Polyol-containing composition and foamable polyurethane composition

Abstract

To provide a polyol-containing composition that can achieve quasi-incombustibility without using a powder fire retardant, and an expandable polyurethane composition using the polyol-containing composition.SOLUTION: A polyol-containing composition is intended to obtain polyurethane foam by being reacted with polyisocyanate, and contains polyol, a blowing agent, a fire retardant, and a catalyst. Phosphorus concentration in the polyol-containing composition is 3 mass% or more in the polyol-containing composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyol-containing composition and a foamable polyurethane composition. [Background technology]

[0002] Due to its excellent heat insulating properties and adhesive properties, polyurethane foam is used as a heat insulating material for buildings such as apartment complexes, detached houses, various school facilities, commercial buildings, etc. Polyurethane foam is obtained by foaming a foamable polyurethane composition containing a polyol-containing composition and a polyisocyanate.

[0003] Because polyurethane foam is flammable, flame retardants are added to the urethane resin when flame retardancy is required. Conventional flame retardants require the inclusion of large amounts of flame retardant to improve flame retardancy, which significantly reduces various physical properties. When a large amount of powdered flame retardant such as expanded graphite is added to the liquid raw material of a urethane resin in order to improve flame retardancy, the raw material may clog the nozzle when it is injected with a syringe, resulting in poor moldability. Furthermore, the viscosity of the raw material increases, reducing the flowability during injection, which can lead to problems with moldability. Furthermore, raw materials containing a large amount of powdered flame retardant have the problem that the flame retardant tends to settle during storage, resulting in poor dispersion.

[0004] In response to the above-mentioned problems, rigid urethane resin compositions have been proposed that contain a flame retardant consisting of a low-temperature flame retardant having a decomposition temperature of less than 250°C, a medium-temperature flame retardant having a decomposition temperature of 250°C or higher but lower than 400°C, and a high-temperature flame retardant having a decomposition temperature of 400°C or higher (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2019-119825 [Patent Document 2] Japanese Patent Application Laid-Open No. 2018-9120 Summary of the Invention [Problem to be solved by the invention]

[0006] The rigid urethane resin compositions disclosed in Patent Documents 1 and 2 are said to be able to achieve good flame retardancy even when the amount of powder flame retardant added is reduced, but they still contain a powder flame retardant as an essential component, making it difficult to completely achieve the above-mentioned objectives.

[0007] Therefore, an object of the present invention is to provide a polyol-containing composition that contains a polyol, a blowing agent, a flame retardant, and a catalyst, and that can achieve quasi-nonflammability without using a powdery flame retardant, and to provide a foamable polyurethane composition using the same. [Means for solving the problem]

[0008] As a result of extensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by providing a polyol-containing composition containing a polyol, a blowing agent, a flame retardant, and a catalyst, and by adjusting the phosphorus concentration in the polyol-containing composition to a certain concentration or higher, and have completed the present invention as described below.

[0009] The present invention is summarized as follows [1] to

[12] . [1] A polyol-containing composition for producing a polyurethane foam by reacting with a polyisocyanate, the polyol-containing composition comprising a polyol, a blowing agent, a flame retardant, and a catalyst, and wherein the phosphorus concentration in the polyol-containing composition is 3% by mass or more. [2] The polyol-containing composition according to [1] above, wherein the flame retardant comprises an aromatic-containing phosphate ester. [3] The polyol-containing composition according to [1] above, wherein the flame retardant comprises a condensed phosphate ester. [4] The polyol-containing composition according to any one of the above [1] to [3], wherein the concentration of chlorine other than that derived from the blowing agent is 10% by mass or more. [5] The polyol-containing composition according to any one of the above [1] to [4], which is substantially free of powder. [6] The polyol-containing composition according to any one of the above [1] to [5], wherein the catalyst comprises a trimerization catalyst. [7] The polyol-containing composition according to any one of the above [1] to [6], wherein the catalyst comprises a urethane-forming metal catalyst. [8] The polyol-containing composition according to any one of the above [1] to [7], which has a viscosity at 20°C of 1000 mPa·s or less. [9] A foamable polyurethane composition comprising the polyol-containing composition according to any one of the above [1] to [8] and a polyisocyanate.

[10] Cone calorimeter test according to ISO-5660 shows a strength of 50 kW / m 2 When heated for 10 minutes, the total calorific value is 8MJ / m 2 The foamable polyurethane composition according to [9] above, which is:

[11] The foamable polyurethane composition according to [9] or

[10] above, which has an isocyanate index of 200 or more.

[12] The foamable polyurethane composition according to any one of the above [9] to

[11] , which is used for spray applications. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a polyol-containing composition that can achieve quasi-nonflammability without using a powdery flame retardant, and a foamable polyurethane composition using the same. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. [Polyol-containing composition] The polyol-containing composition of the present invention is intended to be reacted with a polyisocyanate to obtain a polyurethane foam, and contains a polyol, a blowing agent, a flame retardant, and a catalyst. In the present invention, the phosphorus concentration in the polyol-containing composition is 3% by mass or more. If the phosphorus concentration is lower than 3% by mass, the polyol-containing composition cannot sufficiently improve its flame retardancy even if it contains a flame retardant. On the other hand, by setting the phosphorus concentration to 3% by mass or more, good flame retardancy can be achieved even when the composition does not substantially contain powder, as described below. The phosphorus concentration is preferably 3.2% by mass or more, more preferably 3.5% by mass or more, and is preferably 10% by mass or less, more preferably 6% by mass or less. By keeping the phosphorus concentration at or below the upper limit, foaming is not inhibited.

[0012] <Polyol> The polyol-containing composition of the present invention contains a polyol as a raw material for polyurethane foam. The polyol used in the present invention is not particularly limited, but examples thereof include polylactone polyols, polycarbonate polyols, polyester polyols, polyether polyols, and polymer polyols.

[0013] Examples of polylactone polyols include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol. Examples of polycarbonate polyols include polyols obtained by dealcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, and the like.

[0014] Examples of polyester polyols include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone, and condensates of hydroxycarboxylic acids and the above-mentioned polyhydric alcohols. Examples of polybasic acids include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), and succinic acid. Examples of polyhydric alcohols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, and neopentyl glycol. Examples of hydroxycarboxylic acids include castor oil and reaction products of castor oil and ethylene glycol.

[0015] Examples of polyether polyols include polymers obtained by ring-opening polymerization of at least one alkylene oxide, such as ethylene oxide, propylene oxide, or tetrahydrofuran, in the presence of at least one low-molecular-weight active hydrogen compound having two or more active hydrogens. Examples of low-molecular-weight active hydrogen compounds having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol, triols such as glycerin and trimethylolpropane, and amines such as ethylenediamine and butylenediamine.

[0016] Examples of polymer polyols include polymers obtained by graft polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, or methacrylate with an aromatic polyol, an alicyclic polyol, an aliphatic polyol, or a polyester polyol; polybutadiene polyol; and modified polyols of polyhydric alcohols or hydrogenated products thereof. Examples of aromatic polyols used in the production of polymer polyols include bisphenol A, bisphenol F, phenol novolac, and cresol novolac. Examples of alicyclic polyols used in the production of polymer polyols include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol. Examples of aliphatic polyols used in the production of polymer polyols include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

[0017] Examples of modified polyols of polyhydric alcohols include those obtained by modifying raw material polyhydric alcohols by reacting them with alkylene oxides. Examples of polyhydric alcohols include trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric to octahydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, and dipentaerythritol; sucrose, glucose, mannose, fructose, methyl glucoside, and derivatives thereof; polyols such as phloroglucinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4,5,8-tetrahydroxyanthracene; polyfunctional polyols (e.g., having 2 to 100 functional groups) such as castor oil polyol, (co)polymers of hydroxyalkyl (meth)acrylate, and polyvinyl alcohol; and condensates of phenol and formaldehyde (novolak).

[0018] Although the method for modifying the polyhydric alcohol is not particularly limited, a method of adding alkylene oxide (hereinafter also referred to as "AO") is preferably used. Examples of AO include AOs having 2 to 6 carbon atoms, such as ethylene oxide (hereinafter also referred to as "EO"), 1,2-propylene oxide (hereinafter also referred to as "PO"), 1,3-propylene oxide, 1,2-butylene oxide, and 1,4-butylene oxide. Among these, PO, EO, and 1,2-butylene oxide are preferred from the viewpoints of properties and reactivity, and PO and EO are more preferred. When two or more AOs are used (for example, PO and EO), the addition method may be block addition, random addition, or a combination of these.

[0019] The polyol used in the present invention is preferably at least one selected from the group consisting of polyester polyols and polyether polyols. Furthermore, polyols having two hydroxyl groups are preferred. Among these, aromatic polyester polyols, which are polyester polyols having aromatic rings, are preferred from the viewpoint of enhancing flame retardancy. More preferred aromatic polyester polyols are those obtained by dehydration condensation of polybasic acids having aromatic rings, such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid), with dihydric alcohols, such as bisphenol A, ethylene glycol, and 1,2-propylene glycol.

[0020] The hydroxyl value of the polyol is preferably 20 to 300 mgKOH / g, more preferably 40 to 280 mgKOH / g, even more preferably 100 to 250 mgKOH / g, and particularly preferably 120 to 210 mgKOH / g. When the hydroxyl value of the polyol is equal to or less than the upper limit, the viscosity of the polyol-containing composition tends to decrease, which is preferable from the viewpoint of handleability, etc. On the other hand, when the hydroxyl value of the polyol is equal to or more than the lower limit, the crosslink density of the polyurethane foam increases, thereby increasing its strength. The hydroxyl value of the polyol can be measured in accordance with JIS K 1557-1:2007.

[0021] The polyol content in the polyol-containing composition of the present invention is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass. A polyol content of at least the lower limit is preferred because it facilitates the reaction between the polyol and the polyisocyanate. On the other hand, a polyol content of at most the upper limit is preferred from the viewpoint of ease of handling because the viscosity of the polyol-containing composition does not become too high.

[0022] <Foaming agent> Specific examples of blowing agents include water, low-boiling hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrofluorocarbon compounds, ether compounds, hydrofluoroolefin compounds, etc. Further examples of blowing agents include organic physical blowing agents such as mixtures of these compounds, and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. Examples of the low boiling point hydrocarbon include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane. Examples of the chlorinated aliphatic hydrocarbon compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, and isopentyl chloride. Examples of the fluorine compound include CHF3, CH2F2, and CH3F. Examples of the hydrofluorocarbon compounds include hydrofluorocarbons such as HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane), and chlorine-containing hydrofluorocarbons (hydrochlorofluorocarbons) such as trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane)), HCFC22 (chlorodifluoromethane), and HCFC142b (1-chloro-1,1-difluoroethane). Examples of the ether compounds include diisopropyl ether. Examples of the hydrofluoroolefin compound include hydrofluoroolefins such as HFO-1336mzz(Z) (cis-1,1,1,4,4,4-hexafluorobut-2-ene) and HFO-1234yf (2,3,3,3-tetrafluoro-1-propene), and hydrofluoroolefins (hydrochlorofluoroolefins) having chlorine atoms such as HFO-1224yd(Z) (trans-1-chloro-2,3,3,3-tetrafluoropropene), HFO-1233zd(E) (trans-1-chloro-3,3,3-trifluoropropene), and HFO-1224yd(Z) (trans-1-chloro-2,3,3,3-tetrafluoropropene). As the hydrofluoroolefin compound, hydrochlorofluoroolefins are preferred, and among them, HFO-1233zd(E) is more preferred.

[0023] In the present invention, the blowing agent preferably contains a hydrofluoroolefin compound. The content of the hydrofluoroolefin compound per 100 parts by mass of the polyol compound is preferably 10 to 70 parts by mass, more preferably 20 to 65 parts by mass, and even more preferably 30 to 60 parts by mass.

[0024] In the present invention, it is also preferable that the blowing agent contains water, and more preferably, the blowing agent contains a hydrofluoroolefin compound and water. For example, ion-exchanged water, distilled water, etc. can be used as appropriate as the water. From the viewpoints of foamability and flame retardancy, the amount of water per 100 parts by mass of the polyol compound is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, and is preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, and may even be 1 part by mass. In the present invention, when the water content is below these upper limits, the polyurethane foam is less susceptible to flame spread.

[0025] <Flame retardant> The polyol-containing composition of the present invention contains a flame retardant. The flame retardant used in the present invention preferably contains a phosphate ester-based flame retardant. The foamable urethane resin composition contains a phosphate ester-based flame retardant, thereby improving the flame retardancy. The phosphate ester compounds constituting the phosphate ester flame retardants will be described in detail below.

[0026] <Phosphate ester compounds> The polyol-containing composition of the present invention preferably contains a phosphate ester compound as a flame retardant. By containing the phosphate ester compound, the flame retardancy of the polyol-containing composition is improved, and the flame retardancy of the polyurethane foam is improved. The phosphate ester compound preferably contains an aromatic-containing phosphate ester. Furthermore, examples of the phosphate ester compound include monophosphate esters and condensed phosphate esters, and it is preferable to contain a condensed phosphate ester.

[0027] (monophosphate ester) Monophosphate esters are phosphate esters having one phosphorus atom in the molecule. Examples of monophosphate esters include trialkyl phosphates such as trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate, and tri(2-ethylhexyl)phosphate; halogen-containing phosphate esters such as tris(β-chloropropyl)phosphate, tris(tribromoneopentyl)phosphate, and trischloroethylphosphate; trialkoxy phosphates such as tributoxyethyl phosphate; aromatic-containing monophosphate esters such as tricresyl phosphate (TCP), trixylenyl phosphate (TXP), tris(isopropylphenyl)phosphate, cresyl diphenyl phosphate, and diphenyl(2-ethylhexyl)phosphate; and acidic phosphate esters such as monoisodecyl phosphate and diisodecyl phosphate. Among these monophosphate esters, aromatic-containing monophosphate esters are preferred because of their high flame retardancy improvement effect. From the viewpoint of improving flame retardancy, it is preferable that the resin contains a halogen, and specific examples thereof include compounds such as tris(β-chloropropyl)phosphate and tris(tribromoneopentyl)phosphate. In addition to the above, the phosphate ester compound may also be a phosphite, etc. Examples of the phosphite include triphenyl phosphite, tricresyl phosphite, trisnonylphenyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite. The monophosphate esters may be used alone or in combination of two or more.

[0028] (Condensed phosphate ester) Examples of condensed phosphate esters include aromatic condensed phosphate esters such as resorcinol polyphenyl phosphate (trade name "CR-733S", manufactured by Daihachi Chemical Industry Co., Ltd.), bisphenol A polycresyl phosphate (trade name "CR-741", manufactured by Daihachi Chemical Industry Co., Ltd.), and bisphenol A polyphenyl phosphate (trade name "CR747", manufactured by Daihachi Chemical Industry Co., Ltd.) (trade name ADEKA PFR, manufactured by ADEKA). Other examples include "DAIGUARD-580" and "DAIGUARD-880". As the condensed phosphate ester, aromatic condensed phosphate esters are preferred. Furthermore, as the condensed phosphate ester, a halogen-containing condensed phosphate ester can also be preferably used, and examples of commercially available products include "CR-504L", "CR-570", and "DAIGUARD-540" (all manufactured by Daihachi Chemical Industry Co., Ltd.). The condensed phosphate ester may be used alone or in combination of two or more kinds, or a condensed phosphate ester and a monophosphate ester may be used in combination.

[0029] Furthermore, it is preferable that the phosphate ester compound contains a halogen such as chlorine in order to improve flame retardancy. Specifically, the polyol-containing composition of the present invention preferably has a chlorine concentration other than that derived from the blowing agent of 10% by mass or more. When the chlorine concentration is 10% by mass or more, the total calorific value described below is reduced, and good heat resistance is exhibited. Note that tris(β-chloropropyl)phosphate (TMCPP) is preferred as the halogen-containing phosphate ester. The chlorine concentration is not particularly limited, but is, for example, 20% by mass or less.

[0030] When two or more phosphate ester compounds are used, two or more halogen-containing phosphate esters (hereinafter referred to as "halogen-containing phosphate esters") may be used, or a halogen-containing phosphate ester and a halogen-free phosphate ester (hereinafter referred to as "non-halogen phosphate ester") may be used in combination. For example, a trialkyl phosphate or triaryl phosphate may be used in combination with a halogen-containing phosphate ester. Specifically, it is preferred to use tris(β-chloropropyl)phosphate as the halogen-containing phosphate ester in combination with at least one non-halogen phosphate ester selected from trimethyl phosphate, triethyl phosphate, tricresyl phosphate, and trixylenyl phosphate. It is also preferable to use a halogen-containing phosphate ester in combination with a condensed phosphate ester, and it is particularly preferable to use a halogen-containing monophosphate ester in combination with an aromatic condensed phosphate ester.

[0031] Furthermore, the phosphate ester-based flame retardant is preferably a liquid flame retardant at room temperature. By including a liquid phosphate ester-based flame retardant in the foamable urethane resin composition, the amount of solid flame retardant used can be reduced. This improves the storage stability of the composition, making it less likely to produce precipitates during storage. Furthermore, wear on the equipment used when using the composition can be reduced. In this specification, room temperature means 23°C.

[0032] The content of the phosphate ester in the polyol-containing composition of the present invention is not particularly limited as long as the phosphorus concentration in the polyol-containing composition is 3% by mass or more, but is preferably in the range of 55 to 300 parts by mass, more preferably 60 to 250 parts by mass, and even more preferably 65 to 200 parts by mass, per 100 parts by mass of polyol. When the content is equal to or greater than the lower limit, sufficient flame retardancy can be obtained, and when the content is equal to or less than the upper limit, a decrease in the mechanical strength of the polyurethane foam can be suppressed.

[0033] The flame retardant used in the present invention may contain, in addition to the above-mentioned phosphate ester-based flame retardant, a solid flame retardant or an inorganic filler other than a solid flame retardant, as long as the effects of the present invention are not impaired. However, it is preferable that the flame retardant be substantially free of powder. Here, "substantially free of powder" means that the powder content is 5% by mass or less, preferably 1% by mass or less, based on the total amount of the polyol-containing composition. By being substantially free of powder, it is possible to provide a foamable urethane resin composition that is less likely to produce precipitates during storage, has excellent storage stability, and can suppress wear on equipment used during use. The solid flame retardant is a flame retardant that becomes solid at room temperature and is usually in powder form. Examples of the solid flame retardant include expanded graphite, red phosphorus-based flame retardants, phosphate-containing flame retardants, bromine-containing flame retardants, chlorine-containing flame retardants, antimony-containing flame retardants, boron-containing flame retardants, needle-shaped fillers, and metal hydroxides. The inorganic filler is a particulate inorganic compound, and examples thereof include a solid flame retardant and an inorganic filler other than a solid flame retardant. Examples of inorganic fillers other than solid flame retardants include silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, potassium salts of calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass beads, silica powder, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon powder, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, various magnetic powders, and fly ash.

[0034] <Catalyst> The foamable urethane resin composition of the present invention contains a catalyst. Among the catalysts used, the urethane catalyst preferably contains a urethane metal catalyst. It is also preferable to contain a trimerization catalyst. Note that the catalyst contained in the composition does not fall under the category of inorganic filler in the present invention.

[0035] The urethanization catalyst is a catalyst that promotes the reaction between a polyol compound and a polyisocyanate compound. In addition to the above-mentioned urethanization metal catalyst, an amino compound or an acetylacetone metal salt may also be used as the urethanization catalyst. Some of the above-mentioned catalysts not only contribute to urethanization but also contribute to improving activity in the initial stage of foaming due to their high activity.

[0036] Examples of the urethane-forming metal catalyst include tin compounds, bismuth compounds, etc. Use of the urethane-forming metal catalyst can increase the activity particularly at the initial stage of the reaction, and is effective in cases where high curing speed is required, such as in spraying. Examples of tin compounds include stannous octoate, dibutyltin diacetate, and dibutyltin dilaurate. Examples of the bismuth compound include bismuth neodecanoate and bismuth octoate.

[0037] Examples of the amino compound include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholine bis(2-dimethylaminoethyl) ether, bis(2-dimethylaminoethyl) ether, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl) ether, N-methyl-N',N'-dimethylaminoethylpiperazine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, imidazole compounds such as imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group, N,N-dimethylcyclohexylamine, diazabicycloundecene, guanidine derivatives, triethylenediamine, tetramethylethylenediamine, tetramethylhexamethylenediamine, trimethylaminoethylpiperazine, and tripropylamine. Acid-blocked products of these amino compounds can also be used. Here, examples of the acid-blocked amino compound include those obtained by blocking an amino compound with a carboxylic acid such as formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, octylic acid, or 2-ethylhexanoic acid.

[0038] Examples of acetylacetone metal salts include acetylacetone aluminum, acetylacetone iron, acetylacetone copper, acetylacetone zinc, acetylacetone beryllium, acetylacetone chromium, acetylacetone indium, acetylacetone manganese, acetylacetone molybdenum, acetylacetone titanium, acetylacetone cobalt, acetylacetone vanadium, and acetylacetone zirconium.

[0039] The urethanization catalyst may be a metal urethanization catalyst alone, or may be used in combination with a compound other than the metal urethanization catalyst. As the metal urethanization catalyst, a bismuth compound is preferred from the viewpoint of further enhancing the activity at the initial stage of the reaction. Furthermore, when a compound other than the metal urethanization catalyst is used in combination with the metal urethanization catalyst, an amino compound is preferred, and an imidazole compound is more preferred from the viewpoint of compatibility with the hydrochlorofluoroolefin. When an amino compound is used alone, due to the structure of the corresponding amino compound, it is incompatible with hydrofluoroolefin compounds such as hydrochlorofluoroolefins, resulting in poor long-term storage stability due to catalyst deactivation and other problems, which means that the amount and type of amino compound used are likely to be limited. On the other hand, by using the metal urethanization catalyst in combination, even when a hydrofluoroolefin compound such as hydrochlorofluoroolefins is used, the foamability, reactivity, etc. of the foamable urethane resin composition can be improved from the initial stage while maintaining long-term storage stability.

[0040] The content of the urethanization catalyst in the foamable urethane resin composition of the present invention is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, and more preferably 2 parts by mass or more, relative to 100 parts by mass of the polyol compound. By ensuring that the content is equal to or greater than the above lower limit, the reaction between the polyol compound and the polyisocyanate compound can be promoted at an appropriate reaction rate while improving foamability. Furthermore, in order to improve the reaction rate and make the composition suitable for spray applications, the content of the urethanization catalyst is more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more. Furthermore, from the viewpoint of obtaining foamability and reactivity commensurate with the catalyst content, the content of the urethanization catalyst is preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and even more preferably 10 parts by mass or less.

[0041] The content of the urethanizing metal catalyst is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and even more preferably 0.15 to 1 part by mass, relative to 100 parts by mass of the polyol compound. When an amino compound is contained as the urethanization catalyst, the content of the amino compound is preferably 2 to 14 parts by mass, more preferably 3 to 10 parts by mass, and even more preferably 3.5 to 9 parts by mass, per 100 parts by mass of the polyol compound.

[0042] A trimerization catalyst is a catalyst that promotes trimerization to form isocyanurate bonds. By promoting trimerization of polyurethane resin, the flame retardancy of polyurethane foam is improved. Examples of trimerization catalysts that can be used include aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; alkali metal salts such as potassium acetate, sodium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, potassium formate, potassium octoate, and sodium octoate; aziridines such as 2-ethylaziridine; lead compounds such as lead naphthenate and lead octoate; alcoholates such as sodium methoxide; phenolates such as potassium phenoxide; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt; and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, and tetraphenylammonium salt. Among these, quaternary ammonium salts are preferred. The use of quaternary ammonium salts maintains good catalytic activity, even when a hydrofluoroolefin compound such as a hydrochlorofluoroolefin is used as a blowing agent, resulting in appropriate trimerization and improved flame retardancy. The trimerization catalyst may be used alone or in combination of two or more kinds.

[0043] The content of the trimerization catalyst is not particularly limited, but is preferably in the range of 1 to 15 parts by mass, more preferably 1.5 to 13 parts by mass, and even more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the polyol compound. By setting the content of the trimerization catalyst within the above range, isocyanurate bonds are formed appropriately, and flame retardancy is improved.

[0044] <Foam stabilizer> The polyol-containing composition of the present invention may contain a foam stabilizer. The foam stabilizer improves the foamability of a foamable polyurethane composition containing a polyol-containing composition and a polyisocyanate. A compound having a polar portion and a non-polar portion in the molecule and having a surfactant effect can be suitably used as the foam stabilizer. Specific examples include surfactants such as polyoxyalkylene-based foam stabilizers, e.g., polyoxyalkylene alkyl ethers, and silicone-based foam stabilizers, e.g., organopolysiloxanes. These foam stabilizers may be used alone or in combination of two or more. The amount of the foam stabilizer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of the polyol compound. When the amount of the foam stabilizer is at least these lower limits, the polyurethane composition is easily foamed, making it easier to obtain a homogeneous polyurethane foam. When the amount of the foam stabilizer is at most these upper limits, a good balance between production costs and the obtained effects is achieved.

[0045] <Other ingredients> The polyol-containing composition may contain one or more selected from phenolic, amine, sulfur-based and other antioxidants, heat stabilizers, metal inhibitors, antistatic agents, heat and light stabilizers, crosslinking agents, lubricants, softeners, pigments, etc., as needed, within the scope of the object of the present invention.

[0046] The viscosity of the polyol-containing composition at 20°C is preferably 1000 mPa·s or less. A viscosity of 1000 mPa·s or less provides good handleability. From the above perspectives, the viscosity is more preferably 800 mPa·s or less, and even more preferably 600 mPa·s or less. In the present invention, low viscosity is achieved by substantially not containing powder. There is no particular limitation on the lower limit, and it may be, for example, 100 mPa·s or more.

[0047] <Method of producing polyol-containing composition> There are no particular limitations on the method for producing the polyol-containing composition of the present invention, and it can be produced, for example, by stirring each component using a homodisper or the like for about 30 seconds to 20 minutes.

[0048] [Foamable polyurethane composition and polyurethane foam] The foamable polyurethane composition of the present invention contains the polyol-containing composition of the present invention and a polyisocyanate, and is obtained by mixing them. The polyurethane foam of the present invention is made of the foamable polyurethane composition, and specifically, is a reaction product obtained by reacting and foaming the foamable polyurethane composition.

[0049] <Polyisocyanate> Examples of polyisocyanates 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.

[0050] Examples of alicyclic polyisocyanates include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

[0051] Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

[0052] Among these, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred, from the viewpoints of ease of use and availability. Polyisocyanates may be used singly or in combination of two or more. Furthermore, polyisocyanates may be used that have been subjected to a treatment in advance to enhance affinity with polyols by reacting a portion of the isocyanate active groups in the polyisocyanate compound with a hydroxyl group-containing compound. Furthermore, known additives that are blended into polyisocyanates may be appropriately blended into the polyisocyanate before mixing with the polyol-containing composition.

[0053] <Isocyanate Index> The isocyanate index of the foamable polyurethane composition of the present invention is not particularly limited, but is preferably 200 or greater. If the isocyanate index is equal to or greater than the aforementioned lower limit, the amount of polyisocyanate relative to the polyol becomes excessive, facilitating the formation of isocyanurate bonds due to the trimerization of the polyisocyanate, resulting in improved flame retardancy of the polyurethane foam. Furthermore, if the isocyanate index is equal to or greater than the aforementioned lower limit, combined with the use of the various catalysts described above, it becomes easier to produce a polyurethane foam having sufficient isocyanurate bonds, i.e., a polyurethane foam that combines high levels of flame retardancy and thermal insulation. From these perspectives, the isocyanate index is more preferably 250 or greater, and even more preferably 300 or greater. The isocyanate index is preferably not more than 800, more preferably not more than 600. When the isocyanate index is not more than the upper limit, the resulting polyurethane foam will have a good balance between flame retardancy and production costs.

[0054] 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 equivalent number can be calculated as follows: Polyisocyanate equivalent number = Amount of polyisocyanate used (g) × NCO content (mass%) / Molecular weight of NCO (mol) × 100 Equivalent weight of polyol = OHV × amount of polyol used (g) ÷ molecular weight of KOH (mmol) OHV is the hydroxyl value of the polyol (mg KOH / g). Equivalents 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 (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.

[0055] <Total heat generation> The foamable polyurethane composition of the present invention has a strength of 50 kW / m in a cone calorimeter test in accordance with ISO-5660. 2 When heated for 10 minutes, the total calorific value is 8MJ / m 2 It is preferable that: Total calorific value is 8MJ / m 2 If the total calorific value is less than 7.5MJ / m, it shows sufficient flame retardancy. 2 More preferably, it is:

[0056] The gross calorific value can be measured by a cone calorimeter test, specifically by the method described in the Examples. In the above-mentioned cone calorimeter test, it is preferable that the polyurethane foam used in the test has a shape stability to such an extent that it does not come into contact with the spark igniter of the cone calorimeter.

[0057] <Application> The uses of the foamable polyurethane composition of the present invention and the polyurethane foam formed from the composition are not particularly limited, and they can be used to fill cavities in structures such as buildings, furniture, automobiles, trains, ships, etc., or to be sprayed onto such structures. Among these, the use of spraying onto structures, i.e., spray applications, is preferred. Spraying can be carried out using a spraying device (e.g., GRACO's A-25) and a spray gun (e.g., Gasmar's D-gun). Spraying can be carried out by adjusting the temperature of the polyol composition and polyisocyanate composition contained in separate containers in the spraying device, causing them to collide and mix at the tip of the spray gun, and then turning the mixed liquid into a mist using air pressure. Spraying devices and spray guns are well known, and commercially available products can be used. Furthermore, the temperature settings and pressure of the raw liquid can be set according to general spraying conditions for polyurethane foam. [Example]

[0058] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0059] [Evaluation method] (Total heat generation and maximum heat generation rate) The total heat release amount and maximum heat release rate of the polyurethane foams produced in each of the Examples and Comparative Examples were evaluated by the following methods. The polyurethane foams with gypsum board as a base obtained in each Example and Comparative Example were cut into a length of 10 cm, a width of 10 cm and a thickness of 3.25 cm (within which the gypsum board was 12.5 mm) to prepare samples for cone calorimeter testing. The cone calorimeter test samples were subjected to a radiant heat intensity of 50 kW / m in accordance with the test method of ISO-5660. 2 The total heat release rate and maximum heat release rate were measured when the sample was heated at 40°C for 10 minutes. The evaluation criteria for the total calorific value are as follows: ◎: Total calorific value is 7.5MJ / m 2 The following is the result. 〇: Total calorific value is over 7.5 to 8 MJ / m 2 The range is. ×: Total calorific value is 8MJ / m 2 Exceeds.

[0060] (Physical Properties of Polyol-Containing Composition) The liquid viscosity at 20°C of each of the polyol-containing compositions of the Examples and Comparative Examples was measured. Measurements were made at a liquid temperature of 20°C using a Brookfield viscometer at 60 rpm, with the value measured one minute after the start of rotation. The evaluation criteria were as follows: ○: 1000 mPa·s or less. ×: Exceeds 1000 mPa·s.

[0061] [material] The materials used in each of the examples and comparative examples are as follows. (Polyol) RLK-087: p-phthalic acid polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name Maximol "RLK-087", hydroxyl value: 200 mg KOH / g) RFK-505: p-phthalic acid polyester polyol (manufactured by Kawasaki Chemical Industries, Ltd., product name: Maximol RFK-505, hydroxyl value = 250 mg KOH / g) (Foam stabilizer) SH-193: Silicone foam stabilizer (manufactured by Dow Toray, product name "SH-193") (trimerization catalyst) DABCO® K-15: metal catalyst, potassium 2-ethylhexanoate (manufactured by Evonik, concentration 70-80% by mass) DABCO (registered trademark) TMR-7: ammonium salt, 2,2-dimethylpropanoic acid tetramethylammonium salt (manufactured by Evonik, concentration 45 to 55% by mass) (Urethanization catalyst) TOYOCAT (registered trademark)-DM70: Resinized amine catalyst, 1,2-dimethylimidazole (manufactured by Tosoh Corporation, concentration 65-75% by mass) BI-28 (product name): bismuth 2-ethylhexanoate (manufactured by Nitto Kasei Co., Ltd., concentration 81-90% by mass) (liquid flame retardant) TPCPP: Tris(β-chloropropyl)phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name, halogen-containing phosphate ester) TEP: Triethyl phosphate (non-halogen phosphate ester: manufactured by Daihachi Chemical Industry Co., Ltd.) TCP: Tricresyl phosphate (non-halogen phosphate ester: manufactured by Daihachi Chemical Industry Co., Ltd.) TXP: Trixylenyl phosphate (non-halogen phosphate ester: manufactured by Daihachi Chemical Industry Co., Ltd.) DAIGUARD-540: Halogen-containing condensed phosphate ester (manufactured by Daihachi Chemical Industry Co., Ltd.) DAIGUARD-880: Non-halogen condensed phosphate ester (manufactured by Daihachi Chemical Industry Co., Ltd.) CR-733S: Non-halogen aromatic condensed phosphate ester (manufactured by Daihachi Chemical Industry Co., Ltd.) CR-741: Non-halogen aromatic condensed phosphate ester (manufactured by Daihachi Chemical Industry Co., Ltd.) (foaming agent) Ion-exchanged water HFO-1233ZD; trans-1-chloro-3,3,3-trifluoropropene

[0062] [Examples 1 to 11, Comparative Examples 1 to 3] Polyol, foam stabilizer, catalyst, phosphate ester (liquid flame retardant), and blowing agent were mixed in the amounts shown in Table 1 to obtain a polyol-containing composition, and the total heat release value and maximum heat release rate were evaluated as described above. The liquid viscosity was also measured. The results are shown in Table 1.

[0063] [Table 1]

[0064] As is clear from the results of the above examples, the polyol-containing composition of the present invention, which contains a polyol, a blowing agent, a catalyst, and a phosphate ester, has a low total calorific value and a low maximum heat release rate, despite the use of a liquid flame retardant (phosphate ester) that is substantially free of powder. That is, the polyol-containing composition of the present invention has high flame retardancy, and foamable polyurethane compositions using the polyol-containing composition and urethane foams using the same also have high flame retardancy. Furthermore, since the polyol-containing composition of the present invention does not use a solid flame retardant, the flame retardant does not settle during storage, resulting in poor dispersion. Furthermore, the flowability during raw material injection is good, and good molding processability is obtained. On the other hand, the polyol-containing composition of the comparative example had a large total heat release value and a large maximum heat release rate, and was poor in flame retardancy.

Claims

1. A polyol-containing composition for forming a polyurethane foam on a surface of a structure by spraying a polyol composition and a polyisocyanate composition by collision mixing using a spray device and a spray gun onto the structure, Contains a polyol, a blowing agent, a flame retardant, and a catalyst, the flame retardant contains a halogen-containing phosphate ester, and the content of the halogen-containing phosphate ester is 50 parts by mass or more relative to 100 parts by mass of the polyol; the polyol consists solely of an aromatic polyester polyol, the catalyst contains a urethanization metal catalyst and an imidazole-based compound as a urethanization catalyst, and contains an alkali metal salt and a quaternary ammonium salt as a trimerization catalyst; A polyol-containing composition, characterized in that the phosphorus concentration in the polyol-containing composition is 3% by mass or more and the powder content is 1% by mass or less.

2. The polyol-containing composition of claim 1 , wherein the flame retardant further comprises a condensed phosphate ester.

3. The polyol-containing composition according to claim 1 or 2, wherein the concentration of chlorine other than that derived from the blowing agent is 10% by mass or more.

4. The polyol-containing composition according to any one of claims 1 to 3, which has a viscosity at 20°C of 1000 mPa·s or less.

5. A foamable polyurethane composition comprising the polyol-containing composition according to any one of claims 1 to 4 and a polyisocyanate.

6. Cone calorimeter test according to ISO-5660 shows a strength of 50kW / m ２ The total heat generated when heated for 10 minutes is 8MJ / m ２ 6. The foamable polyurethane composition of claim 5, wherein:

7. 7. The foamable polyurethane composition according to claim 5, having an isocyanate index of 200 or more.

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