Flame-retardant urethane resin composition

Abstract

To provide a flame-retardant urethane resin composition that can form a polyurethane foam having high fireproofing performance, wherein, the composition can prevent a foam stabilizer from bleeding out on the surface of the formed polyurethane foam and also prevent the polyurethane foam from becoming easily burned.SOLUTION: A flame-retardant urethane resin composition contains a polyol composition containing a polyol compound, a liquid flame retardant, a catalyst, and a foamer, and a polyisocyanate composition containing a polyisocyanate compound. The flame-retardant urethane resin composition is free of a foam stabilizer and has a gel time of 20 seconds or shorter.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a flame-retardant urethane resin composition. [Background technology]

[0002] Taking advantage of their excellent heat insulating properties, polyurethane foams are put to practical use for heat insulation and condensation prevention in various structures such as ceilings, roofs, and walls of buildings such as apartment complexes, detached houses, commercial buildings, etc. Polyurethane foams are formed, for example, by spraying a urethane resin composition containing a polyol composition and a polyisocyanate composition onto the surface of each structure, followed by foaming and curing.

[0003] For example, Patent Document 1 describes an invention relating to a spray-on insulation material made of a rigid polyurethane foam obtained by foaming a mixture liquid containing a polyisocyanate component, a polyol component, water, a catalyst, a foam stabilizer, a flame retardant, and powder, and indicates that the spray-on insulation material has excellent flame retardancy, dimensional stability, and the like. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2010-270877 A Summary of the Invention [Problem to be solved by the invention]

[0005] As in Patent Document 1 mentioned above, when a polyurethane foam is formed using a composition containing a foam stabilizer, the foam stabilizer is likely to seep out onto the surface of the foam, i.e., bleed-out, which can cause problems such as contamination of the object of use or the resulting foam being prone to combustion. On the other hand, from the viewpoint of solving the problems of bleed-out and flammability, it is conceivable to produce polyurethane foam without using a foam stabilizer. However, it has been found that if a foam stabilizer is not used, some of the cells forming the polyurethane foam become more prone to cracking, resulting in coarse cells and a decrease in thermal insulation properties. Therefore, an object of the present invention is to provide a flame-retardant urethane resin composition which can suppress cell coarsening and produce a polyurethane foam with excellent thermal insulation properties even when no foam stabilizer is used. [Means for solving the problem]

[0006] As a result of intensive research, the present inventors have found that the above-mentioned problems can be solved by a flame-retardant urethane resin composition containing a polyol composition and a polyisocyanate composition, which does not contain a foam stabilizer and has a gel time of a certain level or less, and have completed the present invention. That is, the present invention provides the following [1] to [7].

[0007] [1] A flame-retardant urethane resin composition containing a polyol composition including a polyol compound, a liquid flame retardant, a catalyst, and a foaming agent, and a polyisocyanate composition including a polyisocyanate compound, the flame-retardant urethane resin composition not containing a foam stabilizer and having a gel time of 20 seconds or less. [2] The flame-retardant urethane resin composition according to [1] above, having a cream time of 8 seconds or less. [3] The flame-retardant urethane resin composition according to the above [1] or [2], wherein the catalyst contains a metallic urethanization catalyst. [4] The flame-retardant urethane resin composition according to any one of the above [1] to [3], wherein the polyol composition further contains a filler. [5] The flame-retardant urethane resin composition according to any one of the above [1] to [4], wherein the catalyst contains a trimerization catalyst. [6] The flame-retardant urethane resin composition according to any one of the above [1] to [5], wherein the content of the liquid flame retardant in the polyol composition is 20 parts by mass or more per 100 parts by mass of the polyol compound. [7] The flame-retardant urethane resin composition according to any one of the above [1] to [6], which is for spray application. Effect of the Invention

[0008] The present invention relates to a flame-retardant urethane resin composition that does not use a foam stabilizer, and therefore it is possible to suppress bleeding of the foam stabilizer onto the surface of the polyurethane foam formed, and to prevent the polyurethane foam from becoming easily combustible. In addition, it is possible to suppress coarsening of cells, thereby obtaining a polyurethane foam with excellent heat insulation properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention relates to a flame-retardant urethane resin composition that contains a polyol composition including a polyol compound, a liquid flame retardant, a catalyst, and a foaming agent, and a polyisocyanate composition including a polyisocyanate compound, the flame-retardant urethane resin composition not including a foam stabilizer and having a gel time of 20 seconds or less.

[0010] (Foam stabilizer) The flame-retardant urethane resin composition of the present invention does not contain a foam stabilizer. By not containing a foam stabilizer, bleeding out of the foam stabilizer onto the surface of the polyurethane foam formed when, for example, a silicone-based foam stabilizer is used is suppressed. In addition, by removing the foam stabilizer component that can be a flammable element, it is possible to prevent the polyurethane foam from becoming easily flammable. The foam stabilizer herein means a foam stabilizer that has a foam stabilizing function in polyurethane foaming and is generally used in the production of polyurethane foams. Examples of the foam stabilizer include silicone-based foam stabilizers and non-silicone-based foam stabilizers. Silicone-based foam stabilizer is a compound having a polysiloxane chain and a polyoxyalkylene chain, and may be a block structure of polysiloxane chain and polyoxyalkylene chain, or a structure in which a polyoxyalkylene chain is grafted as a side chain to a main polysiloxane chain.Specific product names of the silicone-based foam stabilizer include, for example, SH-193, SF-2937F, SF-2945F, etc., manufactured by Toray Dow Corning Co., Ltd. The non-silicone foam stabilizer refers to a foam stabilizer other than a silicone foam stabilizer, and examples of the foam stabilizer include acrylic surfactants, etc. Examples of the acrylic surfactant include acrylic polymers having a polar group on the side chain.

[0011] (Gel Time) The flame-retardant urethane resin composition of the present invention has a gel time of 20 seconds or less. If the gel time exceeds 20 seconds, the balance between the urethane resin formation rate and the foaming ability is lost, and the cells in the polyurethane foam may partially crack, resulting in coarse cells and a decrease in heat insulation properties. From the viewpoint of improving the thermal insulation properties of the polyurethane foam formed, the gel time of the flame-retardant urethane resin composition is preferably 16 seconds or less, more preferably 14 seconds or less, even more preferably 12 seconds or less, and even more preferably 10 seconds or less. The gel time can be adjusted to a desired value by adjusting the type and amount of the catalyst contained in the polyol composition. The gel time is a value measured by the cup foaming method. Specifically, it is measured as follows. The liquid temperatures of the polyol composition and the polyisocyanate composition constituting the flame-retardant urethane resin composition of the present invention are adjusted to 10°C. Then, in a room at 23°C, the polyol composition and the polyisocyanate composition adjusted to 10°C are poured into a 500mL cup so that the total amount of the mixed liquid is 60g at a predetermined mixing ratio. The mixed liquid is then immediately stirred for 2 seconds at 8000 rpm using a Labody Spa (PRIMIX Co., Ltd. high-speed disperser Homo Disper 2.5 type). The time when the stirring started is set as the measurement start time (0 seconds), and the time (seconds) until the foam becomes stringy when a stick is pierced into the foam during foaming is measured, and this is the gel time. In addition, when a trimerization catalyst is included, the foam may become stringy and the internal hardening of the foam may occur almost simultaneously. The above-mentioned predetermined mixing ratio means the mixing ratio of the polyol composition and the polyisocyanate composition when preparing the flame-retardant urethane resin composition of the present invention.

[0012] (Cream Time) The cream time of the flame-retardant urethane resin composition of the present invention is preferably 8 seconds or less. When the cream time is 8 seconds or less, the low thermally conductive blowing agent (e.g., hydrofluoroolefin) contained in the resin composition can be confined in the foam with less scattering outside the system, making it easier to obtain a polyurethane foam with excellent heat insulation. From this viewpoint, the cream time of the flame-retardant urethane resin composition is more preferably 6 seconds or less, even more preferably 5 seconds or less, and even more preferably 4 seconds or less. The cream time can be adjusted to a desired value by adjusting the type and amount of the catalyst contained in the polyol composition. The cream time is a value measured by the cup foaming method. Specifically, it is measured as follows. The liquid temperatures of the polyol composition and the polyisocyanate composition constituting the flame-retardant urethane resin composition of the present invention are adjusted to 10°C. Then, in a room at 23°C, the polyol composition and the polyisocyanate composition adjusted to 10°C are poured into a 500mL cup so that the total amount of the mixed liquid is 60g at a predetermined mixing ratio. Then, the mixed liquid is immediately stirred at 8000rpm for 2 seconds with a Labody Spa (PRIMIX Co., Ltd. high-speed disperser Homo Disper 2.5 type). The time when the stirring started is set as the measurement start time (0 seconds), and the time (seconds) until the mixed liquid changes color and the liquid level starts to rise due to foaming is measured, and this is the cream time. The above-mentioned predetermined mixing ratio means the mixing ratio of the polyol composition and the polyisocyanate composition when preparing the flame-retardant urethane resin composition of the present invention.

[0013] [Polyol composition] The polyol composition of the present invention contains a polyol compound, a liquid flame retardant, a catalyst, and a blowing agent. Each component contained in the polyol composition will be described below.

[0014] <Polyol compound> The polyol compound is not particularly limited, but examples thereof include polyether polyol, polyester polyol, etc. From the viewpoint of improving the flame retardancy of the polyurethane foam, the polyol compound preferably contains polyester polyol. Also, from the viewpoint of improving the flame retardancy, it is preferable to use a halogen-containing polyol or a phosphorus-containing polyol. From this viewpoint, out of 100 parts by mass of the polyol compound, it is preferable that the polyester polyol is 20 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 80 parts by mass or more, and particularly preferably 100 parts by mass.

[0015] When two or more kinds of polyol compounds are used, the hydroxyl value of the polyol compounds may be an average hydroxyl value according to the blending ratio of the two or more kinds of polyol compounds. For example, when two types of polyols, polyol (d1) and polyol (d2), are used as polyol compounds, the hydroxyl value of polyol (d1) is X1, the blending ratio is m1, and the hydroxyl value of polyol (d2) is X2, the blending ratio is m2, the average hydroxyl value is represented by the following formula. Note that the blending ratio is based on mass. Average hydroxyl value (mgKOH / g)=X1×(m1 / (m1+m2))+X2×(m2 / (m1+m2)) The average hydroxyl value of the polyol compound used in the present invention is preferably from 100 to 500 mgKOH / g, more preferably from 150 to 450 mgKOH / g, and even more preferably from 200 to 400 mgKOH / g, from the viewpoint of improving the flame retardancy of the polyurethane foam. The hydroxyl value is a value measured in accordance with JIS K1557-1:2007.

[0016] (Polyester polyol) The polyester polyol may be a polyester polyol having an aromatic ring or an aliphatic polyester polyol, but in consideration of 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. Among them, from the viewpoint of increasing the flame retardancy of the polyurethane foam, it is preferable that the polyol compound contains a phthalic acid-based polyester polyol, which is a condensate of phthalic acid and a glycol, and it is more preferable that the polyol compound contains a p-phthalic acid-based polyester polyol, which is a condensate of p-phthalic acid and a glycol. The glycol is not particularly limited, but it is preferable to use low molecular weight aliphatic glycols known as components of polyester polyols, such as ethylene glycol, propylene glycol, and diethylene glycol.

[0017] The hydroxyl value of the polyester polyol is preferably from 100 to 500 mgKOH / g, more preferably from 150 to 450 mgKOH / g, and further preferably from 200 to 400 mgKOH / g.

[0018] (Polyether polyol) Polyether polyol is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of an alkylene oxide to an initiator having two or more active hydrogen atoms. Specific examples of the initiator include aliphatic polyhydric alcohols (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, and highly functional alcohols such as sucrose and sorbitol), aliphatic amines (e.g., alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine, and alkanolamines such as monoethanolamine and diethanolamine), and aromatic amines (e.g., aniline, tolylenediamine, xylylenediamine, diphenylmethanediamine, and Mannich condensation products). Among these, the polyether polyol produced by using an initiator having an aromatic ring is the polyether polyol having an aromatic ring, for example, the polyether polyol produced by using an aromatic amine as an initiator is the polyether polyol having an aromatic ring. Among the polyether polyols having an aromatic ring, tolylenediamine-based polyether polyols, Mannich-based polyether polyols, etc. can be preferably used.

[0019] The tolylenediamine-based polyether polyol is a tolylenediamine-based polyether polyol produced using tolylenediamine as an initiator. The Mannich polyether polyol is a polyether polyol obtained by utilizing the Mannich reaction, which is a Mannich condensation product having two or more hydroxyl groups in the molecule, or an alkylene oxide added to such a Mannich condensation product. More specifically, it is a Mannich condensation product obtained by the Mannich reaction of at least one of phenol and its alkyl-substituted derivatives, formaldehyde and alkanolamine, or a polyether polyol obtained by ring-opening addition polymerization of at least one of ethylene oxide and propylene oxide to this compound.

[0020] The hydroxyl value of the polyether polyol is preferably from 200 to 2000 mgKOH / g, and more preferably from 300 to 1000 mgKOH / g.

[0021] <Liquid flame retardant> The polyol composition in the present invention preferably contains a liquid flame retardant from the viewpoint of improving the flame retardancy of the polyurethane foam obtained. Among liquid flame retardants, a phosphate-based flame retardant is particularly preferable. The use of a phosphate-based flame retardant can improve the flame retardancy of the polyurethane foam, and can also appropriately control the viscosity of the polyol composition even when a filler described below is used. Here, the liquid flame retardant is a flame retardant that is liquid at 23°C.

[0022] Examples of the phosphate flame retardant include monophosphate and condensed phosphate. Examples of monophosphate esters include, but are not limited to, trimethyl phosphate, triethyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, and tris(β-chloropropyl) phosphate. The condensed phosphate ester is not particularly limited, but examples thereof include resorcinol polyphenyl phosphate (product name: CR-733S), bisphenol A polycresyl phosphate (product name: CR-741), and aromatic condensed phosphate ester (product name: CR747).

[0023] The content of the liquid flame retardant is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more, and preferably 100 parts by mass or less, more preferably 80 parts by mass or less, based on 100 parts by mass of the polyol compound. When the content of the liquid flame retardant is equal to or more than these lower limits, the flame retardancy of the polyurethane foam is improved, and when the content is equal to or less than these upper limits, the mechanical strength of the polyurethane foam can be improved. In addition, by including a certain amount or more of the liquid flame retardant, the compatibility of the polyisocyanate composition and the polyol composition when mixed is improved, so that it is considered that the foam formation can be stabilized even when no foam stabilizer is included.

[0024] <Filler> The polyol composition of the present invention may contain a filler. The filler is a solid component contained in the flame-retardant urethane resin composition, and is generally a component that exists in the form of particles or powder. By containing a filler, various physical properties such as mechanical strength and flame retardancy can be improved depending on the type of filler. The filler may be any component that is solid at room temperature (23° C.) and normal pressure (1 atm) and does not dissolve in the flame-retardant urethane resin composition.

[0025] The filler preferably contains a solid flame retardant. As the solid flame retardant, boron-based flame retardants, bromine-based flame retardants, phosphate-containing flame retardants, antimony-containing flame retardants, phosphinic acid-based flame retardants, metal hydroxide-based flame retardants, red phosphorus, needle-shaped fillers, etc. are preferable. Among these, red phosphorus, needle-shaped fillers, etc. are preferable from the viewpoint of improving the flame retardancy of the polyurethane foam.

[0026] (Boron-based flame retardants) Specific examples of the boron-based flame retardant include alkali metal borate such as lithium borate, sodium borate, potassium borate, and cesium borate, alkaline earth metal borate such as magnesium borate, calcium borate, and barium borate, zirconium borate, zinc borate, aluminum borate, and ammonium borate, etc. Among these, zinc borate is preferred.

[0027] (Brominated flame retardants) There are no particular limitations on the bromine-based flame retardant as long as it is a compound that contains bromine in its molecular structure. Examples of the aromatic brominated compounds include aromatic brominated compounds. Specific examples of the aromatic brominated compound include monomeric organic bromine compounds such as hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylene bis(pentabromophenyl), ethylene bis(tetrabromophthalimide), and tetrabromobisphenol A; polycarbonate oligomers produced using brominated bisphenol A as a raw material; and mixtures of the polycarbonate oligomers and bisphenols. Examples of the brominated epoxy compounds include brominated polycarbonates such as copolymers with brominated bisphenol A, diepoxy compounds produced by the reaction of brominated bisphenol A with epichlorohydrin, and monoepoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin, and halogenated bromine compound polymers such as poly(brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, condensates of cyanuric chloride and brominated phenol, brominated (polystyrene), poly(brominated styrene), brominated polystyrenes such as crosslinked brominated polystyrene, and crosslinked or non-crosslinked brominated poly(α-methylstyrene). Among these, ethylene bis(pentabromophenyl), ethylene bis(tetrabromophthalimide), hexabromobenzene, and the like are preferable.

[0028] (Phosphate-containing flame retardants) Examples of phosphate-containing flame retardants include those containing phosphoric acid and a metal of Groups IA to IVB of the periodic table. At least one metal or compound selected from ammonia, aliphatic amines, and aromatic amines Examples of suitable salts include phosphates, which are salts with phosphates. The phosphoric acid is not particularly limited, but examples thereof include monophosphoric acid, pyrophosphoric acid, polyphosphoric acid, and the like. Can be obtained. Examples of the metals in Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), aluminum, etc. Examples of the aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, etc. Examples of the aromatic amines include pyridine, triazine, melamine, etc. The above phosphate-containing flame retardants are treated with a silane coupling agent and coated with melamine resin. A known water resistance improving treatment such as water-resistant treatment may be applied.

[0029] Specific examples of phosphate-containing flame retardants include monophosphates, pyrophosphates, polyphosphates, and the like. The monophosphate is not particularly limited, but examples thereof include ammonium phosphate and dihydrate phosphoric acid. ammonium salts such as monobasic ammonium and diammonium hydrogen phosphate; monobasic sodium phosphate; Disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite sodium hypophosphite and other sodium salts, potassium phosphate monobasic, potassium phosphate dibasic, Potassium phosphate, tripotassium phosphite, dipotassium phosphite, potassium hypophosphite, etc. Lithium salts, monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite Lithium salts such as lithium diphosphite and lithium hypophosphite, barium dihydrogen phosphate, Barium salts such as barium hydrogen phosphate, barium triphosphate, and barium hypophosphate, Magnesium hydrogen, magnesium hydrogen phosphate, magnesium triphosphate, magnesium hypophosphite Magnesium salts of sodium, dihydrogen calcium phosphate, hydrogen calcium phosphate, trihydrogen calcium phosphate Calcium, calcium hypophosphite and other calcium salts, zinc phosphate, zinc phosphite, hypophosphite Examples include zinc salts such as zinc phosphate.

[0030] The polyphosphate is not particularly limited, but examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium amide polyphosphate, and aluminum polyphosphate. The phosphate-containing flame retardants may be used alone or in combination of two or more.

[0031] (Antimony-containing flame retardants) Examples of the antimony-containing flame retardant used in the present invention include antimony oxide, antimonates, and pyroantimonates. Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of antimonate include sodium antimonate and potassium antimonate. Examples of pyroantimonate include sodium pyroantimonate, Examples thereof include potassium pyroantimonate. Preferably, the antimony-containing flame retardant is antimony oxide. The antimony-containing flame retardants may be used alone or in combination of two or more. Cut.

[0032] (Phosphinic acid flame retardants) Examples of phosphinic acid flame retardants include phosphinic acid, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, and bis(4-methoxyphenyl)phosphinic acid.

[0033] (Metal hydroxide flame retardant) Examples of metal hydroxide flame retardants include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, tin hydroxide, etc. The metal hydroxide flame retardants may be used alone or in combination of two or more.

[0034] (red phosphorus) The red phosphorus may be made of simple red phosphorus, or may be red phosphorus mixed with or coated with a resin, a metal hydroxide, a metal oxide, or the like.

[0035] (Needle filler) Examples of needle-like 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, and stainless steel fibers. These needle-like fillers can be used alone or in combination of two or more.

[0036] The filler may be an inorganic filler other than the flame retardant described above. As the inorganic filler, 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, clay, mica, montmorillonite, bentonite, activated clay, imogolite, sericite, glass beads, silica balloon, aluminum nitride, boron nitride, silicon nitride, graphite, carbon balloon, charcoal powder, various metal powders, magnesium sulfate, lead zirconate titanate, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash, etc. may be appropriately used. The inorganic filler may be used alone or in combination of two or more.

[0037] The content of the filler is preferably 10 parts by mass or more, more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, and preferably 80 parts by mass or less, more preferably 60 parts by mass or less, relative to 100 parts by mass of the polyol compound. When the filler content is equal to or greater than these lower limits, the filler can easily exhibit its function according to its type, and when a solid flame retardant is used as the filler, the flame retardancy of the polyurethane foam is easily improved. When the filler content is equal to or less than these upper limits, clogging of the spraying device is suppressed, and spraying properties can be improved.

[0038] The flame-retardant urethane resin composition may not contain the above-mentioned filler. When the composition does not contain a filler, it is less likely to produce precipitates during storage, has excellent handleability, and can suppress wear on tools and the like used during use.

[0039] <Foaming agent> Specific examples of the blowing agent include water, low-boiling point hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, hydrofluoroolefins, etc. Further examples of the blowing agent 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 hydrochlorofluorocarbon compounds include trichloromonofluoromethane, trichlorotrifluoroethane, and dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), and HCFC142b (1-chloro-1,1-difluoroethane)). Examples of the hydrofluorocarbon include HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane). The ether compound may, for example, be diisopropyl ether. Examples of the hydrofluoroolefin include HFO-1233zd(E) (trans-1-chloro-3,3,3-trifluoropropene), HFO-1234yf (2,3,3,3-tetrafluoro-1-propene), HFO-1336mzz(Z) (cis-1,1,1,4,4,4-hexafluorobut-2-ene), and HFO-1224yd(Z).

[0040] Among the above, preferred foaming agents are hydrofluoroolefins, water, and the like, and it is more preferred to use hydrofluoroolefins and water in combination. From the viewpoint of adjusting the density of the foam within a desired range, the content of the foaming agent is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 50 parts by mass, relative to 100 parts by mass of the polyol compound.

[0041] The amount of the hydrofluoroolefin used as a blowing agent is preferably 3 to 60 parts by mass, more preferably 8 to 57 parts by mass, and even more preferably 19 to 49 parts by mass, per 100 parts by mass of the polyol compound, from the viewpoint of setting the density of the polyurethane foam in the desired range. As the water used as a foaming agent, for example, ion-exchanged water, distilled water, etc. can be appropriately used. The amount of water per 100 parts by mass of the polyol compound is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 3 parts by mass, and further preferably 0.2 to 2 parts by mass, from the viewpoint of adjusting the isocyanate index to a certain level or higher and adjusting the density of the polyurethane foam to a desired range.

[0042] <Catalyst> The polyol composition contains a catalyst. Examples of the catalyst include a urethane catalyst and a trimerization catalyst. The trimerization catalyst is a catalyst that promotes trimerization to form an isocyanurate bond. From the viewpoint of improving the flame retardancy of the polyurethane foam and adjusting the gel time of the flame-retardant urethane resin composition to a certain level or less, the catalyst preferably contains a trimerization catalyst.

[0043] As the trimerization catalyst, nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine, etc., carboxylate alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate, potassium octylate, etc., tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt, etc., tetramethylammonium salt, tetraethylammonium salt, tetraphenylammonium salt, triethylmonomethylammonium salt, carboxylate quaternary ammonium salt, etc. can be used. A suitable specific example of the carboxylic acid in the carboxylate ammonium salt is at least one selected from the group consisting of 2-ethylhexanoic acid, 2,2-dimethylpropanoic acid, acetic acid, and formic acid. The trimerization catalyst may be used alone or in combination of two or more, but it is preferable to use two or more in combination. The trimerization catalyst is preferably at least one selected from the group consisting of alkali metal carboxylates and quaternary ammonium carboxylates, and it is preferable to use an alkali metal carboxylate and a quaternary ammonium carboxylate in combination.

[0044] The content of the trimerization catalyst is preferably 1 to 30 parts by mass, and more preferably 2 to 15 parts by mass, based on 100 parts by mass of the polyol compound.

[0045] In the present invention, the catalyst preferably contains a urethanization catalyst, and more preferably contains both the above-mentioned trimerization catalyst and urethanization catalyst.

[0046] The urethanization catalyst is a catalyst that promotes the reaction between a polyol compound and a polyisocyanate compound. Specific examples of the urethanization catalyst include amino compounds and metal-based urethanization catalysts. Examples of metal-based urethane catalysts include tin compounds, bismuth compounds, and acetylacetone metal salts. Among these, from the viewpoint of adjusting the gel time and cream time of the flame-retardant urethane resin composition to a certain level or less, one or more compounds selected from bismuth compounds and tin compounds are preferred.

[0047] Examples of the amino compound include imidazole compounds such as 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group; pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinebis(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, N,N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylethylenediamine, tetramethylhexamethylenediamine, trimethylaminoethylpiperazine, tripropylamine, N,N,N',N'-tetramethylguanidine, and acid block products thereof. Among the amino compounds, imidazole compounds are preferred from the viewpoint of storage stability.

[0048] Examples of tin compounds include stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, etc. Examples of bismuth compounds include bismuth neodecanoate, bismuth octoate, etc. 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. The catalyst in the present invention preferably contains the above-mentioned bismuth compound from the viewpoint of keeping the gel time and cream time of the flame-retardant urethane resin composition at or below a certain level.

[0049] The catalyst preferably contains a metal-based urethane catalyst, and the content of the metal-based urethane catalyst is preferably 0.5 to 15 parts by mass, more preferably 1 to 13 parts by mass, and even more preferably 1.5 to 10 parts by mass, relative to 100 parts by mass of the polyol compound.

[0050] From the viewpoint of keeping the gel time at a certain level or less, it is preferable to use a metal urethanization catalyst in combination with an amino compound as the urethanization catalyst, and among these, it is more preferable to use a bismuth compound in combination with an imidazole compound. When a metallic urethanization catalyst and an amino compound are used in combination, the mass ratio of the amino compound to the metallic urethanization catalyst (mass of amino compound / mass of metallic urethanization catalyst) is preferably 0.1 to 10, more preferably 0.5 to 8, and even more preferably 1 to 5.

[0051] The content of the urethanization catalyst is not particularly limited, but is preferably 1 to 30 parts by mass, and more preferably 5 to 25 parts by mass, relative to 100 parts by mass of the polyol compound.

[0052] The total amount of the catalyst is preferably from 2 to 60 parts by mass, and more preferably from 7 to 40 parts by mass, based on 100 parts by mass of the polyol compound.

[0053] <Polyisocyanate compounds> As the polyisocyanate compound contained in the polyisocyanate composition of the present invention, various polyisocyanate compounds having two or more isocyanate groups, such as aromatic, alicyclic, and aliphatic polyisocyanate compounds, can be used. It is preferable to use liquid diphenylmethane diisocyanate (MDI) because of its ease of handling, rapid reaction, excellent physical properties of the resulting polyurethane foam, and low cost. Examples of liquid MDI include crude MDI (also called polymeric MDI). Specific examples of commercially available liquid MDI include "44V-10" and "44V-20" (manufactured by Sumika Covestro Urethane Co., Ltd.) and "Millionate MR-200" (Nippon Polyurethane Industry Co., Ltd.). In addition, uretonimine-containing MDI (for example, a commercially available product "Millionate MTL": manufactured by Nippon Polyurethane Industry Co., Ltd.) may also be used. In addition, a part of the isocyanate active group in the isopolycyanate compound may be reacted with a hydroxyl group-containing compound to enhance the affinity with polyol in advance. In addition to liquid MDI, other polyisocyanate compounds may be used in combination, and any polyisocyanate compound known in the technical field of polyurethane may be used as the polyisocyanate compound without any limitations. The polyisocyanate composition may consist of only polyisocyanate compounds.

[0054] The mixing ratio of the polyol composition and the polyisocyanate composition of the present invention is preferably adjusted so that the isocyanate index of the flame-retardant urethane resin composition is as follows: When the flame-retardant urethane resin composition is used for spraying, the volume ratio of the polyisocyanate composition to the polyol composition (polyisocyanate composition / polyol composition) is not particularly limited, but is preferably 0.8 to 1.2, and more preferably 0.9 to 1.1.

[0055] The isocyanate index of the flame-retardant urethane resin composition is preferably 150 to 600, and more preferably 200 to 500. When the isocyanate index is equal to or more than these lower limits, a polyurethane foam having high flame retardancy is easily obtained, and when the isocyanate index is equal to or less than these upper limits, good foamability during foam formation can be achieved. The isocyanate index (INDEX) is the value obtained by dividing the number of moles of isocyanate groups in a polyisocyanate by the total number of moles of hydroxyl groups of a polyol and active hydrogen groups of water used as a blowing agent, and multiplying the result by 100, and is calculated by the following method.

[0056] INDEX = equivalents of isocyanate ÷ (equivalents of polyol + equivalents of water) × 100 Where: Isocyanate equivalent number = number of parts of polyisocyanate used x NCO content (%) x 100 / NCO molecular weight Polyol equivalent number = OHV × number of parts of polyol used ÷ molecular weight of KOH, OHV is the hydroxyl value of polyol (mgKOH / g), Equivalents of water = parts of water used × number of OH groups in water / molecular weight of water In the above formula, the unit of the parts used is weight (g), the molecular weight of the NCO group is 42, the NCO content is the proportion of NCO groups in the polyisocyanate compound expressed as mass%, and for convenience of unit conversion in the above formula, the molecular weight of KOH is 56100, the molecular weight of water is 18, and the number of OH groups in water is 2.

[0057] In addition to the components described above, the flame-retardant urethane resin composition may contain other additives, such as phenol-based, amine-based, or sulfur-based antioxidants, heat stabilizers, light stabilizers, metal damage inhibitors, antistatic agents, crosslinking agents, lubricants, softeners, pigments, dyes, and tackifying resins, so long as the effects of the present invention are not impaired.

[0058] The flame-retardant urethane resin composition of the present invention is cured by the reaction of the polyol compound and the polyisocyanate compound, and therefore the viscosity of the composition changes over time. Therefore, before using the composition, the composition is divided into two or more portions to prevent the composition from curing by reaction. When using the composition, it is preferable to mix the two or more portions of the composition. When the flame-retardant urethane resin composition is divided into two or more, each component of the flame-retardant urethane resin composition divided into two or more components does not start curing by itself, and the components are divided so that the curing reaction starts after mixing the components of the flame-retardant urethane resin composition. Usually, the flame-retardant urethane resin composition is divided into a polyol composition containing a polyol compound, a flame retardant, a catalyst, and a foaming agent, and a polyisocyanate composition containing a polyisocyanate compound. Then, the polyol composition and the polyisocyanate composition are mixed to prepare the flame-retardant urethane resin composition.

[0059] [Polyurethane foam] The polyurethane foam of the present invention is formed from the above-mentioned flame-retardant urethane resin composition, specifically, is obtained by foaming and curing the flame-retardant urethane resin composition.

[0060] (density) The density of the polyurethane foam is not particularly limited, but is preferably 20 to 200 kg / m 3 It is preferable that the density is in the range of 200 kg / m 3 By setting the density to 20kg / m or less, the polyurethane foam becomes lighter and easier to apply to structures. 3 From these viewpoints, the density of the polyurethane foam is preferably 20 to 100 kg / m 3 More preferably, the range is 23 to 80 kg / m 3 It is more preferable that the density of the polyurethane foam is in the range of 9. The density of the polyurethane foam can be measured in accordance with JIS K7222.

[0061] The polyurethane foam of the present invention can be obtained by mixing a polyol composition and a polyisocyanate composition to prepare a flame-retardant urethane resin composition, and foaming the composition. The mixing and foaming of each component can be performed by a known method. For example, the polyurethane foam can be obtained by using a known device such as a high-pressure foaming machine, a low-pressure foaming machine, a spray foaming machine, or a hand mixer.

[0062] (Application) The applications of the flame-retardant urethane resin composition of the present invention and the polyurethane foam obtained by foaming the composition are not particularly limited, and the composition can be used for filling cavities in structures such as buildings, furniture, automobiles, trains, ships, etc., or for spraying onto such structures. Among these, the composition is preferably used for spraying onto structures, i.e., as a flame-retardant urethane resin composition for spraying. Spraying can be performed using a spraying device (e.g., A-25 manufactured by GRACO) and a spray gun (e.g., D gun manufactured by Gasmar). Spraying can be performed by adjusting the temperature of the polyol composition and the polyisocyanate composition contained in separate containers in the spraying device, mixing them by collision at the tip of the spray gun, and turning the mixed liquid into mist by air pressure. The volume ratio of the polyisocyanate composition to the polyol composition in the mixed liquid (polyisocyanate composition / polyol composition) is not particularly limited, but is usually 0.8 to 1.2, more generally 0.9 to 1.1. The spraying equipment and spray guns are well known and commercially available products can be used. The temperature settings and pressure of the raw liquid can be the same as those for spraying general polyurethane foam. EXAMPLES

[0063] The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples in any way.

[0064] Details of each component used in each example and comparative example are as follows. <Polyol compound> p-Phthalic acid-based polyester polyol (Kawasaki Chemical Industries, Ltd., product name: RFK-505, hydroxyl value = 250 mg KOH / g)

[0065] <Catalyst> (i) Trimerization catalyst: potassium 2-ethylhexanoate (manufactured by Evonik Japan, product name: DABCO K-15), concentration 70 to 80% by mass (ii) Trimerization catalyst: quaternary ammonium carboxylate (manufactured by Evonik Japan, product name: DABCO TMR-7), concentration 45 to 55% by mass (iii) Urethane catalyst: 1,2-dimethylimidazole (Kao Corporation, product name: Kaolizer No. 390) concentration: 65 to 75% by mass (iv) Urethane catalyst: bismuth 2-ethylhexanoate (manufactured by Nitto Chemical Industries, Ltd., product name: BI28), concentration 81 to 90% by mass (v) Urethane catalyst: N,N,N',N'-tetramethylguanidine (manufactured by Evonik Japan, product name: POLYCAT 201), concentration 60%

[0066] <Liquid flame retardant> Phosphate ester flame retardant Tris(β-chloropropyl)phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name: TMCPP) <Filler> Filler: Red phosphorus (Rinkagaku Kogyo, product name: Nova Excel 140), solid flame retardant Filler: Wollastonite (SiO2·CaO) (Kinseimatec Co., Ltd., product name: SH-1250), solid flame retardant

[0067] <Foaming agent> ·water HFO-1233zd <hydrofluoroolefin> (Honeywell product name: Solstice LBA) HFO-1336mzz(Z) (manufactured by Chemours, product name: OPTEON1100)

[0068] <Polyisocyanate compounds> MDI (manufactured by Sumika Covestro Urethane Co., Ltd., product name: 44V-20)

[0069] <Foam stabilizer> Silicone foam stabilizer (Toray Dow Corning, product name: SF-2945F)

[0070] The flame-retardant urethane resin compositions of the respective Examples and Comparative Examples and the polyurethane foams formed from the compositions were evaluated as follows.

[0071] [Gel time] The liquid temperature of the polyol composition having the composition shown in Table 1 and the polyisocyanate composition consisting of the polyisocyanate compound (MDI) was adjusted to 10°C. In a room at 23°C, the polyol composition and the polyisocyanate composition adjusted to 10°C were poured into a 500mL cup so that the total amount of the mixed liquid was 60g at the mixing ratio shown in the table. Then, the mixed liquid was immediately stirred for 2 seconds at 8000 rpm using a Labody Spa (PRIMIX Co., Ltd. high-speed disperser Homo Disper 2.5 type). The time when the stirring started was set as the measurement start time (0 seconds), and the time (seconds) until the foam started to draw strings when a stick was pierced into the foam during foaming was measured, and this was taken as the gel time.

[0072] [Cream Time] The liquid temperature of the polyol composition having the composition shown in Table 1 and the polyisocyanate composition consisting of the polyisocyanate compound (MDI) was adjusted to 10°C. Then, in a room at 23°C, the polyol composition and the polyisocyanate composition adjusted to 10°C were poured into a 500mL cup so that the total amount of the mixed liquid was 60g at the mixing ratio shown in the table. Then, the mixed liquid was immediately stirred at 8000rpm for 2 seconds with a Labody Spa (PRIMIX Co., Ltd. high-speed disperser Homo Disper 2.5 type). The time when the stirring started was set as the measurement start time (0 seconds), and the time (seconds) until the mixed liquid changed color and the liquid level started to rise due to foaming was measured, and this was taken as the cream time.

[0073] [Observation of the cell state of polyurethane foam] The polyurethane foams produced in each of the Examples and Comparative Examples were visually observed and rated as "O" if the cells were fine with no noticeable broken cells, and "X" if the cells were cracked or otherwise coarse.

[0074] [Thermal Conductivity] The polyurethane foams produced in Example 7 and Comparative Examples 1 and 4 were cut into pieces having a length of 200 mm, a width of 200 mm and a thickness of 25 mm to prepare samples for measuring thermal conductivity. The thermal conductivity was measured in the thickness direction of the sample by the heat flow meter method using "HC-074" manufactured by Eiko.

[0075] [External contamination (bleed)] A line was drawn on the surface of the polyurethane foam produced in each Example and Comparative Example with a marker (ZEBRA's "Mackie Extra Fine" oil-based black), and those that did not repel the marker ink were rated as "◯", and those that repelled the marker ink were rated as "X". Note that if the marker ink is repelled, this means that a foam stabilizer or the like has bled out onto the surface of the polyurethane foam, indicating that it is likely to contaminate objects to which it is used.

[0076] [Flammability] The polyurethane foams produced in each of the Examples and Comparative Examples were cut to a length of 10 cm, a width of 10 cm and a thickness of 3.25 cm (within a gypsum board of 12.5 mm) to prepare samples for cone calorimeter testing. The test samples were subjected to a radiant heat intensity test of 50 kW / m in accordance with the ISO-5660 test method. 2 The duration of combustion after the sample was ignited when heated at 100° C. was measured. Burning durations of 100 seconds or less were evaluated as "Good", and burning durations of more than 100 seconds were evaluated as "Poor".

[0077] [Examples 1 to 7, Comparative Examples 1 to 4] A polyol composition was prepared according to the formulation in Table 1. Furthermore, a polyisocyanate composition made of MDI was prepared. Each composition was introduced into a spraying device (A-25, manufactured by GRACO). The temperature was adjusted in the device, and a flame-retardant urethane resin composition made of a mixed solution of a polyol composition and a polyisocyanate composition was sprayed onto a gypsum board having a thickness of 12.5 mm using a spray gun (AP gun, manufactured by GRACO), to form a polyurethane foam. The polyurethane foam thus formed was evaluated for the above-mentioned "observation of the cell state of the polyurethane foam" and "thermal conductivity", and the evaluation results are shown in Table 1.

[0078] The polyol composition obtained according to the formulation shown in Table 1 and the polyisocyanate composition consisting of the polyisocyanate compound were stirred at a liquid temperature of 10°C and 8000 rpm for 2 seconds to obtain a flame-retardant urethane resin composition so that the total amount was 200 g. The flame-retardant urethane resin composition was then sprayed in a box measuring 180 mm x 180 mm and 100 mm deep to form a polyurethane foam. The polyurethane foam thus formed was evaluated for the above-mentioned "external contamination (bleed)". In the evaluation of "flammability," a 12.5 mm thick gypsum board was set at the bottom as a base for the box, and a polyurethane foam formed by spraying a flame-retardant urethane resin composition inside the box was used as a sample.

[0079] [Table 1]

[0080] The parts by mass of each catalyst are parts by mass of the product.

[0081] The flame-retardant urethane resin composition in each Example did not contain a foam stabilizer, so the polyurethane foam obtained had little bleeding on the surface and was difficult to burn. In addition, despite not containing a foam stabilizer, the cell condition was good, the thermal conductivity was low, and the heat insulation was excellent. On the other hand, the flame-retardant urethane resin composition of Comparative Example 1 contained a foam stabilizer, and therefore the polyurethane foam obtained had many surface bleeds and was more susceptible to combustion. The flame-retardant urethane resin compositions of Comparative Examples 2 to 4 did not contain a foam stabilizer, but had long gel times and therefore coarse cells, and therefore had high thermal conductivity and poor insulation.

Claims

1. The flame-retardant urethane resin composition contains a polyol composition containing a polyol compound, a liquid flame retardant, a catalyst, and a foaming agent, and a polyisocyanate composition containing a polyisocyanate compound, the flame-retardant urethane resin composition not containing a foam stabilizer and having a gel time of 20 seconds or less.

2. 2. The flame-retardant urethane resin composition according to claim 1, which has a cream time of 8 seconds or less.

3. The flame-retardant urethane resin composition according to claim 1 or 2, wherein the catalyst comprises a metal-based urethanization catalyst.

4. The flame-retardant urethane resin composition according to any one of claims 1 to 3, wherein the polyol composition further contains a filler.

5. The flame-retardant urethane resin composition according to any one of claims 1 to 4, wherein the catalyst contains a trimerization catalyst.

6. The flame-retardant urethane resin composition according to any one of claims 1 to 5, wherein the content of the liquid flame retardant in the polyol composition is 20 parts by mass or more per 100 parts by mass of the polyol compound.

7. The flame-retardant urethane resin composition according to any one of claims 1 to 6, which is for spray application.

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