Polyol-containing composition, foamed 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 foamed polyurethane composition, and a polyurethane foam. [Background technology]

[0002] Due to its excellent heat insulation and adhesive properties, polyurethane foam is used as insulation in buildings such as apartment buildings, detached houses, various school facilities, and commercial buildings. Polyurethane foam is obtained by mixing a polyol composition and polyisocyanate, foaming the mixture, and then spraying it onto objects such as ceilings, walls, and roofs using a spray device. As such polyurethane foam is used in buildings, it is required to be flame-retardant in the event of a fire, in order to prevent the fire from spreading to the polyurethane foam and causing a fire throughout the entire building. For this reason, polyurethane foam is sometimes blended with solid flame retardants such as red phosphorus, which have a high flame-retardant effect.

[0003] Furthermore, in recent years, as the applications of polyurethane foam have expanded, it has come to be used in visible areas, and surface aesthetics have become increasingly important. Consequently, the demand for colored polyurethane foam is also increasing. One method for coloring polyurethane foam is, for example, to include a dye in the polyol composition for forming polyurethane foam, as described in Patent Document 1. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 6621571 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, when these conventional polyol compositions contain dyes as colorants, the dyes can dissolve in the polyol composition and react with other components such as solid flame retardants and catalysts, particularly ammonium salt-based catalysts. As a result, when the polyol composition is foamed after being stored for a long period of time, the dyes may have already faded, making it impossible to color the polyurethane foam to the desired color.

[0006] Therefore, the object of the present invention is to provide a polyurethane foam that is flame-retardant and aesthetically pleasing, along with a polyol-containing composition that suppresses discoloration of the colorant even when stored for a long period of time. [Means for solving the problem]

[0007] As a result of diligent research, the inventors have found that the above problems can be solved by a polyol-containing composition for obtaining polyurethane foam by reacting with polyisocyanate, the polyol-containing composition containing a polyol, a blowing agent, a catalyst, a flame retardant, and a pigment, wherein the flame retardant includes a solid flame retardant, and thus the inventors have completed the present invention.

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

[13] . [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, wherein the flame retardant comprises a solid flame retardant. [2] The polyol-containing composition according to [1], wherein the solid flame retardant comprises a red phosphorus-based flame retardant. [3] The polyol-containing composition according to [1] or [2], wherein the catalyst comprises a trimerizing catalyst. [4] The polyol-containing composition according to [3], comprising the trimerizing catalyst, a quaternary ammonium salt. [5] The polyol-containing composition according to any one of [1] to [4], wherein the catalyst comprises an imidazole derivative. [6] The polyol-containing composition according to any one of [1] to [5], wherein the catalyst comprises a metal catalyst selected from the group consisting of bismuth or tin. A foamed polyurethane composition comprising a polyol-containing composition described in any one of items [7][1] to [6] and a polyisocyanate. [8] The foamable 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 obtained by storing the polyol-containing composition at 55°C for 3 days and the polyisocyanate is 3 or less. [9] A foamable polyurethane composition comprising a polyol, a polyisocyanate, a blowing agent, a catalyst, a flame retardant, and a pigment, wherein the flame retardant comprises a solid flame retardant.

[10] A foamed polyurethane composition according to any one of items [7] to [9], wherein the isocyanate index is 200 or higher.

[11] A foamed polyurethane composition according to any one of items [7] to

[10] , used for spraying applications. A polyurethane foam obtained by foaming a foamed polyurethane composition described in any one of items

[12] [7] to

[11] .

[13] A method for producing 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, reacting and foaming the mixture, wherein the pigment is added to the polyol-containing composition or polyisocyanate in advance, or added when mixing the polyol-containing composition with the polyisocyanate. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a polyol-containing composition in which discoloration of the colorant is suppressed even when stored for a long period of time, and a polyurethane foam that is flame-retardant and has a high aesthetic appeal. [Modes for carrying out the invention]

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

[0011] [Pigment]< The polyol-containing composition of the present invention contains a pigment as a colorant. The pigment 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. Further, since the pigment does not react with other components in the polyol-containing composition, by using a pigment instead of a dye that has been conventionally known to be used as a colorant, decolorization of the colorant is suppressed, and it becomes possible to color the polyurethane foam in 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 a black pigment and a blue-based pigment. When the pigment is a black pigment, the color of the polyurethane foam becomes black or gray close to black. Therefore, even if the polyurethane foam is colored in a red-based color such as red or pink by containing a flame retardant described later, the red-based color can be effectively masked to enhance the design property. Further, when the pigment is a blue-based pigment, the pigment exhibits a complementary color effect, the red-based color is more effectively masked, the color of the polyurethane foam becomes gray or close to gray, and the design property can be enhanced. The term "blue-based pigment" used in the present invention may be not only a blue pigment but also a pigment having a color approximate to blue, specifically, a purple pigment, a light blue pigment, etc.

[0012] As the black pigment or blue-based pigment used in the present invention, one kind of compound alone may exhibit a black or blue-based color, or a combination of two or more kinds of compounds may exhibit a black or blue-based color. 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) and the like 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. Specific examples of purple pigments include, for example, cobalt violet (cobalt arsenate, cobalt phosphate, cobalt lithium phosphate, ammonium cobalt hydrate phosphate, cobalt borate, etc.), purple ultramarine, iron oxide purple, manganese violet, mineral violet and other inorganic pigments, indigoid-based, quinacridone-based, oxazine-based, anthraquinone-based, carbonium-based, xanthene-based and other organic pigments. Also, as blue pigments, various pigment blues described in the Color Index can be used, and as purple pigments, various pigment violets can also be used.

[0015] Commercially available blue pigments can be used, such as DispersiTech Blue 2402 (Milliken & Company), Mitsui PS Blue RR, PET Blue 2000 (all manufactured by Mitsui Chemicals Fine), and Mitsui PS Violet RC (manufactured by Mitsui Chemicals Fine). In this invention, when using blue pigments, one type may be used alone, or two or more types may be used in combination, similar to black pigments.

[0016] The pigment contained in the polyol-containing composition of the present invention is more preferably a blue pigment, and even more preferably a blue pigment. Since blue pigments can suppress the red color of flame retardants more effectively than black pigments, using blue pigments can further enhance the aesthetic appeal of polyurethane foam, and since a lower content is required compared to when black pigments are used, the effect is commensurate with the production cost.

[0017] The pigment content is not particularly limited, but it is preferably 0.2 to 10 parts by mass per 100 parts by mass of polyol. A pigment content of 0.2 parts by mass or more allows the effects of the pigment to be obtained, resulting in good coloration of the polyurethane foam. Conversely, a pigment content of 10 parts by mass or less allows for effects commensurate with the amount added, making it less likely for problems such as deterioration of the polyurethane foam's performance to occur due to the pigment addition. From these perspectives, the pigment content is more preferably 1 to 10 parts by mass, and even more preferably 2 to 8 parts by mass, in the case of black pigments. In the case of blue pigments, 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, but examples include polyether polyols and polyester polyols. From the viewpoint of improving the flame retardancy of polyurethane foam, it is preferable that the polyol contains polyester polyol. Furthermore, from the viewpoint of improving flame retardancy, the use of halogen-containing polyols and phosphorus-containing polyols is also preferable. From this viewpoint, it is preferable that of 100 parts by mass of polyol, polyester polyol be 20 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 80 parts by mass or more, and particularly preferably 100 parts by mass.

[0019] The average hydroxyl value of the polyol used in the present invention is preferably 100 to 500 mg KOH / g, more preferably 150 to 450 mg KOH / g, and even more preferably 200 to 400 mg KOH / g, from the viewpoint of improving the flame retardancy of the polyurethane foam.

[0020] Note that the average hydroxyl value refers to the hydroxyl value of a single polyol when only one type of polyol is used. When two or more types of polyols are used, the average hydroxyl value of the polyols is the weighted average value of the hydroxyl groups according to the blending ratio of the two or more polyol compounds. For example, when using two types of polyols, (d1) and (d2), if the hydroxyl value of polyol (d1) is X1, the mixing ratio is m1, the hydroxyl value of polyol (d2) is X2, and the mixing ratio is m2, then the average hydroxyl value is expressed by the following formula. Note that the mixing ratio is on a mass basis. Average hydroxyl value (mgKOH / g)=X1×(m1 / (m1+m2))+X2×(m2 / (m1+m2)) The hydroxyl value is a value measured in accordance with JIS K1557-1:2007.

[0021] (Polyester polyol) The polyester polyol may be a polyester polyol having an aromatic ring or an aliphatic polyester polyol, but when considering the flame retardancy of the resulting polyurethane foam, it is preferable to use a polyester polyol having an aromatic ring. The polyester polyol having an aromatic ring is preferably a condensate of an aromatic dicarboxylic acid such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), or naphthalenedicarboxylic acid with a glycol. In particular, from the viewpoint of improving the flame retardancy of the polyurethane foam, the polyol compound preferably includes a phthalic acid-based polyester polyol, which is a condensate of phthalic acid and glycol, and more preferably includes a p-phthalic acid-based polyester polyol, which is a condensate of p-phthalic acid and glycol. While the glycol is not particularly limited, it is preferable to use a low molecular weight aliphatic glycol known as a component of polyester polyols, such as ethylene glycol, propylene glycol, or diethylene glycol.

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

[0023] (Polyether polyol) Polyether polyols are polyoxyalkylene polyols obtained by ring-opening addition polymerization of alkylene oxide to an initiator having two or more active hydrogen atoms. Examples of initiators include aliphatic polyhydric alcohols (e.g., glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, and cyclohexanedimethanol; triols such as trimethylolpropane and glycerin; tetrafunctional alcohols such as pentaerythritol; highly functional alcohols such as sucrose and sorbitol); aliphatic amines (e.g., alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine; alkanolamines such as monoethanolamine and diethanolamine); and aromatic amines (e.g., aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, Mannich condensates, etc.). Polyether polyols preferably have an aromatic ring. Among the above, polyether polyols produced using an initiator having an aromatic ring are polyether polyols having an aromatic ring. For example, polyether polyols produced using an aromatic amine as an initiator are polyether polyols having an aromatic ring. Among polyether polyols having an aromatic ring, tolylenediamine-based polyether polyols and Mannich-based polyether polyols can be suitably used.

[0024] Tolylenediamine-based polyether polyols are tolylenediamine-based polyether polyols manufactured using tolylenediamine as an initiator. The above-mentioned Mannich-type polyether polyols are obtained using the Mannich reaction and are Mannich condensates having two or more hydroxyl groups in the molecule, or polyether polyols obtained by adding alkylene oxide to such Mannich condensates. More specifically, they are Mannich condensates obtained by the Mannich reaction of at least one of phenol and its alkyl-substituted derivatives, formaldehyde and alkanolamines, or polyether polyols obtained by ring-opening addition polymerization of these compounds with at least one of ethylene oxide and propylene oxide.

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

[0026] <Catalyst> (Metal catalyst (resin-based 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 that it contains both. The resin catalyst preferably contains a metal catalyst. This metal catalyst is generally referred to as a resin-based metal catalyst. In the present invention, the inclusion of the above-mentioned resin-based metal catalyst promotes the reaction between the polyol and the polyisocyanate, and in particular, the initial reaction rate can be increased. Furthermore, while the reactivity of polyurethane foam tends to decrease and the foamability is reduced when a certain amount or more of fillers such as solid flame retardants, which will be described later, are included, the inclusion of a resin-based metal catalyst makes it easier to maintain good foamability of the polyurethane foam. From the viewpoint of foamability and other factors, the above-mentioned metal catalyst is preferably selected from the group consisting of bismuth or tin, and more preferably contains bismuth.

[0027] The resinified metal catalyst described above is preferably a metal salt selected from bismuth salts and tin salts, and more preferably a bismuth salt. The metal salt is preferably an organic acid metal salt, and more preferably a metal salt of a carboxylic acid having 5 or more carbon atoms. Having 5 or more carbon atoms in the carboxylic acid provides good stability against blowing agents, especially hydrofluoroolefins. Furthermore, from the viewpoint of catalytic activity, the number of carbon atoms in the carboxylic acid is preferably 18 or less, and more preferably 12 or less. The carboxylic acid is preferably an aliphatic carboxylic acid, and more preferably a saturated aliphatic carboxylic acid. The carboxylic acid may be linear or have a branched structure, but it is preferable to have a branched structure. Specific examples of carboxylic acids include octyl acid, lauryl acid, versatic acid, pentanoic acid, and acetic acid, with octyl acid being preferred among these. In other words, the transition metal salt is preferably a metal salt of octyl acid. These carboxylic acids may be linear as described above, but they may also have a branched structure. An example of octyl acid having a branched structure is 2-ethylhexanoic acid. Preferred metal salts of carboxylic acids include bismuth salts and tin salts of carboxylic acids, with bismuth salts of octic acid being particularly preferred. Alternatively, the metal salt of the carboxylic acid may be an alkyl metal carboxylic acid salt. For example, the tin salt of the carboxylic acid may be a dialkyltin carboxylic acid salt, and preferably a dioctyltin carboxylic acid salt. Specific examples of metal salts of carboxylic acids include bismastrioctate, dioctyl tin versatate, dibutyl tin dilaurate, dioctyl tin dilaurate, and tin dioctylate, with bismastrioctate and dioctyl tin versatate being preferred, and bismastrioctate being more preferred.

[0028] The content of the 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, even more preferably 1.5 to 8 parts by mass, and still more preferably 2 to 5 parts by mass per 100 parts by mass of polyol.

[0029] (Imidazole derivatives) The catalyst used in the polyol-containing composition of the present invention preferably contains a resin-forming amine catalyst as a resin-forming catalyst, and more preferably contains an imidazole derivative as the resin-forming amine catalyst. Imidazole derivatives are less affected by hydrofluoroolefins and facilitate the reaction between polyols and polyisocyanates while increasing the stability of polyol-containing compositions. Therefore, by including imidazole derivatives in addition to the metal catalysts mentioned above, the reactivity between polyols and polyisocyanates in polyol-containing compositions is enhanced, resulting in even better foaming properties. The imidazole derivative is preferably an imidazole in which the 1st and 2nd positions are independently substituted with alkyl groups having 8 or fewer carbon atoms, and the alkyl groups preferably have 6 or fewer carbon atoms, more preferably 4 or fewer carbon atoms. A suitable specific example of an imidazole derivative is represented by the following general formula (1).

[0030] [ka] (In general formula (1), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms.

[0031] R in general formula (1) 1 and R 2 Each of these independently represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. The alkyl group and alkenyl group may each be linear or have a branched structure. Specific examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, isopentyl group, sec-pentyl group, hexyl group, heptyl group, octyl group, and the like. Specific examples of the alkenyl group include a vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, and the like. R 1 and R 2 When the number of carbon atoms of the alkyl group or alkenyl group of R and R is not less than the lower limit value, the steric hindrance becomes large and it is less likely to be affected by a blowing agent such as hydrofluoroolefin, which is preferable. On the other hand, when the number of carbon atoms of the alkyl group of R and R is not more 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 foaming property is also good. 1 and R 2 When the number of carbon atoms of the alkyl group of R and R is not more 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 foaming property is also good. From these viewpoints, R and R 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. 1 and R 2 From these viewpoints, R and R 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, 1-isobutyl-2-methylimidazole, and the like. 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 not less than the lower limit value, the formation of urethane bonds is likely to occur, the reaction proceeds rapidly, and the foaming property is good. On the other hand, when the content of the imidazole derivative is not more than the upper limit value, the reaction rate is easily controlled, which is preferable.

[0034] (trimerization catalyst) The polyol-containing composition of the present invention preferably further contains a trimerizing catalyst. The trimerizing catalyst is a catalyst that reacts with the isocyanate groups contained in the polyisocyanate to trimerize them and promote the formation of an isocyanurate ring. The advantage of containing a trimerizing catalyst is that a good polyurethane foam can be obtained by completing the reaction of unreacted isocyanate groups. Examples of trimerizing catalysts include metal catalysts and ammonium salts. Examples of metal catalysts used as trimerization catalysts (trimerization metal catalysts) include potassium organic acids, preferably potassium octoates such as potassium 2-ethylhexanoate, potassium acetate, potassium propionate, potassium butanoate, potassium benzoate, and other potassium carboxylates having 2 to 8 carbon atoms. As the ammonium salt, tertiary ammonium salts such as triethylammonium salt and triphenylammonium salt, and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, and tetraphenylammonium salt can be used, but among these, quaternary ammonium salts are preferred. The ammonium salt is, for example, an ammonium salt of a carboxylic acid. Examples of carboxylic acids in the ammonium salt include saturated fatty acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms. The hydrocarbon group of the saturated fatty acid may be linear or branched, but branching is preferred. Specific examples of carboxylic acids include 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid, but among these, 2,2-dimethylpropanoic acid is preferred. The trimerization catalyst may be used alone or two or more may be used in combination. The trimerizing catalyst preferably contains a quaternary ammonium salt. In this invention, since a pigment is used as a coloring agent, even if a quaternary ammonium salt is used, problems such as decolorization of the coloring agent are less likely to occur. The trimerizing catalyst more preferably uses a combination of a quaternary ammonium salt and a metal catalyst.

[0035] The content of the trimerizing catalyst in the polyol-containing composition is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, even more preferably 2 to 20 parts by mass, and still more preferably 5 to 15 parts by mass, per 100 parts by mass of polyol. If the content of the trimerizing catalyst is above the lower limit, there will be no significant difference in the activity between resinification and trimerization, preventing foaming from occurring in two stages and resulting in good foamability. On the other hand, if the content of the trimerizing catalyst is below the upper limit, the resinification reaction will proceed actively, and the heat of the resinification reaction will assist the activity of trimerization, resulting in good foamability and the formation of a good polyurethane foam.

[0036] From the above viewpoint, for example, when an ammonium salt is included as the trimerizing 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, even more preferably 1.5 to 15 parts by mass, and still more preferably 3 to 11 parts by mass, per 100 parts by mass of polyol. Furthermore, when a metal catalyst is included as the trimerizing 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, even more preferably 0.5 to 5 parts by mass, and still more preferably 2 to 4 parts by mass, per 100 parts by mass of polyol.

[0037] <Solid flame retardant> The polyol-containing composition of the present invention contains a solid flame retardant as a flame retardant. Here, a solid flame retardant is a flame retardant that is solid at room temperature (23°C) and normal pressure (1 atm), and is generally a component that exists in granular or powder form in polyol-containing compositions. By including such a solid flame retardant, the polyol-containing composition of the present invention can improve the flame retardancy of polyurethane foam.

[0038] The solid flame retardant is a component that is solid at room 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 is preferably non-hygroscopic and non-deliquescent. The catalyst mentioned above is not included in the solid flame retardant. Specific examples of solid flame retardants in the present invention include red phosphorus-based flame retardants, phosphinate metal salts, phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, chlorine-containing flame retardants, and metal hydroxides. These solid flame retardants may be used individually or in combination of two or more.

[0039] (Red phosphorus-based flame retardant) Red phosphorus-based flame retardants may consist of pure red phosphorus, but they may also be coated with a resin, metal hydroxide, metal oxide, etc., or they may be a mixture of red phosphorus and a resin, metal hydroxide, metal oxide, etc. The resin used to coat or mix with red phosphorus is not particularly limited, but examples include thermosetting resins such as phenolic resins, epoxy resins, unsaturated polyester resins, melamine resins, urea resins, aniline resins, and silicone resins. From the viewpoint of flame retardancy, metal hydroxides are preferred as the compound used for coating or mixing. The metal hydroxides described later may be appropriately selected and used.

[0040] (Phosphinate metal salt) Metal phosphinate salts are metal salts of organic phosphinic acids. Specific examples of metal phosphinate salts 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, and titanium tetrakis-diphenylphosphinate.

[0041] (Phosphate-containing flame retardant) Examples of phosphate-containing flame retardants include phosphates composed of salts of various phosphoric acids with at least one metal or compound selected from metals of groups IA to IVB of the periodic table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. The term "various phosphoric acids" is a concept that includes not only phosphoric acid but also phosphorous acid, hypophosphorous acid, etc. Examples of metals in groups IA through IVB of the periodic table include lithium, sodium, calcium, barium, iron(II), iron(III), and aluminum. Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and piperazine. Examples of aromatic amines include aniline, o-triidine, 2,4,6-trimethylaniline, anisidine, and 3-(trifluoromethyl)aniline. Examples of heterocyclic compounds containing nitrogen in the ring include pyridine, triazine, and melamine.

[0042] Specific examples of phosphate-containing flame retardants include monophosphates and polyphosphates. Monophosphates are not particularly limited, but examples include ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate; sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, and sodium hypophosphite; potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, and potassium hypophosphite; lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, and lithium hypophosphite; barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, and barium hypophosphite; magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, and magnesium hypophosphite; calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite; and zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite. Here, the polyphosphate is not particularly limited, but examples include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, and aluminum polyphosphate. The phosphate-containing flame retardants may be used individually from the above-mentioned types, or two or more types may be used in combination.

[0043] (Bromine-containing flame retardant) Bromine-containing flame retardants are not particularly limited as long as they contain bromine in their molecular structure and are solid at room temperature (23°C) and normal pressure (1 atm), but examples include aromatic compounds containing brominated aromatic rings. Examples of brominated aromatic ring-containing aromatic compounds include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylenebis(pentabromophenyl), ethylenebis(tetrabromophthalimide), and tetrabromobisphenol A.

[0044] Furthermore, the brominated aromatic ring-containing aromatic compound may also be a brominated polymer. Specifically, examples include polycarbonate oligomers produced using brominated bisphenol A as a raw material, brominated polycarbonates such as copolymers of this polycarbonate oligomer and bisphenol A, and diexo compounds produced by the reaction of brominated bisphenol A and epichlorohydrin. In addition, examples include brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin, condensates of brominated polyphenylene ether, brominated bisphenol A, and cyanuryl chloride, and uncrosslinked or crosslinked brominated polystyrene. Furthermore, compounds other than brominated aromatic ring-containing aromatic compounds such as hexabromocyclododecane may also be used. These bromine-containing flame retardants may be used individually or in combination of two or more types.

[0045] (Boron-containing flame retardant) Examples of boron-containing flame retardants used in the present invention include borax, boron oxide, boric acid, and borates. Examples of boron oxides include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide. Examples of borates include alkali metals, alkaline earth metals, elements from groups 4, 12, and 13 of the periodic table, and ammonium borates. Specifically, examples include alkali metal borates such as lithium borate, sodium borate, potassium borate, and cesium borate; alkaline earth metal borates such as magnesium borate, calcium borate, and barium borate; zirconium borate, zinc borate, aluminum borate, and ammonium borate. Boron-containing flame retardants may be used alone or in combination of two or more types. The boron-containing flame retardant used in the present invention is preferably a borate, and more preferably zinc borate.

[0046] (Antimony-containing flame retardant) Examples of antimony-containing flame retardants include antimony oxide, antimonate salts, and pyroantimonate salts. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimonate salts include sodium antimonate and potassium antimonate. Examples of pyroantimonate salts include sodium pyroantimonate and potassium pyroantimonate. Antimony-containing flame retardants may be used alone or in combination of two or more types. The antimony-containing flame retardant used in this invention is preferably antimony oxide.

[0047] (Chlorine-containing flame retardant) Examples of chlorine-containing flame retardants commonly used in polyurethane foam include polychlorinated naphthalene, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclooctene, which is sold under the trade name "Dechloran Plus."

[0048] (metal hydroxide) Examples of metal hydroxides used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, and tin hydroxide. A single metal hydroxide may be used, or two or more may be used in combination. Aluminum hydroxide is preferred as the metal hydroxide.

[0049] As a solid flame retardant to be contained in the polyol-containing composition of the present invention, from the viewpoint of imparting good flame retardancy to polyurethane foam, at least one selected from the group consisting of red phosphorus-based flame retardants and phosphinate metal salts is preferred, and it is more preferable to contain at least a red phosphorus-based flame retardant.

[0050] The amount of 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 even more preferably 30 to 120 parts by mass, per 100 parts by mass of polyol. When a red phosphorus-based flame retardant is included as a 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 even more preferably 20 to 40 parts by mass, per 100 parts by mass of polyol. Furthermore, when a metal phosphinate salt is included as a solid flame retardant, the content of the metal phosphinate salt is preferably 35 to 120 parts by mass, more preferably 50 to 100 parts by mass, and even more preferably 60 to 90 parts by mass. When the content of these solid flame retardants is above the lower limit, 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 below the upper limit, the handling properties and foaming properties when mixing the polyol-containing composition with polyisocyanate are improved.

[0051] <Liquid Flame Retardant> The polyol-containing composition of the present invention may contain a liquid flame retardant that is liquid at room temperature (23°C) and atmospheric pressure (1 atm). Specific examples of liquid flame retardants include phosphate esters. Using phosphate esters helps maintain the fluidity of the polyol-containing composition, facilitating the formation of polyurethane foam.

[0052] As phosphate esters, monophosphate esters, condensed phosphate esters, etc., can be used. A monophosphate ester is a phosphate ester that has one phosphorus atom in its molecule. Examples of monophosphate esters include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, and tri(2-ethylhexyl) phosphate; halogen-containing phosphate esters such as tris(β-chloropropyl) phosphate; trialkoxy phosphates such as tributoxyethyl phosphate; aromatic ring-containing phosphate esters such as tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, cresyldiphenyl phosphate, and diphenyl(2-ethylhexyl) phosphate; and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate.

[0053] Examples of condensed phosphate esters include aromatic condensed phosphate esters such as trialkyl polyphosphates, resorcinol polyphenyl phosphates, bisphenol A polycresyl phosphates, and bisphenol A polyphenyl phosphates. Examples of commercially available condensed phosphate esters include "CR-733S," "CR-741," and "CR747" from Daihachi Chemical Industry Co., Ltd., and "ADEKA Stab PFR" and "FP-600" from ADEKA Corporation.

[0054] The phosphate esters may be used individually from the above-mentioned types, or two or more may be used in combination. Among these, monophosphate esters are preferred from the viewpoint of making it easier to adjust the viscosity of the polyol-containing composition and from the viewpoint of improving the flame retardancy of the polyurethane foam, and halogen-containing phosphate esters such as tris(β-chloropropyl)phosphate are more preferred. The content of phosphate ester in the polyol-containing composition is preferably 5 to 100 parts by mass, more preferably 12 to 90 parts by mass, even more preferably 20 to 75 parts by mass, and still more preferably 30 to 60 parts by mass, per 100 parts by mass of polyol.

[0055] <Inorganic fillers> The filler contained in the polyol-containing composition of the present invention may be an inorganic filler other than the solid flame retardant described above. Suitable inorganic fillers include needle-shaped 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. These inorganic fillers may be used individually or in combination of two or more. While the inorganic fillers used in the present invention are not particularly limited, from the viewpoint of imparting good mechanical properties to polyurethane foam, it is preferable to include needle-shaped fillers among those described above. Furthermore, it is even more preferable that the polyol-containing composition contains at least one selected from the group consisting of red phosphorus-based flame retardants and phosphinate metal salts, and a needle-shaped filler.

[0056] (Needle-shaped filler) Examples of needle-shaped fillers include potassium titanate whiskers, aluminum borate whiskers, magnesium-containing whiskers, silicon-containing whiskers, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fibers, carbon fibers, graphite fibers, metal fibers, slag fibers, gypsum fibers, silica fibers, alumina fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, stainless steel fibers, and the like. These needle-shaped fillers can be used individually or in combination of two or more types. The aspect ratio (length / diameter) of the needle-shaped filler used in the present invention is preferably in the range of 5 to 50, and more preferably in the range of 10 to 40. This aspect ratio can be determined by observing the needle-shaped filler with a scanning electron microscope and measuring its length and width.

[0057] The amount of 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 even more preferably 40 to 80 parts by mass, per 100 parts by mass of polyol. If the amount of inorganic filler is above the lower limit, it becomes possible to impart good mechanical properties to the polyurethane foam. On the other hand, if the amount of inorganic filler is below the upper limit, the handling properties and foaming properties when mixing the polyol-containing composition with polyisocyanate are improved. Furthermore, when using needle-shaped fillers as inorganic fillers, the content of needle-shaped fillers is preferably 20 to 100 parts by mass, more preferably 25 to 95 parts by mass, and even more preferably 30 to 90 parts by mass, per 100 parts by mass of polyol.

[0058] <Foaming agent> The blowing agent promotes the foaming of the foamable polyurethane composition described later. Examples of blowing agents include organic physical blowing agents such as water, low boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane; chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride; ether compounds such as hydrofluoroolefins (hereinafter sometimes referred to as "HFO") and diisopropyl ether; or mixtures of these compounds; and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Of these, it is preferable to include hydrofluoroolefin (HFO), which has high stability as a blowing agent, is less prone to a decrease in catalytic activity, and also has a low environmental impact.

[0059] Suitable HFOs as blowing agents include fluoroalkenes with approximately 3 to 6 carbon atoms. Alternatively, the HFO may be a hydrochlorofluoroolefin containing a chlorine atom, and therefore may also be a chlorofluoroalkene with approximately 3 to 6 carbon atoms. Examples of HFOs include trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorodifluoropropene, chlorotrifluoropropene such as HFO-1233, and chlorotetrafluoropropene. More specifically, 3,3,3-trifluoropropene (HFO-1243zf), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,1,3,3-tetrafluoropropene, cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)), trans-1,2,3,3,3-penta Examples include fluoropropene (HFO-1225ye(E)), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1,1,2,3,3-pentafluoropropene (HFO-1225yc), trans-1-chloro-3,3,3-trifluoropropene (HFO-1233zd(E)), and 1,1,1,4,4,4-hexafluorobuto-2-ene (HFO-1336mzz). Among these, HFO-1233zd(E) is preferred.

[0060] The content of the blowing agent is not particularly limited, but is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and even more preferably 35 to 60 parts by mass, per 100 parts by mass of polyol. If the content of the blowing agent is above the lower limit, foaming is promoted, resulting in good foamability and a reduction in the density of the polyurethane foam. On the other hand, if the content of the blowing agent is below the upper limit, excessive foaming can be suppressed.

[0061] The above-mentioned foaming agents can be used one or more types. In the foamed 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 have excellent handling properties. Water is particularly preferred from the viewpoint of adjusting the isocyanate index and ease of handling.

[0062] The HFO content is not particularly limited, but is preferably 19 to 75 parts by mass, more preferably 29 to 67 parts by mass, and even more preferably 34 to 58 parts by mass, per 100 parts by mass of polyol. If the foaming agent content is above the lower limit, foaming is promoted, resulting in good foamability and a reduction in the density of the polyurethane foam. On the other hand, if the foaming agent content is below the upper limit, excessive foaming can be suppressed.

[0063] The water content is not particularly limited, but is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, and even more preferably 0.5 to 2 parts by mass, per 100 parts by mass of polyol. If the foaming agent content is above the lower limit, foaming is promoted, resulting in good foamability and a reduction in the density of the polyurethane foam. On the other hand, if the foaming agent content is below the upper limit, excessive foaming can be suppressed.

[0064] <Foam stabilizer> The polyol-containing composition of the present invention may also contain a foam stabilizer. The inclusion of a foam stabilizer improves the foaming properties of the polyurethane foam, for example, promoting foaming when reacting it with polyisocyanate in spray application. Examples of foam stabilizers include surfactants, more specifically, nonionic surfactants, cationic surfactants, anionic surfactants, and the like. 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 this invention is not particularly limited, but silicone foam stabilizers are preferred from the viewpoint of foaming properties. The foam stabilizer may be used alone or in combination of two or more types.

[0065] The foam stabilizer content 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 even more preferably 2 to 8 parts by mass, per 100 parts by mass of polyol. When the foam stabilizer content is above the lower limit, the mixture of the polyol-containing composition and polyisocyanate is easily foamed, making it possible to obtain a homogeneous polyurethane foam. Furthermore, when the foam stabilizer content is below the upper limit, the balance between manufacturing cost and the obtained effect is optimized.

[0066] <Other ingredients> The polyol-containing composition may, as necessary and within the limits that do not impair the objectives of the present invention, contain one or more additives selected from phenolic, amine, and sulfur-based antioxidants, heat stabilizers, metal damage inhibitors (metal deactivators), antistatic agents, stabilizers, crosslinking agents, lubricants, softeners, plasticizers, tackifying resins, polybutene, petroleum resins, and other tackifying agents.

[0067] [Foamed polyurethane composition and polyurethane foam] The present invention also provides a foamed polyurethane composition. It contains polyols, blowing agents, catalysts, flame retardants, and pigments, in addition to polyisocyanate. Furthermore, the foamed polyurethane composition may contain fillers other than flame retardants, liquid flame retardants such as phosphate esters, foam stabilizers, and other components. The details of each component contained in the foamed polyurethane composition are as described above, and their explanation is omitted here.

[0068] The foamed polyurethane composition of the present invention preferably comprises the above polyol-containing composition and poly It contains isocyanates and is obtained by mixing them. It is advisable to store the polyol-containing composition and the polyisocyanate in separate containers before mixing. Furthermore, as will be described later, the foamed 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. Furthermore, the foamed polyurethane composition may be obtained by separately preparing a polyol-containing composition without pigment, a polyisocyanate without pigment, and a pigment, and mixing them immediately before use.

[0069] <Polyisocyanate> Examples of polyisocyanates in the present invention include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates. Examples of aromatic polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate (polymeric MDI).

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

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

[0072] Among these, aromatic polyisocyanates are preferred from the viewpoint of ease of use and availability, diphenylmethane diisocyanate, polymeric MDI, or mixtures thereof are more preferred, with diphenylmethane diisocyanate being even more preferred, and 4,4'-diphenylmethane diisocyanate being particularly preferred. Polyisocyanates may be used individually or as a mixture of two or more. Furthermore, before mixing the polyisocyanate with the polyol-containing composition, known additives that are incorporated into polyisocyanates may be added as appropriate.

[0073] Furthermore, it is preferable that the polyol-containing composition and the polyisocyanate mixed with the polyol-containing composition have substantially the same volume. Specifically, the volume ratio of polyisocyanate to 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 are no particular limitations on the isocyanate index in the foamed polyurethane composition of the present invention, but a value of 200 or higher is preferred. When the isocyanate index is above the lower limit, the amount of polyisocyanate relative to the polyol becomes excessive, making it easier to form isocyanurate bonds by the trimer of polyisocyanate, resulting in improved flame retardancy of the polyurethane foam. It also becomes possible to impart flame retardancy. Furthermore, when the index is above the lower limit, in combination with the various catalysts described above, it becomes easier to produce polyurethane foam with sufficient isocyanurate bonds, that is, polyurethane foam that combines flame retardancy and heat insulation at a high level. From these viewpoints, an isocyanate index of 250 or higher is more preferred, and 300 or higher is even more preferred. Furthermore, 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 below the above upper limit, flame retardancy that is sufficiently commensurate with the manufacturing cost can be obtained.

[0075] The isocyanate index can be calculated using the following method. Isocyanate Index = Equivalents of polyisocyanate ÷ (Equivalents of polyol + Equivalents of water) × 100 Here, each equivalent number can be calculated as follows: • Equivalent weight of polyisocyanate = Amount of polyisocyanate used (g) × NCO content (mass%) / Molecular weight of NCO (moles) × 100 • Equivalent weight of polyol = OHV × Amount of polyol used (g) ÷ Molecular weight of KOH (millimoles) OHV is the hydroxyl value (mgKOH / g) of a polyol. • Equivalent amount of water = Amount of water used (g) / Molecular weight of water (moles) × Number of OH groups in water In the above formulas, the molecular weight of NCO is 42 moles, the molecular weight of KOH is 56,100 millimoles, the molecular weight of water is 18 moles, and the number of OH groups in water is 2.

[0076] <Total calorific value> The polyurethane foam comprising the foamed polyurethane composition of the present invention exhibits a radiant thermal intensity of 50 kW / m² in accordance with the ISO-5660 test method. 2 The total heat output when heated for 10 minutes was 8 MJ / m². 2 The following is preferable: Total heat generation is 8 MJ / m³. 2 As a result of the following, the polyurethane foam made from the foamed polyurethane composition of the present invention has a predetermined flame retardancy. From the viewpoint of further improving the flame retardancy of the foam, the total heat output is set to 7.5 MJ / m³. 2 It is more preferable that the following conditions are met: 7 MJ / m 2 The following is even more preferable: Furthermore, the polyurethane foam made from the foamed polyurethane composition of the present invention generates a total heat output of 8 MJ / m² even when heated for 20 minutes in the same manner as described above. 2 It is even more preferable that the following conditions are met: 7.5 MJ / m 2 The following is particularly preferable:

[0077] In the present invention, it is preferable that the color difference ΔE(1) of polyurethane foam A, obtained by mixing a polyol-containing composition containing a pigment with a polyisocyanate, and polyurethane foam B, obtained by mixing a polyol-containing composition obtained by storing the polyol-containing composition at 55°C for 3 days with a polyisocyanate, is 3 or less. When the above-mentioned 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 of time. Taking these points into consideration, a color difference ΔE(1) of 2 or less is preferable, and 1 or less is more preferable. The above color difference ΔE(1) can be determined by preparing polyurethane foams A and B using a polyol-containing composition and polyisocyanate, which constitute the foamed polyurethane composition, according to the method described in the examples, and then measuring the color difference between polyurethane foams A and B.

[0078] Furthermore, it is preferable that the foamable polyurethane composition of the present invention has a color difference ΔE(2) of 3 or more between polyurethane foam A, obtained by mixing the above polyol-containing composition with polyisocyanate, and polyurethane foam C, obtained by mixing a polyol-containing composition without a colorant with polyisocyanate. A color difference ΔE(2) of 4 or more is more preferable, and 5 or more is even more preferable. If the color difference ΔE(2) is above the lower limit, it can be said that the polyurethane foam can be colored well. Furthermore, a polyol-containing composition without colorants refers to a polyol-containing composition that has the same composition as a polyol-containing composition, except that it does not contain colorants such as pigments. The above color difference ΔE(2) can be determined by preparing polyurethane foams A and C using a polyol-containing composition and polyisocyanate, which constitute the foamed polyurethane composition, or by using a colorant-free polyol-containing composition and polyisocyanate, according to the method described in the examples, and then measuring the color difference between the polyurethane foams A and C.

[0079] <Application> The foamed polyurethane composition of the present invention can preferably be used for spraying applications. Therefore, the foamed polyurethane composition and polyurethane foam of the present invention, which have excellent flame retardancy and heat insulation properties, can be suitably used in buildings such as walls, ceilings, roofs, and floors, and it is preferable to mold the polyurethane foam onto surfaces such as walls, ceilings, roofs, and floors that are to be sprayed.

[0080] <Method for manufacturing polyurethane foam> The present invention provides a method for producing polyurethane foam, which involves 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, and then mixing the polyol-containing composition with polyisocyanate and foaming it to produce polyurethane foam. In the method for manufacturing polyurethane foam, the pigment may be added in advance to either the polyol-containing composition or the polyisocyanate, or it may be added when mixing the polyol-containing composition and the polyisocyanate.

[0081] Below, as the first embodiment, we will describe a method in which the pigment is added to the polyol-containing composition in advance. The method for producing polyurethane foam according to the first embodiment of the present invention first involves preparing a polyol-containing composition by blending at least a polyol, a blowing agent, a catalyst, a flame retardant including a solid flame retardant, and a pigment. There are no particular restrictions 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 using a homodisperser or the like for about 30 seconds to 20 minutes. The polyol-containing composition obtained by this method contains a pigment, and its details are as described above.

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

[0083] Next, a method in which the pigment is added to the polyisocyanate in advance will be described as a second embodiment. A method for producing polyurethane foam according to a second embodiment of the present invention involves first 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. The method for preparing the polyol-containing composition is as described above. Furthermore, the polyol-containing composition obtained 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 manner and the polyisocyanate to which the pigment has been added are brought to the construction site, mixed on-site to obtain a foamable polyurethane composition, and the foamable polyurethane composition is reacted and foamed to produce polyurethane foam.

[0085] Furthermore, a third embodiment will describe a method of adding the pigment when mixing the polyol-containing composition with the polyisocyanate. In other words, in the third embodiment, a polyol-containing composition is prepared by blending at least a polyol, a blowing agent, a catalyst, and a flame retardant including a solid flame retardant. In this case, the polyol-containing composition does not need to contain a pigment. The polyol-containing composition prepared 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, polyisocyanate, and pigment are brought to the construction site, and the pigment is added (also called post-addition) when the polyol-containing composition and polyisocyanate are mixed at the construction site. By adding the pigment post-addition, the desired color tone can be adjusted on-site. In this context, "when mixing a polyol-containing composition and polyisocyanate" does not strictly mean that the pigment must be added simultaneously with the mixing of the polyol-containing composition and polyisocyanate. It also includes cases where the pigment is added to the polyol-containing composition or polyisocyanate immediately before mixing, brought to the construction site. "Immediately before mixing" refers, for example, to within about one week before mixing, preferably within about three days, and more preferably within about one day. A polyol-containing composition or polyisocyanate to which pigment has been added can be reused regardless of the storage period, provided it is re-stirred.

[0086] Therefore, the pigment may be added to the polyol-containing composition at the construction site, and the polyol-containing composition with the added pigment may be further mixed with polyisocyanate. Alternatively, the pigment may be added to the polyisocyanate at the construction site, and the polyisocyanate with the added pigment may be mixed with the polyol-containing composition. Furthermore, the pigment, polyol-containing composition, and polyisocyanate may be mixed simultaneously at the construction site. Among these, it is preferable to add the pigment to the polyol-containing composition at the construction site, and then further mix the polyol-containing composition with the added pigment into the polyisocyanate.

[0087] Polyurethane foam is preferably manufactured using, for example, a foaming machine. For instance, a polyol-containing composition can be mixed with polyisocyanate in a foaming machine, and the resulting mixture (foamable polyurethane composition) can be foamed. A spray device with a spray gun can be used as the foaming machine. In this case, as described above, it is preferable that the pigment be included in either the polyol-containing composition or the polyisocyanate, but it is preferable that the pigment be included in the polyol-containing composition. The polyol-containing composition is supplied to a foaming machine and mixed with polyisocyanate supplied from another container inside the machine. The resulting mixture (foamable polyurethane composition) is then discharged from a nozzle such as a spray gun, and polyurethane foam is formed using the discharged foamable polyurethane composition.

[0088] This manufacturing method is preferably applicable to spray applications. Therefore, the mixed liquid discharged from the foaming machine is sprayed onto the surface to be treated with a constant discharge pressure and foamed, thereby forming polyurethane foam on the surface to be treated. [Examples]

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

[0090] [Materials used] <Polyisocyanate> • 4,4'-Diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Manka Chemical Japan Co., Ltd., product name: PM200)

[0091] <Polyol-containing composition> (Polyol) • p-phthalate polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RLK-087, hydroxyl value = 200 mg KOH / g)

[0092] (catalyst) • Ammonium salt (trimerization catalyst), tetramethylammonium 2,2-dimethylpropanoate (Air Products, product name: DABCO® TMR7), concentration 45-55% by mass • Metal catalyst (trimerization catalyst), potassium 2-ethylhexanoate (Air Products Co., Ltd., product name: DABCO(registered trademark) K-15), concentration 70-80% by mass • Resinized amine catalyst, 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT DM70), concentration 65-75% by mass • Resin-based metal catalyst, bismastrioctate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-600), concentration 55-58% by mass • Resin-based metal catalyst, dioctyl (2-ethylhexyl) suzubatesate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-830), concentration approximately 99% by 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 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 salt (Clariant Corporation, product name: EXOLIT OP930)

[0096] (Inorganic fillers) • Wollastonite (SiO2·CaO) (manufactured by Kinsei Matec Co., Ltd., product name: SH-1250)

[0097] (Coloring agent) • Black coloring agents: Black pigment (Milliken & Company, product name: DispersiTech Black 2140), black dye (Milliken & Company, product name: REACTINT BLACK X95AB) • Blue coloring agent: Blue pigment (Milliken & Company, product name: DispersiTech Blue 2402)

[0098] [Manufacturing of polyurethane foam] Formulas listed in Table 1 A polyol-containing composition was prepared by mixing each component accordingly. A polyurethane foam was manufactured using this polyol-containing composition and polyisocyanate under the following conditions. <Manufacturing conditions> • Spraying machine: Graco H-25 spraying device • Settings (Heater settings) Isocyanate heater: 38℃ Premix heater (for heating polyol-containing compositions): 38℃ Hose heater (for pre-mixing heating of polyisocyanate and polyol-containing compositions): 38°C Pressure: Adjust as needed to ensure the mist forms a wide, circular area. • Substrate temperature (temperature of the surface to be sprayed): 20℃±1℃

[0099] [Evaluation methods for polyurethane foam] 1.Decolorization degree Polyurethane foam B was obtained by placing a foamable polyurethane composition in a pail, storing it at 55°C for 3 days, and then performing spray foaming. Similarly, polyurethane foam A was obtained by placing a foamable polyurethane composition in another pail and immediately performing spray foaming without any storage. The surface of the polyurethane foam obtained as described above was measured using a colorimeter (KONICA MINOLTA, product name: SPECTROPHOTOMETER CM-5), and the degree of surface decolorization was evaluated by the color difference ΔE(1) between the two polyurethane foams A and B. The evaluation criteria for the degree of decolorization are as follows. ○: ΔE(1) = 3 or less, no decolorization. ×: ΔE(1) greater than 3, decolorization present.

[0100] 2. Flame retardant The polyurethane foam produced under the above manufacturing conditions is cut into 10cm x 10cm x 5cm squares to serve as test specimens. These test specimens are subjected to a radiant thermal intensity test of 50kW / m² in accordance with ISO 5660. 2The total heat generated was measured when the material was heated for 10 to 20 minutes. Based on the total heat generated in this manner, the flame retardancy of the polyurethane foam was evaluated. The criteria for evaluating flame retardancy are as follows. ○: 8 MJ / m² at 20 minutes from the start of heating 2 below △: 8 MJ / m³ at 10 minutes from the start of heating 2 below ×: 8 MJ / m² at 10 minutes from the start of heating 2 super

[0101] 3. Colorability Polyurethane foam A was formed from a polyol-containing composition containing a pigment, and polyurethane foam C was formed from a polyol-containing composition without a colorant (colorant-free polyol-containing composition). A colorimeter (KONICA MINOLTA, product name: SPECTROPHOTOMETER CM-5) was then applied to the surface of each foam. The color difference ΔE(2) of the two polyurethane foams A and C obtained in this way was used to evaluate the colorability of the surface. The evaluation criteria for colorability are as follows. Note that the colorant-free polyol-containing composition is a polyol-containing composition with the same formulation as each example and comparative example, except that it does not contain a colorant. ○: ΔE(2) = 3 or greater, colored. ×: ΔE(2) = less than 3, no coloring.

[0102] [Examples 1-7, Comparative Examples 1-4] A polyol-containing composition was prepared by mixing each component according to the formulations shown in Table 1. A polyurethane foam was manufactured using the polyol-containing composition and polyisocyanate, and evaluated according to evaluation methods 1 to 3 described above. The results are shown in Table 1. The mixing ratio of the polyol-containing composition to the polyisocyanate was 1:1 by volume.

[0103] [Table 1] The catalyst content values ​​are those for the product as a whole.

[0104] As is clear from the results of the above examples and comparative examples, the polyol-containing composition of the present invention does not decolorize the colorant, and the polyurethane foam formed from the composition exhibits good flame retardancy and colorability. In contrast, the polyol-containing compositions of Comparative Examples 1-3 contained dyes as colorants, resulting in discoloration of the colorants. In addition to discoloration of the colorants, the polyol-containing composition of Comparative Example 3 did not contain a solid flame retardant, thus impairing the flame retardancy of the polyurethane foam. Furthermore, the polyol-containing composition of Comparative Example 4 did not contain any colorants, and therefore could not color the polyurethane foam.

Claims

1. A polyol-containing composition for reacting with polyisocyanate to obtain polyurethane foam used as an insulating material, It contains a polyol, a blowing agent, a catalyst, a flame retardant, and a pigment, and the flame retardant includes a solid flame retardant. The solid flame retardant is a component that is solid at room temperature (23°C) and normal pressure (1 atm) and does not dissolve in the polyol-containing composition. The catalyst is not included in the solid flame retardant. A polyol-containing composition wherein the pigment is a blue pigment, and the blue pigment is solid at room temperature (23°C) and normal pressure (1 atm), and does not react with other components in the polyol-containing composition.

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 comprises a trimerizing catalyst.

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

5. The polyol-containing composition according to 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 a metal catalyst selected from the group consisting of bismuth or tin.

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

8. The foamable 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 obtained by storing the polyol-containing composition at 55°C for 3 days with the polyisocyanate is 3 or less.

9. A foamable polyurethane composition for obtaining a polyurethane foam used as a thermal insulation material, comprising a polyol, polyisocyanate, blowing agent, catalyst, flame retardant, and pigment, wherein the flame retardant includes a solid flame retardant, The solid flame retardant is solid at room temperature (23°C) and normal pressure (1 atm), and is a component that does not dissolve in a polyol-containing composition containing components other than the polyisocyanate among the components contained in the foamed polyurethane composition. The catalyst is not included in the solid flame retardant. A foamable polyurethane composition wherein the pigment is a blue pigment, and the blue pigment is solid at room temperature (23°C) and normal pressure (1 atm), and does not react with other components in the polyol-containing composition.

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

11. A foamed polyurethane composition according to any one of claims 7 to 10, for use in spray applications.

12. A polyurethane foam used as a thermal insulation material, obtained by foaming a foamable polyurethane composition according to any one of claims 7 to 11.

13. A polyol-containing composition is prepared by blending at least a polyol, a blowing agent, a catalyst, and a flame retardant including a solid flame retardant. The solid flame retardant is a solid at room temperature (23°C) and normal pressure (1 atm), and is a component that does not dissolve in the polyol-containing composition. The catalyst is not included in the solid flame retardant. A method for producing polyurethane foam used as an insulating material, comprising mixing the polyol-containing composition with a polyisocyanate, reacting and foaming the mixture, A method for producing polyurethane foam, comprising adding a blue pigment, which is solid at room temperature (23°C) and atmospheric pressure (1 atm), and does not react with other components in the polyol-containing composition, to the polyol-containing composition or polyisocyanate beforehand, or adding the pigment when mixing the polyol-containing composition and polyisocyanate.

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