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

Abstract

To provide a polyol-containing composition that can form a polyurethane foam having flame retardancy and resistance to yellowing.SOLUTION: The present invention relates to a polyol-containing composition that is reacted with a polyisocyanate to yield a polyurethane foam. The polyol-containing composition contains a polyol, a foamer, a catalyst, a red phosphorus flame retardant, and a colorant. The colorant is at least one selected from the group consisting of a black colorant and a blue colorant.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-containing 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.

[0003] Although polyurethane foam is lightweight, it is an organic substance and thus flammable. In the event of a fire, there is a risk that the fire will spread to the polyurethane foam and cause a fire to spread. Therefore, as a means of imparting flame retardancy to polyurethane foam, adding a flame retardant containing red phosphorus as an essential component to the urethane resin composition can be mentioned (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, although conventional red phosphorus-containing polyurethane foam has good flame retardancy due to red phosphorus, it has a reddish color derived from red phosphorus and may be avoided in applications where design is required. Furthermore, there is also a problem that polyurethane foam undergoes yellowing due to deterioration over time after construction, thereby deteriorating the appearance and impairing the design.

[0006] Therefore, an object of the present invention is to provide a polyol-containing composition that has flame retardancy, suppresses the occurrence of yellowing even after long-term use, and can form a polyurethane foam with high design quality.

Means for Solving the Problems

[0007] As a result of intensive studies, the present inventor has found that in a polyol-containing composition containing a polyol, a foaming agent, a catalyst, and a flame retardant, by using a red phosphorus-based flame retardant, which has been avoided in applications where design quality is required, in combination with a specific colorant, while enhancing the flame retardancy, yellowing is surprisingly suppressed by the complementary color effect even when deteriorating over time, and a polyurethane foam with high design quality can be obtained. The present invention has been completed based on the above findings and provides the following [1] to

[11] . [1] A polyol-containing composition for obtaining a polyurethane foam by reacting with a polyisocyanate, the composition containing a polyol, a foaming agent, a catalyst, a red phosphorus-based flame retardant, and a colorant, wherein the colorant is at least one selected from the group consisting of a black colorant and a blue-based colorant. [2] The polyol-containing composition according to [1], wherein the colorant is a blue-based colorant. [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 bismuth or tin. [7] The polyol-containing composition according to any one of [1] to [6], wherein the foaming agent contains a hydrofluoroolefin. [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 red phosphorus-based flame retardant, and a colorant, wherein the colorant is at least one selected from the group consisting of a black colorant and a blue-based colorant. The foaming polyurethane composition is characterized by this.

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

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

[10] .

Effect of the Invention

[0008] According to the present invention, it is possible to provide a polyol-containing composition capable of forming a polyurethane foam having flame retardancy, suppressing yellowing even when used for a long period of time, and having high design properties.

Embodiments for Carrying Out the Invention

[0009] [Polyol-containing Composition] The polyol-containing composition of the present invention is a polyol-containing composition for obtaining a polyurethane foam by reacting with a polyisocyanate, and contains a polyol, a foaming agent, a catalyst, a red phosphorus-based flame retardant, and a colorant.

[0010] [Colorant] The colorant of the present invention is at least one selected from the group consisting of a black colorant and a blue-based colorant. When the colorant is a black colorant, the color of the polyurethane foam becomes black or gray close to black, so that the red color of the red phosphorus-based flame retardant and yellowing due to deterioration over time can be effectively masked to enhance the design properties. In addition, when the colorant is a blue-based colorant, combined with being colored red by the red phosphorus-based flame retardant, the coloring due to yellowing is effectively masked by the complementary color effect, and the color of the polyurethane foam becomes gray or close to gray, enhancing the design properties. In the present invention, from the viewpoint of further enhancing the design property, the colorant is preferably a blue-based colorant. The term "blue-based colorant" used in the present invention includes not only blue colorants but also colorants of colors approximating blue, specifically, purple colorants, light blue colorants, etc., but blue colorants are preferred.

[0011] The colorant may be a dye, a pigment, or a combination thereof. The colorant may be a dispersion or solution of any of the above dyes and pigments in an organic solvent, water, etc. That is, the dye can be used in various forms, such as solvent dyes, disperse dyes, etc., and the dye may also be a reactive dye. A reactive dye is a dye capable of reacting with components constituting polyurethane such as polyol. Also, the pigment may be either an inorganic pigment or an organic pigment. The colorant may be one that exhibits a blue-based color or black when a single compound is used, or may be one that exhibits a blue-based color or black when a combination of two or more compounds is used. Hereinafter, some specific examples of dyes and pigments will be listed in more detail as colorants, but the colorants used in the present invention are not limited to these, and colorants other than those listed below may be used as long as they can effectively suppress the yellowing of the polyurethane foam.

[0012] The black colorant may be a black pigment or a black dye. 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. Also, as black dyes, nigrosine dyes, azo dyes, azine-based dyes, etc. can be used, and various solvent blacks, reactive blacks, and disperse blacks described in the Color Index can be used. When using a black colorant in the present invention, any one of the above black dyes and black pigments may be used alone, or a combination of at least two or more selected from the above black dyes and black pigments may be used.

[0013] As the black pigment and black dye, commercially available products may be used. As the black dye, reactive dyes such as Reactint Black X95AB, Reactint Black 1852, Reactint Black 2256, Reactint Black X77, Reactint Black 454SS (all manufactured by Milliken&Company) can be used. As the black pigment, DispersiTech Black2140 (manufactured by Milliken&Company) etc. can be mentioned. Even when using commercially available products, one kind may be used alone, or a combination of at least two or more kinds may be used.

[0014] The blue-based colorant may be a blue colorant such as a blue pigment or a blue dye, or may be a purple colorant such as a purple pigment or a purple dye. Also, the blue colorant may be a light blue colorant. 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 - silicon oxide, cobalt - zinc - silicon oxide, manganese blue, phthalocyanine, etc. Also, specific examples of purple pigments include, for example, inorganic pigments such as cobalt violet (cobalt arsenate, cobalt phosphate, cobalt lithium phosphate, 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 can be used, and as the purple pigment, various pigment violets can also be used. As the blue dye, various solvent blues, reactive blues, disperse blues, etc. described in the Color Index can be used. As the purple dye, various solvent violets, reactive violets, disperse violets, etc. described in the Color Index can be used.

[0015] As the blue-based colorant, commercially available products may be used. Examples of reactive dyes of blue dyes include Reactint Blue X17AB and Reactint Blue X77 (both manufactured by Milliken & Company). As the blue dye, Cool Dye Navy Blue (manufactured by Keiya Fine Goods Co., Ltd.) or light blue dyes such as Cool Dye Sky Blue (manufactured by Keiya Fine Goods Co., Ltd.) may also be used. Examples of blue pigments include DispersiTech Blue2402 (manufactured by Milliken & Company), Mitsui PS Blue RR, and PET Blue 2000 (all manufactured by Mitsui Chemicals Fine Co., Ltd.). Examples of reactive dyes of purple dyes include Reactint Violet X80LT (manufactured by Milliken & Company). Examples of purple pigments include Mitsui PS Violet RC (manufactured by Mitsui Chemicals Fine Co., Ltd.). In the present invention, when using the blue-based colorant, similar to the black colorant, one kind may be used alone, or a combination of at least two or more kinds may be used.

[0016] In the present invention, as described above, a black colorant or a blue colorant may be used alone. A black colorant and a blue colorant may be used in combination. Furthermore, as long as the effect of the present invention is not impaired, a colorant having a third color, such as red, yellow, or green, other than the black colorant and the blue colorant (hereinafter referred to as a third colorant) may be used in combination with the black colorant or the blue colorant. In addition, a commercially available colorant may be used as the third colorant. Examples of commercially available products include Mitsui PS Yellow GG, PET Yellow 1000, Mitsui PS Red G, Mitsui PS Brilliant Red HEY, PET Red 1000, and Mitsui PS Green B (all manufactured by Mitsui Chemicals Fine Co., Ltd.).

[0017] In the present invention, by using a black colorant, the polyurethane foam obtained using the polyol-containing composition is black or gray even immediately after production, and even if it deteriorates over time, the black or gray color is maintained due to the action of the black colorant, thereby ensuring high design properties. In addition, the use of a blue-based colorant has a complementary color effect with the red phosphorus-based flame retardant and the yellowing of the polyurethane foam, and the polyurethane foam obtained using the polyol-containing composition has a gray or gray-like color, but the polyurethane foam immediately after production may have a slightly bluish color. If the polyurethane foam has a bluish color immediately after production, even if it discolors due to deterioration over time, it will be about gray, and it is easy to ensure high designability both immediately after production and after long-term use.

[0018] The content of the colorant is not particularly limited, but is preferably 0.4 to 24 parts by mass relative to 100 parts by mass of the polyol compound. When the content of the colorant is 0.4 parts by mass or more, the effect of using the colorant can be obtained, and even if the polyurethane foam changes over time, yellowing can be prevented. In addition, when the content is 24 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 blending of the colorant are unlikely to occur. From these viewpoints, the content of the colorant is more preferably 8 to 22 parts by mass, and even more preferably 12 to 20 parts by mass, in the case of a black colorant, for example. Also, the content of the colorant is more preferably 1.2 to 12 parts by mass, and even more preferably 2 to 8 parts by mass, in the case of a blue-based colorant, for example. Since the blue-based colorant can suppress the yellowing of the polyurethane foam more effectively than the black colorant, it is possible to suppress yellowing with a smaller content.

[0019] <Polyol> The polyol is not particularly limited, and examples thereof include polyether polyol, polyester polyol, and the like. 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, the use of halogen-containing polyol, phosphorus-containing polyol, and the like 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, even 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 even 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 (d1) and (d2) as the polyol, let the hydroxyl value of polyol (d1) be X 1 , and the blending ratio be m 1 , and the hydroxyl value of polyol (d2) be X 2 , and the blending ratio be m2 If so, the average hydroxyl value is represented by the following formula. The blending ratio is based on mass. Average hydroxyl value (mgKOH / g) = X 1 ×(m 1 / (m 1 +m 2 )) + X 2 ×(m 2 / (m 1 +m 2 )) 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 component 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) Polyether polyol is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of 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 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.

[0025] 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 utilizing 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.

[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 tends to decrease. However, by containing the 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 preferably contains bismuth or tin, and more preferably contains bismuth.

[0028] The above-mentioned resinified metal catalyst preferably contains a metal salt selected from bismuth and tin, 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 a foaming agent, particularly a hydrofluoroolefin. Further, from the viewpoint 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. In addition, 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. Further, 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, and 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, and more preferably bismuth trioctoate.

[0029] The content of the above-mentioned resinified metal catalyst in the polyol-containing composition is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, still more preferably 1.5 to 10 parts by mass, and even more preferably 2 to 8 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 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, by containing an imidazole derivative in addition to the above-described metal catalyst, the polyol-containing composition has enhanced reactivity between the polyol and the polyisocyanate and better foaming properties. 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 fewer carbon atoms, and the alkyl group preferably has 6 or fewer carbon atoms, more preferably 4 or fewer carbon atoms. Preferred specific examples of the imidazole derivative are represented by the following general formula (1).

[0031] [Chemical formula] (In 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 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 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 hydrofluorolefin, which is preferable. On the other hand, R 1 and R 2 When the number of carbon atoms in the alkyl group of R is equal to or less than the upper limit value, the steric hindrance does not become extremely large, so that the reaction between the polyol and the polyisocyanate can proceed rapidly and the foamability also becomes 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.

[0033] 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 hydrofluorolefin 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.

[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, 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 becomes 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.

[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 them 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. The trimerization catalyst may be used alone or in combination of two or more. When using two or more in combination, it is 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 0.4 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 4 to 18 parts by mass with respect to 100 parts by mass of the polyol. When the content of the trimerization catalyst is equal to or higher than the lower limit value, there is no significant difference in the activities of 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 equal to or lower than the 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] <Filler> The polyol-containing composition of the present invention contains, as a filler, a red phosphorus-based flame retardant which is one of the solid flame retardants. Here, the solid flame retardant is a flame retardant that is solid at normal temperature (23 °C) and normal pressure (1 atm). The filler is included as a solid content in the polyol-containing composition and is generally a component present in the form of granules or powder in the polyol-containing composition. In the present invention, by containing a red phosphorus-based flame retardant as a filler, the flame retardancy of the polyurethane foam can be improved.

[0038] The filler may be a 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, it is preferable that the filler does not have hygroscopicity and deliquescence. Note that the above-described catalyst is not included in the filler. As the filler in the present invention, from the viewpoint of improving flame retardancy, in addition to the red phosphorus-based flame retardant, a solid flame retardant other than the red phosphorus-based flame retardant may be used. Specific examples of the solid flame retardant other than the red phosphorus-based flame retardant include phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, chlorine-containing flame retardants, metal hydroxides, needle-like fillers, and the like. 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 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 and 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 preferred as the compound for coating or mixing. The metal hydroxides described later may be appropriately selected and used.

[0040] (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.

[0041] Specific examples of the phosphate-containing flame retardant include, for example, monophosphates, polyphosphates, etc. The monophosphate is not particularly limited, and examples thereof include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, sodium hypophosphite, potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, potassium hypophosphite, lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, lithium hypophosphite, barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, barium phosphate, barium hypophosphite, magnesium salts such as magnesium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, magnesium hypophosphite, calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite, 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, etc. The phosphate-containing flame retardant may be used alone or in combination of two or more thereof.

[0042] (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). Examples thereof include aromatic compounds containing brominated aromatic rings. Examples of brominated aromatic ring-containing aromatic compounds include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

[0043] Also, the brominated aromatic ring-containing aromatic compound may be a bromine compound polymer. Specifically, examples include 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, etc. Furthermore, examples include brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, condensates of brominated polyphenylene ether, brominated bisphenol A, and cyanuric chloride, uncrosslinked or crosslinked brominated polystyrene, etc. Also, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may be used. These bromine-containing flame retardants may be used alone or in combination of two or more.

[0044] (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, etc. 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. may be mentioned. 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.

[0045] (Antimony-containing flame retardant) Examples of antimony-containing flame retardants include antimony oxides, antimonates, pyroantimonates, etc. Examples of antimony oxides 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.

[0046] (Chlorine-containing flame retardant) Examples of chlorine-containing flame retardants include those commonly used in polyurethane foams, such as polychlorinated naphthalenes, chlorendic acid, dodecachlorododecahydrodimethanodibenzocyclooctene sold under the trade name "Dechlorane Plus", etc.

[0047] (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, and the like. The metal hydroxide may be used alone or in combination of two or more. Aluminum hydroxide is preferable as the metal hydroxide.

[0048] (Needle-shaped filler) Examples of the needle-shaped filler include potassium titanate whisker, aluminum borate whisker, magnesium-containing whisker, silicon-containing whisker, wollastonite, sepiolite, zonolite, eleustonite, 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. By using the needle-shaped filler, the mechanical properties of the polyurethane foam can be effectively improved. One or more of these needle-shaped fillers can be used. The aspect ratio (length / diameter) of the needle-shaped 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 needle-shaped filler with a scanning electron microscope and measuring its length and width.

[0049] In addition, inorganic fillers other than the above-mentioned solid flame retardants may be used. Examples of such inorganic fillers include 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 disulfide, 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. These fillers may be used alone or in combination of two or more.

[0050] The content of the red phosphorus-based flame retardant in the polyol-containing composition is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and still more preferably 15 to 35 parts by mass with respect to 100 parts by mass of the polyol. When the content of the red phosphorus-based flame retardant filler is at least the above lower limit value, it becomes possible to impart good flame retardancy to the polyurethane foam. Further, by setting it to be at most the above upper limit value, the handleability and foamability are improved when the polyol-containing composition is mixed with the polyisocyanate. Further, when it is within the above range, by using it in combination with a blue-based colorant, the designability can be enhanced due to an appropriate complementary color relationship. The content of the filler in the polyol-containing composition 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. When the content of the filler is at least 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 the 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.

[0051] <Phosphate ester> The polyol-containing composition of the present invention may contain a flame retardant other than the above-mentioned solid flame retardant. Examples of such a flame retardant include a liquid flame retardant that is liquid at normal temperature (23°C) and normal pressure (1 atm), and specifically, a phosphate ester. By using a phosphate ester, it becomes easier to improve the flame retardancy of the polyurethane foam without reducing the fluidity of the polyol-containing composition.

[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, cresyl diphenyl 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 viewpoints of easily adjusting 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] <Foaming agent> The foaming agent promotes the foaming of the foamable 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, and cycloheptane; chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride; 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, and carbon dioxide gas. Among these, it is preferable to contain a hydrofluoroolefin (HFO) which has high stability as a foaming agent, is less likely to cause a decrease in catalytic activity, and further has a lower environmental load.

[0056] Examples of suitable HFOs as the foaming agent include fluoroalkenes having about 3 to 6 carbon atoms. The HFO may also be a hydrochlorofluoroolefin having a chlorine atom, and thus may be a chlorofluoroalkene having about 3 to 6 carbon atoms. Examples of HFOs include trifluoropropene, tetrafluoropropenes such as HFO-1234, pentafluoropropenes such as HFO-1225, chlorodifluoropropene, chlorotrifluoropropenes 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. Among these, HFO-1233zd(E) is preferred.

[0057] The content of the blowing agent is not particularly limited. With respect to 100 parts by mass of the polyol, 20 to 80 parts by mass is preferred, 30 to 70 parts by mass is more preferred, and 35 to 60 parts by mass is even more preferred. When the content of the blowing agent is at least the 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 blowing agent is at most the upper limit value, it is possible to suppress the excessive progress of foaming.

[0058] As described above, one or more blowing 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 blowing agents. For example, HFO can 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.

[0059] The content of HFO is not particularly limited. With respect to 100 parts by mass of the polyol, 19 to 75 parts by mass is preferable, 29 to 67 parts by mass is more preferable, and 34 to 58 parts by mass is even more preferable. When the content of the blowing agent is at least the lower limit value, foaming is promoted, the foaming property 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.

[0060] The content of water is not particularly limited. With respect to 100 parts by mass of the polyol, 0.1 to 5 parts by mass is preferable, 0.3 to 3 parts by mass is more preferable, and 0.5 to 2 parts by mass is even more preferable. When the content of the blowing agent is at least the lower limit value, foaming is promoted, the foaming property 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.

[0061] <Foam stabilizer> The polyol-containing composition of the present invention may contain a foam stabilizer. By containing a foam stabilizer, the foaming property of the polyurethane foam can be improved. For example, when reacting with polyisocyanate in spray spraying, foaming can be promoted. As the foam stabilizer, specifically, surfactants can be exemplified, and more specifically, nonionic surfactants, cationic surfactants, anionic surfactants, etc. can be exemplified. Specific examples of nonionic surfactants 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 silicone foam stabilizers are preferred from the viewpoint of foamability. The foam stabilizer may be used alone or in combination of two or more.

[0062] 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, 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.

[0063] <Other components> The polyol-containing composition may contain 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, etc., and tackifiers such as polybutene and petroleum resins, as necessary, within a range not impairing the object of the present invention.

[0064] <Method for producing polyol-containing composition> There is no particular limitation on the method for producing the polyol-containing composition of the present invention. For example, it can be produced by stirring each component at about 20 to 40°C for about 30 seconds to 20 minutes using a homodisper or the like. In addition, when preparing the polyol-containing composition, the above-mentioned colorant may be mixed with each component other than the colorant, or after preparing the polyol-containing composition from each component other than the colorant, it may be post-added to the polyol-containing composition. Examples of the timing of post-addition include immediately before mixing the polyol-containing composition with the polyisocyanate.

[0065] [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 polyol, a foaming agent, a catalyst, a red phosphorus-based flame retardant, and a colorant, in addition to a polyisocyanate. In addition, the foamable polyurethane composition may contain fillers other than the red phosphorus-based flame retardant, liquid flame retardants such as phosphate esters, 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.

[0066] The foamable polyurethane composition of the present invention preferably includes the above polyol-containing composition and a polyisocyanate, and is obtained by mixing these. Further, the polyurethane foam of the present invention is a reaction product obtained by reacting and foaming the foamable polyurethane composition. However, the colorant does not necessarily need to be contained in the polyol-containing composition, and may be mixed together at the time of mixing the polyol and the isocyanate, or may be mixed with the polyisocyanate in advance.

[0067] The polyurethane foam of the present invention is one in which yellowing is suppressed because the color of the colorant contained in the polyol-containing composition is at least one selected from black and blue colors. That is, the polyurethane foam of the present invention has a black or gray color after construction as described above. However, the color of the polyurethane foam immediately after construction does not necessarily have to be a complete black or gray color, and as described above, it may contain a slight amount of other colors in black or gray, such as a slightly bluish black or gray.

[0068] <Polyisocyanate> In the present invention, examples of the polyisocyanate include aromatic polyisocyanates, alicyclic polyisocyanates, aliphatic polyisocyanates, and the like. 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).

[0069] Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0070] Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0071] 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, among which 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, the polyisocyanate may be appropriately blended with known additives to be blended in the polyisocyanate.

[0072] In addition, 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 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.

[0073] <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 least the lower limit value, the amount of polyisocyanate relative to the polyol becomes excessive, and isocyanurate bonds are easily formed by the trimer of polyisocyanate, resulting in improved flame retardancy of the polyurethane foam. In addition, it becomes possible to impart flame retardancy. Furthermore, when it is at least the above lower limit value, together with the combined use of the various catalysts described above, 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.

[0074] 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.

[0075] <Method for producing polyurethane foam> The method for producing the polyurethane foam is not particularly limited, but a polyol-containing composition may be mixed with a polyisocyanate in a foaming machine or the like, and the resulting mixed solution (foamable polyurethane composition) may be reacted and foamed to produce the polyurethane foam. As the foaming machine, a spraying device having a spray gun or the like may be used. 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 solution (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.

[0076] This production method can preferably be applied to spraying applications. Therefore, the mixed solution discharged from the foaming machine may be sprayed onto the construction target surface at a certain discharge pressure and foamed to form the polyurethane foam on the construction target surface.

[0077] <Uses of polyurethane foam> The use of the polyurethane foam of the present invention is not particularly limited, but since it is excellent in flame retardancy and heat insulation, it can be preferably used in buildings such as walls, ceilings, roofs, and floors of buildings, and the polyurethane foam may be formed with walls, ceilings, roofs, floors, etc. as the spraying target surface.

Examples

[0078] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

[0079] [Materials Used] <Polyol-containing Composition> (Polyol) · p-Phthalic Acid Polyester Polyol (manufactured by Kawasaki Chemical Industry Co., Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mgKOH / g)

[0080] (Catalyst) · Ammonium Salt (trimerization catalyst), Tetramethylammonium 2,2-dimethylpropanoate (manufactured by Air Products and Chemicals, Inc., product name: DABCO® TMR7) concentration 45 - 55 mass% · Metal Catalyst (trimerization catalyst), Potassium 2-ethylhexanoate (manufactured by Air Products and Chemicals, Inc., product name: DABCO® K-15) concentration 70 - 80 mass% · Resinified Amine Catalyst, 1,2-Dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT®-DM70) concentration 65 - 75 mass% · Resinified Metal Catalyst, Bismuth Trioctoate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600) concentration 55 - 58 mass% · Resinified Metal Catalyst, Dioctyltin Versatate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-830) concentration approximately 99 mass%

[0081] (Blowing Agent) · Hydrofluoroolefin (HFO), trans-1-Chloro-3,3,3-trifluoropropene (manufactured by Honeywell Japan Ltd., product name: Soltis LBA) · Water

[0082] (Phosphate Ester (Liquid Flame Retardant)) · Tris(β-chloropropyl) Phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name: TMCPP)

[0083] (Filler) · Red Phosphorus-based Flame Retardant (manufactured by Phosphorus Chemical Industry Co., Ltd., product name: Nova Excel 140) · Wollastonite (SiO 2 · CaO) (manufactured by Kinsai Mateck Co., Ltd., product name: SH-1250)

[0084] <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 dye (manufactured by Milliken & Company, product name: Reactint Blue X77), blue pigment (manufactured by Milliken & Company, product name: DispersiTech Blue 2402) ·Purple colorant: Purple dye (manufactured by Milliken & Company, product name: Reactint Violet X80LT) ·Light blue colorant: Light blue dye (manufactured by Keiya Fine Goods Co., Ltd., product name: Cool Dye Sky Blue) ·Red colorant: Red dye (manufactured by Milliken & Company, product name: Reactint Red X64) ·Yellow colorant: Yellow dye (manufactured by Milliken & Company, product name: Reactint Yellow X15) ·Orange colorant: Orange dye (manufactured by Milliken & Company, product name: Reactint Orange X94)

[0085] <Polyisocyanate> ·4,4'-Diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Wanhua Chemical Japan Co., Ltd., product name: PM200)

[0086] [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 ·Settings (Heater settings) Isocyanate heater: 38 °C Premix Heater (for heating the polyol-containing composition): 38°C Hose Heater (for preheating the polyisocyanate and polyol-containing composition before mixing): 38°C Pressure: Appropriately adjusted so that the mist forms a wide circular shape · Substrate temperature (temperature of the spraying target surface): 20°C ± 1°C

[0087] [Evaluation Method of Polyurethane Foam] 1. Yellowing Suppression Polyurethane foam was spray-applied onto a gypsum board under the above manufacturing conditions, and the polyurethane foam was irradiated with direct sunlight for 1 day. The polyurethane foam after irradiation was visually inspected, and the yellowing suppression of the polyurethane foam was evaluated based on the visual inspection results. The evaluation criteria for yellowing suppression are as follows. 〇: The appearance of the polyurethane foam is gray or black ×: The appearance of the polyurethane foam is a color other than the above (mainly yellow or loess color)

[0088] 2. Flame Retardancy The polyurethane foam prepared under the above manufacturing conditions was cut into a size of 10 cm × 10 cm × 5 cm to obtain test pieces. The total heat release amount of the test pieces when heated at a radiant heat intensity of 50 kW / m 2 for 10 to 20 minutes in accordance with ISO 5660 was measured. The evaluation criteria for flame retardancy are as follows. 〇: 8 MJ or less at the 10-minute mark from the start of heating ×: Exceeding 8 MJ at the 10-minute mark from the start of heating

[0089] [Examples 1 to 14, Comparative Examples 1 to 5] 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, polyurethane foam was produced, and the evaluations of Evaluation Methods 1 to 3 were carried out. The results are shown in Table 1. The mixing ratio of the polyol-containing composition and polyisocyanate was 1:1 by volume.

[0090]

Table 1

[0091] As is clear from the results of the above examples and comparative examples, the polyurethane foam using the polyol-containing composition of the present invention has good flame retardancy and sufficient suppression of yellowing. In Examples 1 to 3, 9, 11, and 13 using a black colorant, the polyurethane foam was black or gray close to black immediately after production, and was still black or gray close to black even after being irradiated with direct sunlight for one day, showing excellent design properties. On the other hand, in Examples 4 to 8, 10, 12, and 14 using a blue-based colorant, the polyurethane foam had a slightly bluish tint immediately after production, but became achromatic gray after being irradiated with direct sunlight for one day, showing excellent design properties both immediately after production and after aging over time. Also, even when the content was reduced, the design properties were excellent. In contrast, Comparative Examples 1 to 4 did not contain either a black colorant system or a blue-based colorant, so yellowing occurred in the polyurethane foam. Further, Comparative Example 5 shows the case where a red phosphorus-based flame retardant is not contained. While yellowing in the polyurethane foam was suppressed, the flame retardancy was impaired.

Claims

1. 1. A polyol-containing composition for reacting with a polyisocyanate to obtain a polyurethane foam, comprising: Contains polyol, foaming agent, catalyst, red phosphorus flame retardant, and colorant, The polyol-containing composition, wherein the colorant is at least one selected from the group consisting of black colorants and blue colorants.

2. The polyol-containing composition according to claim 1 , wherein the colorant is a blue-based colorant.

3. The polyol-containing composition of claim 1 or 2, wherein the catalyst comprises a trimerization catalyst.

4. The polyol-containing composition of claim 3 , wherein the trimerization catalyst comprises a quaternary ammonium salt.

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

6. The polyol-containing composition according to any one of claims 1 to 5, wherein the catalyst comprises bismuth or tin.

7. The polyol-containing composition of any one of claims 1 to 6, wherein the blowing agent comprises a hydrofluoroolefin.

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

9. A foamable polyurethane composition comprising a polyol, a polyisocyanate, a foaming agent, a catalyst, a red phosphorus-based flame retardant, and a colorant, 1. A foamable polyurethane composition, wherein the colorant is at least one selected from the group consisting of black colorants and blue colorants.

10. 10. The foamable polyurethane composition according to claim 8 or 9, having an isocyanate index of 200 or more.

11. A polyurethane foam obtained by reacting and foaming the foamable polyurethane composition according to any one of claims 8 to 10.

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