polyol-containing composition prepared in this way and the polyisocyanate added with a pigment 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.

[0085] Furthermore, a method of adding a pigment when mixing the polyol-containing composition and the polyisocyanate will be described as a third embodiment. That is, in the third embodiment, a polyol-containing composition is prepared by blending at least a polyol, a foaming agent, a catalyst, and a flame retardant containing a solid flame retardant. At this time, the polyol-containing composition may not contain a pigment. 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 pigment. Then, the polyol-containing composition, the polyisocyanate, and the pigment are brought to the construction site, and the pigment is added (also referred to as post-added) when the polyol-containing composition and the polyisocyanate are mixed on-site. By post-adding the pigment, it is possible to adjust to a preferred color tone on-site. Note that when mixing the polyol-containing composition and the polyisocyanate, strictly speaking, it is not necessary to add the pigment simultaneously with the mixing of the polyol-containing composition and the polyisocyanate. This also includes the mode of adding the pigment to the polyol-containing composition or the polyisocyanate immediately before mixing, which is brought to the construction site. Note that "immediately before mixing" means, for example, within about one week before mixing, preferably within about three days, and more preferably within about one day. Note that the polyol-containing composition or the polyisocyanate to which the pigment has been added once can be used if re-stirred at the time of re-use regardless of the storage period.

[0086] Therefore, at the construction site, the pigment may be added to the polyol-containing composition, and the polyol-containing composition to which the pigment has been added may be further mixed with the polyisocyanate. Also, the pigment may be added to the polyisocyanate at the construction site, and the polyisocyanate to which the pigment has been added may be mixed with the polyol-containing composition. Further, at the construction site, the pigment, the polyol-containing composition, and the polyisocyanate may be mixed together simultaneously. Among these, it is preferable that at the construction site, the pigment is added to the polyol-containing composition, and the polyol-containing composition to which the pigment has been added is further mixed with the polyisocyanate.

[0087] 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 foaming the obtained 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 pigment is blended 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 a foaming machine and collided and mixed with 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 a polyurethane foam may be formed with the discharged foamable polyurethane composition.

[0088] 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 constant discharge pressure and foamed to form a polyurethane foam on the surface to be constructed.

Examples

[0089] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

[0090] [Materials Used] [Polyisocyanate] ·4,4'-Diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Wanhua Chemical Japan Co., Ltd., product name: PM200)

[0091] [Polyol-Containing Composition] [Polyol] ·p-Phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mgKOH / g)

[0092] [Catalyst] ·Ammonium salt (trimerization catalyst), tetramethylammonium 2,2-dimethylpropanoate (manufactured by Air Products, product name: DABCO® TMR7) concentration 45 - 55% by mass ·Metal catalyst (trimerization catalyst), potassium 2-ethylhexanoate (manufactured by Air Products, product name: DABCO® K-15) concentration 70 - 80% by mass ·Resinified amine catalyst, 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT DM70) concentration 65 - 75% by mass · Resin-metallized catalyst, bismuth trioctoate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600) concentration 55 - 58 mass% · Resin-metallized catalyst, dioctyl (2-ethylhexyl)tin versatate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-830) concentration approximately 99 mass%

[0093] (Foaming agent) · Hydrofluoroolefin (HFO), trans-1-chloro-3,3,3-trifluoropropene (manufactured by Honeywell, product name: Solstice LBA) · Water

[0094] (Liquid flame retardant) · Phosphate ester plasticizer tris(β-chloropropyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name: TMCPP)

[0095] (Solid flame retardant) · Red phosphorus-based flame retardant (manufactured by Phosphorus Chemical Industry Co., Ltd., product name: Nova Excel 140) · Metal phosphinate (manufactured by Clariant, product name: Exolit OP930)

[0096] (Inorganic filler) · Wollastonite (SiO2·CaO) (manufactured by Kinsai Matech Co., Ltd., product name: SH-1250)

[0097] (Colorant) · Black colorant: Black pigment (manufactured by Milliken&Company, product name: DispersiTech Black 2140), black dye (manufactured by Millilken&Company, product name: REACTINT BLACK X95AB) · Blue colorant: Blue pigment (manufactured by Milliken&Company, product name: DispersiTech Blue 2402)

[0098] [Manufacture of polyurethane foam] The formulation described in Table 1 Each component was mixed according to the following to prepare a polyol-containing composition. Using the polyol-containing composition and polyisocyanate, a polyurethane foam was produced under the following conditions. <Manufacturing Conditions> · Spraying machine: Graco spraying device H-25 · Settings (heater settings) Isocyanate heater: 38°C Premix heater (for heating the polyol-containing composition): 38°C Hose heater (for pre-heating before mixing of 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

[0099] [Evaluation Method for Polyurethane Foam] 1. Degree of discoloration The foaming polyurethane composition was put into a pale can and stored at 55°C for 3 days, and then sprayed and foamed to obtain polyurethane foam B. Similarly, the foaming polyurethane composition was put into another pale can, and without storage, it was sprayed and foamed immediately after being put into the pale can to obtain polyurethane foam A. A color difference meter (manufactured by KONICA MINOLTA, product name: SPECTROPHOTOMETER CM-5) was applied to the surface of the polyurethane foam obtained as described above, and the degree of surface discoloration was evaluated by the color difference ΔE(1) between the two polyurethane foams A and B. The evaluation criteria for the degree of discoloration are as follows. 〇: ΔE(1) = 3 or less, no discoloration ×: ΔE(1) > 3, discoloration

[0100] 2. Flame retardancy The polyurethane foam prepared under the above manufacturing conditions was cut into a 10 cm × 10 cm × 5 cm square 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. Based on the results of the total calorific value thus obtained, the flame retardancy of the polyurethane foam was evaluated. The evaluation criteria for flame retardancy are as follows. 〇: 8 MJ / m at the 20-minute mark from the start of heating 2 or less △: 8 MJ / m at the 10-minute mark from the start of heating 2 or less ×: More than 8 MJ / m at the 10-minute mark from the start of heating 2 exceeding

[0101] 3. Colorability After obtaining polyurethane foam A formed from a polyol-containing composition containing a pigment and polyurethane foam C formed from a polyol-containing composition not containing a colorant (colorant-free polyol-containing composition), a color difference meter (manufactured by KONICA MINOLTA, product name: SPECTROPHOTOMETER CM-5) was applied to the surface of each. The surface colorability was evaluated based on the color difference ΔE(2) of the two polyurethane foams A and C thus obtained. The evaluation criteria for colorability are as follows. Note that the colorant-free polyol-containing composition is a polyol-containing composition having the same formulation as in each example and comparative example except for not containing a colorant. 〇: ΔE(2) = 3 or more, coloring present ×: ΔE(2) < 3, no coloring

[0102] [Examples 1 to 7, Comparative Examples 1 to 4] 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 produced, and evaluations were performed based on the above evaluation methods 1 to 3. The results are shown in Table 1. The mixing ratio of the polyol-containing composition and polyisocyanate was 1:1 by volume.

[0103]

Table 1

[0104] As is clear from the results of the above Examples and Comparative Examples, in the polyol-containing composition of the present invention, the colorant has not decolorized, and the polyurethane foam formed from the composition has good flame retardancy and colorability. On the other hand, in the polyol-containing compositions of Comparative Examples 1 to 3, since they contained a dye as a colorant, decolorization of the colorant occurred. In the polyol-containing composition of Comparative Example 3, in addition to the decolorization of the colorant, since it did not contain a solid flame retardant, the flame retardancy of the polyurethane foam was impaired. Further, in the polyol-containing composition of Comparative Example 4, since it did not contain any colorant, the polyurethane foam could not be colored.

Claims

1. A polyol-containing composition for reacting with a polyisocyanate to obtain a polyurethane foam, comprising: a polyol, a blowing agent, a catalyst, a flame retardant, and a pigment, and wherein the flame retardant includes a solid flame retardant.

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

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

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

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

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

7. A foaming polyurethane composition comprising the polyol-containing composition according to any one of claims 1 to 6 and a polyisocyanate.

8. The foaming polyurethane composition according to claim 7, wherein the color difference between polyurethane foam A obtained by mixing the polyol-containing composition and the polyisocyanate and polyurethane foam B obtained by mixing the polyol-containing composition stored at 55 °C for 3 days and the polyisocyanate is 3 or less.

9. A foaming polyurethane composition comprising a polyol, a polyisocyanate, a blowing agent, a catalyst, a flame retardant, and a pigment, and wherein the flame retardant includes a solid flame retardant.

10. The foaming polyurethane composition according to any one of claims 7 to 9, wherein the isocyanate index is 200 or more.

11. The foaming polyurethane composition according to any one of claims 7 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 7 to 11.

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

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