JP2022086832A - Flame-retardant urethane resin composition - Google Patents

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

The present invention relates to a flame-retardant urethane resin composition.

Utilizing its excellent heat insulating properties, polyurethane foam is practically used for heat insulating and preventing dew condensation on ceilings, roofs, walls, and other structures of apartment buildings such as condominiums, detached houses, and commercial buildings. ing. The polyurethane foam is formed, for example, by spraying, foaming and curing a urethane resin composition containing a polyol composition and a polyisocyanate composition on the surface of each structure.

For example, Patent Document 1 describes an invention relating to a spray heat insulating material made of a rigid polyurethane foam obtained by foaming a compounding liquid containing a polyisocyanate component, a polyol component, water, a catalyst, a foam stabilizer, a flame retardant, and a powder. Has been done. The sprayed heat insulating material has been shown to be excellent in flame retardancy and dimensional stability.

Japanese Unexamined Patent Publication No. 2010-270877

When a polyurethane foam is formed using a composition containing a foam stabilizer as in Patent Document 1 described above, bleed-out in which the foam stabilizer exudes to the surface of the foam is likely to occur, and therefore the object to be used is Problems such as contamination or the resulting foam being easily burned may occur.
On the other hand, from the viewpoint of solving the problems of bleed-out and flammability, it is conceivable to produce a polyurethane foam without using a defoaming agent. However, it was found that when the defoaming agent was not used, some of the cells forming the polyurethane foam tended to crack, and the cells became rough and the heat insulating property tended to decrease.
Therefore, an object of the present invention is to provide a flame-retardant urethane resin composition capable of suppressing the coarsening of cells and obtaining a polyurethane foam having excellent heat insulating properties when a defoaming agent is not used. ..

As a result of diligent studies, the present inventor is 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. We have found that the above-mentioned problems can be solved by the urethane resin composition, and have completed the present invention. That is, the present invention provides the following [1] to [7].

[1] A flame-retardant urethane resin composition containing a polyol composition containing a polyol compound, a liquid flame-retardant agent, a catalyst, and a foaming agent, and a polyisocyanate composition containing a polyisocyanate compound, wherein the foam-regulating agent is used. A flame-retardant urethane resin composition that does not contain and has a gel time of 20 seconds or less.
[2] The flame-retardant urethane resin composition according to the above [1], wherein the cream time is 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 [1] to [4] above, wherein the catalyst contains a quantification catalyst.
[6] The flame-retardant urethane resin according to any one of [1] to [5] above, wherein the content of the liquid flame retardant in the polyol composition is 20 parts by mass or more with respect to 100 parts by mass of the polyol compound. Composition.
[7] The flame-retardant urethane resin composition according to any one of the above [1] to [6], which is used for spraying.

Since the present invention is a flame-retardant urethane resin composition that does not use a foam stabilizer, it is possible to prevent the foam stabilizer from bleeding out on the surface of the formed polyurethane foam, and the polyurethane foam is easily burned. It can be prevented from becoming. In addition to this, a polyurethane foam having excellent heat insulating properties can be obtained by suppressing the cells from becoming rough.

The present invention is a flame-retardant urethane resin composition containing a polyol composition containing a polyol compound, a liquid flame-retardant agent, a catalyst, and a foaming agent, and a polyisocyanate composition containing a polyisocyanate compound, and is a foam-regulating agent. It is a flame-retardant urethane resin composition which does not contain the above-mentioned material and has a gel time of 20 seconds or less.

(Defoamer)
The flame-retardant urethane resin composition of the present invention does not contain a defoaming agent. By not containing the defoaming agent, it is possible to prevent the defoaming agent from bleeding out on the surface of the polyurethane foam formed when, for example, a silicone-based defoaming agent is used. Further, by removing the defoaming agent component that can be a combustion element, it is possible to prevent the polyurethane foam from being easily burned.
Here, the foam-regulating agent has a foam-regulating function in polyurethane foaming, and means a foam-regulating agent generally used for producing a polyurethane foam. Examples of the defoaming agent include silicone-based defoaming agents and non-silicone-based defoaming agents.
The silicone-based foam stabilizer is a compound having a polysiloxane chain and a polyoxyalkylene chain, and even if it has a block-type structure of the polysiloxane chain and the polyoxyalkylene chain, it is poly as a side chain on the polysiloxane chain of the main chain. It may have a structure in which an oxyalkylene chain is grafted. Specific product names of the silicone-based defoaming agent include, for example, SH-193, SF-2937F, and SF-2945F manufactured by Toray Dow Corning.
The non-silicone-based defoaming agent refers to a defoaming agent other than the silicone-based defoaming agent, and examples thereof include an acrylic-based surfactant. Examples of the acrylic surfactant include an acrylic polymer having a polar group in the side chain.

(Gel time)
The flame-retardant urethane resin composition of the present invention has a gel time of 20 seconds or less. When the gel time exceeds 20 seconds, the balance between the urethane resin forming speed and the foam-regulating force is lost, the cells in the polyurethane foam are partially cracked, and the cells become rough, and the heat insulating property tends to deteriorate.
From the viewpoint of improving the heat insulating property of the formed polyurethane foam, the gel time of the flame-retardant urethane resin composition is preferably 16 seconds or less, more preferably 14 seconds or less, still more preferably 12 seconds or less. , 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, the measurement is performed 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., respectively. Then, in a room at 23 ° C., the above-mentioned polyol composition and polyisocyanate composition adjusted to 10 ° C. are put into a 500 mL cup so as to be a mixed solution having a total amount of 60 g at a predetermined mixing ratio. Then, the mixed solution is immediately stirred at 8000 rpm for 2 seconds at Labody Spa (High-speed disperser Homo Disper 2.5 type manufactured by PRIMIX Corporation). The time at which stirring is started is defined as the measurement start time (0 seconds), and the time (seconds) until the foam begins to pull a string on the rod pierced by the foaming foam is measured, and this is defined as the gel time. In addition, when a quantification catalyst is included, the foam may pull a string and the foam internal curing may occur almost at the same 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.

(Cream time)
The flame-retardant urethane resin composition of the present invention preferably has a cream time of 8 seconds or less. When the cream time is 8 seconds or less, the low thermal conductivity foaming agent (for example, hydrofluoroolefin) contained in the resin composition can be less scattered to the outside of the system and can be confined in the foam, resulting in heat insulating properties. It becomes easy to obtain an excellent polyurethane foam. From such a viewpoint, the cream time of the flame-retardant urethane resin composition is more preferably 6 seconds or less, further preferably 5 seconds or less, still 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, the measurement is performed 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., respectively. Then, in a room at 23 ° C., the above-mentioned polyol composition and polyisocyanate composition adjusted to 10 ° C. are put into a 500 mL cup so as to be a mixed solution having a total amount of 60 g at a predetermined mixing ratio. Then, the mixed solution is immediately stirred at 8000 rpm for 2 seconds at Labody Spa (High-speed disperser Homo Disper 2.5 type manufactured by PRIMIX Corporation). The time at which stirring is started is defined as the measurement start time (0 seconds), and the time (seconds) until the mixture discolors and the liquid level starts to rise due to foaming is measured, and this is defined as 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.

[Polyol composition]
The polyol composition in the present invention contains a polyol compound, a liquid flame retardant, a catalyst, and a foaming agent. Hereinafter, each component contained in the polyol composition will be described.

<polyol compound>
The polyol compound is not particularly limited, and examples thereof include polyether polyols and polyester polyols. From the viewpoint of improving the flame retardancy of the polyurethane foam, the polyol compound preferably contains a polyester polyol. Further, from the viewpoint of improving flame retardancy, it is also preferable to use a halogen-containing polyol or a phosphorus-containing polyol.
From such a viewpoint, the polyester polyol is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 80 parts by mass or more, and 100 parts by mass, out of 100 parts by mass of the polyol compound. It is particularly preferable to use parts by mass.

When two or more kinds of polyol compounds are used, the average hydroxyl value according to the blending ratio of the two or more kinds of polyol compounds may be used as the hydroxyl value of the polyol compound.
For example, when two types of polyol (d1) and polyol (d2) are used as the polyol compound, the hydroxyl value of the polyol (d1) is X ₁ , the compounding ratio is m ₁ , and the hydroxyl value of the polyol (d2) is X ₂ . Assuming that the compounding ratio is m ₂ , the average hydroxyl value is expressed by the following formula. The blending ratio is based on mass.
Average hydroxyl value (mgKOH / g) = X ₁ x (m ₁ / (m ₁ + m ₂ )) + X ₂ x (m ₂ / (m ₁ + m ₂ ))
The average hydroxyl value of the polyol compound used in the present invention is preferably 100 to 500 mgKOH / g, more preferably 150 to 450 mgKOH / g, still more preferably 200 to 400 mgKOH / g, from the viewpoint of improving the flame retardancy of the polyurethane foam. ..
The hydroxyl value is a value measured according to JIS K1557-1: 2007.

(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 obtained polyurethane foam, it is preferable to use a polyester polyol having an aromatic ring. The polyester polyol having an aromatic ring is a condensate of an aromatic dicarboxylic acid such as o-phthalic acid (phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid), and naphthalenedicarboxylic acid and glycol. It is preferable to have. Above all, from the viewpoint of enhancing the flame retardancy of the polyurethane foam, the polyol compound preferably contains a phthalic acid-based polyester polyol which is a condensate of phthalic acid and glycol, and is a condensate of p-phthalic acid and glycol. It is more preferable to contain some p-phthalic acid-based polyester polyols.
The glycol is not particularly limited, but it is preferable to use known low molecular weight aliphatic glycols as constituents of polyester polyols such as ethylene glycol, propylene glycol and diethylene glycol.

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

(Polyether polyol)
The 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 (eg, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexane). Glycols such as diols, neopentyl glycols, cyclohexylene glycols and cyclohexanedimethanol, triols such as trimethylolpropane and glycerin, tetrafunctional alcohols such as pentaerythritol, high functionalities such as sucroses and sorbitols), Aliper amines (eg, alkylene diamines such as ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, neopentyldiamine, alkanol amines such as monoethanolamine, diethanolamine), aromatic amines (eg, aniline, tolylene diamine, xylyl). Rangeamine, diphenylmethanediamine, Mannig condensate, etc.) and the like.
Among these, the polyether polyol produced by using the initiator having an aromatic ring is a polyether polyol having an aromatic ring, and for example, the polyether polyol produced by using an aromatic amine as an initiator has an aromatic ring. It is a polyether polyol having. Among the polyether polyols having an aromatic ring, tolylene diamine-based polyether polyols, Mannig-based polyether polyols and the like can be preferably used.

The tolylene diamine-based polyether polyol is a tolylene diamine-based polyether polyol produced by using tolylene diamine as an initiator.
The Mannich-based polyether polyol is obtained by utilizing the Mannich reaction, and is obtained by adding an alkylene oxide to a Mannich condensate having two or more hydroxyl groups in the molecule, or such a Mannich condensate. It is a polyether polyol. More specifically, at least one of phenol and an alkyl substituted derivative thereof, a Mannich condensate obtained by the Mannich reaction of formaldehyde and alkanolamine, or at least one of ethylene oxide and propylene oxide in this compound is ring-opened addition polymerization. It is a polyether polyol obtained by making it.

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

<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 obtained polyurethane foam. Among the liquid flame retardants, a phosphoric acid ester flame retardant is particularly preferable. When a phosphoric acid ester flame retardant is used, the flame retardancy of the polyurethane foam can be improved, and the viscosity of the polyol composition can be appropriately controlled even when a filler described later is used. Here, the liquid flame retardant is a flame retardant that is liquid at 23 ° C.

Examples of the phosphoric acid ester-based flame retardant include monophosphate ester and condensed phosphoric acid ester.
The monophosphate ester is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, and tris (β-chloropropyl) phosphate.
The condensed phosphoric acid ester is not particularly limited, and is, for example, resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycredyl phosphate (trade name CR-741), and aromatic condensed phosphoric acid ester (trade name CR747). ) And so on.

The content of the liquid flame retardant is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, still more preferably 45 parts by mass or more, and preferably 100 parts by mass with respect to 100 parts by mass of the polyol compound. It is not less than parts by mass, and more preferably 80 parts by mass or less. When the content of the liquid flame retardant is at least these lower limit values, the flame retardancy of the polyurethane foam can be improved, and when it is at least these upper limit values, the mechanical strength of the polyurethane foam can be improved. Further, by containing a certain amount or more of the liquid flame retardant, the compatibility between the polyisocyanate composition and the polyol composition at the time of mixing is improved, and it is considered that the bubble formation can be stabilized even when the foam stabilizer is not contained.

<Filler>
The polyol composition in the present invention may contain a filler. The filler is contained as a solid component in the flame-retardant urethane resin composition, and is a component that generally exists in the form of granules or powder. By containing the filler, various physical properties such as mechanical strength and flame retardancy can be improved depending on the type of the filler.
The filler may be a 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.

The filler preferably contains a solid flame retardant. Examples of solid flame retardants include boron-based flame retardants, brominated flame retardants, phosphate-containing flame retardants, antimony-containing flame retardants, phosphinic acid-based flame retardants, metal hydroxide-based flame retardants, red phosphorus, and needle-like fillers. Is preferable. Among these, red phosphorus, needle-like filler and the like are preferable from the viewpoint of improving the flame retardancy of the polyurethane foam.

(Boron flame retardant)
Specific examples of the boron-based flame retardant include alkali metal borate salts such as lithium borate, sodium borate, potassium borate, and cesium borate, and boric acid such as magnesium borate, calcium borate, and barium borate. Examples thereof include alkaline earth metal salts, zirconium borate, zinc borate, aluminum borate, and ammonium borate. Of these, zinc borate is preferable.

(Brominated flame retardant)
The brominated flame retardant is not particularly limited as long as it is a compound containing bromine in its molecular structure, and examples thereof include aromatic brominated compounds.
Specific examples of the aromatic brominated compound include, for example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, and bis. (Pentabromophenoxy) Monomer-based organic bromine compounds such as ethane, ethylenebis (pentabromophenyl), ethylenebis (tetrabromophthalimide), tetrabromobisphenol A, polycarbonate oligomers produced from brominated bisphenol A, the above. Bromine such as brominated polycarbonate such as a copolymer of polycarbonate oligomer and bisphenol A, diepoxy compound produced by reaction between brominated bisphenol A and epichlorohydrin, and bromine such as monoepoxy compound obtained by reaction between brominated phenols and epichlorohydrin. Epoxy compounds, poly (brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, condensates of cyanur chloride and brominated phenol, brominated (polystyrene), poly (brominated styrene), crosslinked brominated polystyrene, etc. Examples thereof include halogenated bromine compound polymers such as brominated polystyrene, cross-linked or non-cross-linked brominated poly (α-methylstyrene).
Among these, ethylene bis (pentabromophenyl), ethylene bis (tetrabromophthalimide), hexabromobenzene and the like are preferable.

(Phosphate-containing flame retardant)
Examples of the phosphate-containing flame retardant include phosphoric acid and metals of the Group IA to Group IVB of the Periodic Table.
Phosphates consisting of salts with at least one metal or compound selected from ammonia, aliphatic amines and aromatic amines can be mentioned.
The phosphoric acid is not particularly limited, and examples thereof include various phosphoric acids such as monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid.
Examples of the metals of Group IA to Group IVB of the Periodic Table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum. Examples of the aliphatic amine include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like. Further, examples of the aromatic amine include pyridine, triazine, melamine and the like.
The above-mentioned phosphate-containing flame retardant may be subjected to a known water resistance improving treatment such as a silane coupling agent treatment or a coating with a melamine resin.

Specific examples of the phosphate-containing flame retardant include monophosphate, pyrophosphate, polyphosphate and the like.
The monophosphate is not particularly limited, but for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, monosodium phosphate, and the like.
Sodium salts such as disodium phosphate, trisodium phosphate, monosodium phosphite, dissodium phosphite, sodium hypophosphite, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, phosphite Potassium salts such as monopotassium, dipotassium phosphite, potassium hypophosphite, monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, hypophosphite Lithium salt such as lithium, barium dihydrogen phosphate,
Barium salts such as barium hydrogen phosphate, tribarium phosphate, barium hypophosphite, magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium salts such as magnesium hypophosphite, dihydrogen phosphate Examples thereof include calcium salts such as calcium, calcium hydrogen phosphate, tricalcium phosphate and calcium hypophosphite, and zinc salts such as zinc phosphate, zinc phosphite and zinc hypophosphite.

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

(Antimony-containing flame retardant)
Examples of the antimony-containing flame retardant used in the present invention include antimony oxide, antimony acid salt, pyroantimony acid salt and the like.
Examples of antimony oxide include antimony trioxide and antimony pentoxide. Examples of the antimonate include sodium antimonate, potassium antimonate and the like. Examples of the pyroantimonate include sodium pyroantimonate,
Examples thereof include potassium pyroantimonate.
The antimony-containing flame retardant is preferably antimony oxide.
The antimony-containing flame retardant may be used alone or in combination of two or more.

(Phosphinic acid flame retardant)
Examples of the phosphinic acid-based flame retardant 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 and the like can be mentioned.

(Metal hydroxide flame retardant)
Examples of the metal hydroxide-based flame retardant include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, and hydroxide. Examples include vanadium and tin hydroxide. The metal hydroxide-based flame retardant may be used alone or in combination of two or more.

(Red phosphorus)
The red phosphorus may be composed of a simple substance of red phosphorus, or may be a mixture or a coating of red phosphorus with a resin, a metal hydroxide, a metal oxide or the like.

(Needle filler)
Examples of the needle-shaped filler include potassium titanate whisker, aluminum borate whisker, magnesium-containing whisker, silicon-containing whisker, wollastonite, sepiolite, zonolite, elestadite, boehmite, rod-shaped hydroxyapatite, glass fiber, carbon fiber, and graphite fiber. , Metal fiber, slag fiber, gypsum fiber, silica fiber, alumina fiber, silica alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, stainless fiber and the like.
These needle-shaped fillers may be used alone or in combination of two or more.

Further, the filler may be an inorganic filler other than the above-mentioned flame retardant. As inorganic fillers, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate , Barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite, active white clay, imogolite, sericite, glass beads, silica balun, aluminum nitride, boron nitride, silicon nitride, graphite, carbon balun, charcoal powder, various metals Powder, magnesium sulfate, lead zirconate titanate, molybdenum sulfide, silicon carbide, various magnetic powders, fly ash and the like can be appropriately used. The inorganic filler may be used alone or in combination of two or more.

The content of the filler is preferably 10 parts by mass or more, more preferably 25 parts by mass or more, still more preferably 30 parts by mass or more, and preferably 80 parts by mass with respect to 100 parts by mass of the polyol compound. It is less than or equal to, more preferably 60 parts by mass or less.
When the content of the filler is at least these lower limit values, it becomes easy to exert the function according to the type of the filler used. For example, when a solid flame retardant is used as the filler, the flame retardancy of the polyurethane foam is improved. It will be easier to do. When the content of the filler is not more than these upper limit values, clogging of the spraying device and the like can be suppressed, and the spraying property can be improved.

The flame-retardant urethane resin composition may not contain the above-mentioned filler. When the filler is not contained, a precipitate is unlikely to be generated during storage, the handling property is excellent, and the wear of the equipment used at the time of use can be suppressed.

<Effervescent agent>
Specific examples of the foaming agent include water, low boiling hydrocarbons, chlorinated aliphatic hydrocarbon compounds, fluorine compounds, hydrochlorofluorocarbon compounds, hydrofluorocarbons, ether compounds, hydrofluoroolefins and the like. Further, examples of the effervescent agent include organic physical effervescent agents such as a mixture of these compounds, and inorganic physical effervescent 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, cycloheptane and the like.
Examples of the chlorinated aliphatic hydrocarbon compound include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride and the like.
Examples of the fluorine compound include CHF ₃ , CH ₂ F ₂ , CH ₃ F and the like.
Examples of the hydrochlorofluorocarbon compound include trichlormonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (). 1-chloro-1,1-difluoroethane)) and the like can be mentioned.
Examples of the hydrofluorocarbon include HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane).
Examples of the ether compound include diisopropyl ether and the like.
Examples of the hydrofluoroolefin include HFO-1233zd (E) (trans-1-chloro-3,3,3-trifluoropropene) and HFO-1234yf (2,3,3,3-tetrafluoro-1-. Propene), HFO-1336mzz (Z) (cis-1,1,1,4,4,4-hexafluorobut-2-en), HFO-1224yd (Z) and the like.

Among the above, as the foaming agent, hydrofluoroolefin, water and the like are preferable, and it is more preferable to use hydrofluoroolefin and water in combination.
The content of the foaming agent is preferably 5 to 70 parts by mass, and more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the polyol compound from the viewpoint of adjusting the density of the foam to a desired range. , More preferably 20 to 50 parts by mass.

The amount of the hydrofluoroolefin used as the foaming agent is preferably 3 to 60 parts by mass, more preferably 8 to 60 parts by mass with respect to 100 parts by mass of the polyol compound from the viewpoint of keeping the density of the polyurethane foam in a desired range. It is 57 parts by mass, more preferably 19 to 49 parts by mass.
As the water used as the foaming agent, for example, ion-exchanged water, distilled water and the like can be appropriately used. The amount of water with respect to 100 parts by mass of the polyol compound is preferably 0.05 to 10 parts by mass, preferably 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. It is preferably 0.1 to 3 parts by mass, and more preferably 0.2 to 2 parts by mass.

<Catalyst>
The polyol composition contains a catalyst. Examples of the catalyst include a urethanization catalyst and a trimerization catalyst. A quantification catalyst is a catalyst that promotes quantification to form an isocyanate 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.

As the trimerization catalyst, nitrogen-containing aromatic compounds such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, and 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine. , Carvone alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate, potassium octylate, tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt, tetramethylammonium salt, tetraethylammonium salt, etc. A quaternary ammonium salt such as a tetraphenylammonium salt, a triethylmonomethylammonium salt, or a quaternary ammonium salt of a carboxylic acid can be used. A preferred specific example of the carboxylic acid in the ammonium carboxylic acid 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.
As the trimerization catalyst, at least one selected from the group consisting of a carboxylic acid alkali metal salt and a carboxylic acid quaternary ammonium salt is preferable, and it is preferable to use a carboxylic acid alkali metal salt and a carboxylic acid quaternary ammonium salt in combination. ..

The content of the trimerization catalyst is preferably 1 to 30 parts by mass, and more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the polyol compound.

Further, in the present invention, the catalyst preferably contains a urethanization catalyst, and more preferably contains both the above-mentioned trimerization catalyst and urethanization catalyst.

The urethanization catalyst is a catalyst that promotes the reaction between the polyol compound and the polyisocyanate compound. Specifically, examples of the urethanization catalyst include amino compounds and metal-based urethanization catalysts.
Examples of the metal-based urethanization catalyst include tin compounds, bismuth compounds, and acetylacetone metal salts. Among these, bismuth compounds and tin are used 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 selected from the compounds is preferable.

Examples of the amino compound include 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2methylimidazole, and an imidazole compound in which the secondary amine functional group in the imidazole ring is replaced with a cyanoethyl group. , Pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinbis (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'-dimethylaminoethyl piperazine, N, N-dimethylcyclohexylamine, diazabicycloundecene , Triethylenediamine, tetramethylethylenediamine, tetramethylhexamethylenediamine, trimethylaminoethylpiperazine, tripropylamine, N, N, N', N'-tetramethylguanidine and their acid blocks. Among the amino compounds, imidazole compounds are preferable from the viewpoint of storage stability.

Examples of the tin compound include stannous octylate, dibutyl tin diacetate, and dibutyl tin dilaurate. Examples of the bismuth compound include bismuth neodecanoate and bismuth octylate.
Examples of the acetylacetone metal salt include acetylacetone aluminum, acetylacetone iron, acetylacetone copper, acetylacetone zinc, acetylacetone verylium, acetylacetone chromium, acetylacetone indium, acetylacetone manganese, acetylacetone molybdenum, acetylacetone titanium, acetylacetone cobalt, acetylacetone vanadium, acetylacetone zirconium and the like. ..
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 below a certain level.

The catalyst preferably contains a metal-based urethanization catalyst, and the content of the metal-based urethanization catalyst is preferably 0.5 to 15 parts by mass, more preferably 1 to 1 to 100 parts by mass with respect to 100 parts by mass of the polyol compound. It is 13 parts by mass, more preferably 1.5 to 10 parts by mass.

Further, from the viewpoint of keeping the gel time below a certain level, it is preferable to use a metal-based urethanization catalyst and an amino compound in combination as the urethanization catalyst, and more preferably, a bismuth compound and an imidazole-based compound are used in combination.
When the metal-based urethanization catalyst and the amino compound are used in combination, the mass ratio of the amino compound to the metal-based urethanization catalyst (mass of the amino compound / mass of the metal-based urethanization catalyst) is preferably 0.1 to 10. , More preferably 0.5 to 8, and even more preferably 1 to 5.

The content of the urethanization catalyst is not particularly limited, but is preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the polyol compound.

The total amount of the catalyst is preferably 2 to 60 parts by mass, more preferably 7 to 40 parts by mass with respect to 100 parts by mass of the polyol compound.

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

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. It is 1.2, more preferably 0.9 to 1.1.

The isocyanate index of the flame-retardant urethane resin composition is preferably 150 to 600, more preferably 200 to 500. When the isocyanate index is at least these lower limit values, a polyurethane foam having high flame retardancy can be easily obtained, and when the isocyanate index is at least these upper limit values, the foamability at the time of forming the foam can be improved.
The isocyanate index (INDEX) is a value obtained by dividing the number of moles of isocyanate groups in polyisocyanate by the total number of moles of active hydrogen groups of water used as a hydroxyl group of a polyol and a foaming agent, and multiplying by 100. It is calculated by.

INDEX = equivalent of isocyanate ÷ (equivalent of polyol + equivalent of water) x 100
here,
Equivalent number of isocyanate = number of copies of polyisocyanate used x NCO content (%) x 100 / NCO molecular weight Equivalent number of polyol = OHV x number of copies of polyol ÷ molecular weight of KOH, OHV is the hydroxyl value of the polyol (mgKOH / g),
Equivalent number of water = number of copies of water used x number of OH groups of water / molecular weight of water. In the above formula, the unit of the number of copies used is the weight (g), the molecular weight of the NCO group is 42, and the NCO content is the ratio of the NCO group in the polyisocyanate compound expressed by mass%. For convenience of unit conversion, the molecular weight of KOH is 56100, the molecular weight of water is 18, and the number of OH groups of water is 2.

In addition to the above-mentioned components, the flame-retardant urethane resin composition may contain other additives such as phenol-based, amine-based, and sulfur-based antioxidants, and heat, as long as the effects of the present invention are not impaired. Stabilizers, light stabilizers, metal damage inhibitors, antistatic agents, cross-linking agents, lubricants, softeners, pigments, dyes, tackifier resins and the like can be included.

Since the flame-retardant urethane resin composition of the present invention is cured by reacting the polyol compound with the polyisocyanate compound, its viscosity changes with time. Therefore, before using the composition, the composition is divided into two or more to prevent the composition from reacting and curing. Then, when using the composition, it is preferable to mix the composition divided into two or more.
When the flame-retardant urethane resin composition is divided into two or more, curing does not start with each component of the flame-retardant urethane resin composition divided into two or more, and each of the flame-retardant urethane resin compositions does not start curing. The components may be divided so that the curing reaction starts after the components of the above are mixed. 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 a flame-retardant urethane resin composition.

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

(density)
The density of the polyurethane foam is not particularly limited, but is preferably in the range of 20 to 200 kg / m ³ . By setting the density to 200 kg / m ³ or less, the polyurethane foam becomes lightweight and the workability on the structure is improved. Further, when the weight is 20 kg / m ³ or more, the desired flame retardancy can be easily developed. From these viewpoints, the density of the polyurethane foam is more preferably in the range of 20 to 100 kg / m ³ , and further preferably in the range of 23 to 80 kg / m ³ . The density of the polyurethane foam can be measured according to JIS K7222.

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. Mixing and foaming of each component can be performed by a known method. For example, it can be obtained by using a known device such as a high-pressure foaming machine, a low-pressure foaming machine, a spray foaming machine, and a hand mixer.

(Use)
The use of the flame-retardant urethane resin composition of the present invention and the polyurethane foam obtained by foaming the composition is not particularly limited, but it is filled in cavities of structures such as buildings, furniture, automobiles, trains and ships. It can be used for the purpose of spraying on the structure or for spraying on the structure. Above all, it is preferable to use it as a flame-retardant urethane resin composition for spraying on a structure, that is, for spraying.
The spraying can be carried out by using a spraying device (for example, GRACO: A-25) and a spray gun (for example, Gasmer: D gun). The spraying can be carried out by adjusting the temperature of the polyol composition and the polyisocyanate composition contained in separate containers in a spraying device, colliding and mixing the two with the tip of a spray gun, and mistizing the mixed solution by air pressure. The volume ratio of the polyisocyanate composition to the polyol composition (polyisocyanate composition / polyol composition) in the mixed solution is not particularly limited, but is usually 0.8 to 1.2, and more generally. It is 0.9 to 1.1.
Spraying devices and spray guns are known, and commercially available products can be used. In addition, general urethane foam spraying conditions can be applied to the undiluted solution temperature setting, pressure, etc.

The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

The details of each component used in each Example and Comparative Example are as follows.
<polyol compound>
-P-Phthalic acid polyester polyol (manufactured by Kawasaki Kasei Co., Ltd., product name: RFK-505, hydroxyl value = 250 mgKOH / g)

<Catalyst>
(I) Triquantization catalyst: 2-ethylhexanoic acid potassium salt (manufactured by Evonik Japan, product name: DABCO K-15), concentration 70-80% by mass
(Ii) Trimerization catalyst: Carboxylic acid quaternary ammonium salt (manufactured by Evonik Japan, product name: DABCO TMR-7), concentration 45-55% by mass
(Iii) Urethane catalyst: 1,2-dimethylimidazole (manufactured by Kao Corporation, product name: Kaorizer No. 390) Concentration 65-75% by mass
(Iv) Urethane catalyst: Bismuth 2-ethylhexanoate (manufactured by Nitto Kasei Co., Ltd., product name: BI28), concentration 81-90% by mass
(V) Urethane catalyst: N, N, N', N'-tetramethylguanidine (manufactured by Evonik Japan, product name: POLYCAT 201), concentration 60%

<Liquid flame retardant>
・ Phosphate ester flame retardant Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)
<Filler>
・ Filler red phosphorus (Phosphorus chemical industry, product name: Nova Excel 140), solid flame retardant ・ Filler wollastonite (SiO2 ・ CaO) (manufactured by Kinsei Matek, product name: SH-1250), solid flame retardant

<Effervescent agent>
-Water-HFO-1233zd <hydrofluoroolefin> (manufactured by Honeywell, product name: Solstice LBA)
・ HFO-1336mzz (Z) (manufactured by The Chemours Company, product name: OPTEN1100)

<Polyisocyanate compound>
・ MDI (manufactured by Sumika Covestro Urethane Co., Ltd., product name: 44V-20)

<Foam control agent>
-Silicone-based defoaming agent (manufactured by Toray Dow Corning, product name: SF-2945F)

The flame-retardant urethane resin composition of each Example and Comparative Example and the polyurethane foam formed by the composition were evaluated as follows.

[Gel time]
The liquid temperatures of the polyol composition having the composition shown in Table 1 and the polyisocyanate composition composed of the polyisocyanate compound (MDI) were adjusted to 10 ° C., respectively. Then, in a room at 23 ° C., the above-mentioned polyol composition and polyisocyanate composition adjusted to 10 ° C. are put into a 500 mL cup so as to be a mixed solution having a total amount of 60 g at the mixing ratio as shown in the table. did. Then, the mixed solution was immediately stirred at 8000 rpm for 2 seconds at Labody Spa (High-speed disperser Homo Disper 2.5 type manufactured by PRIMIX Corporation). The time at which stirring was started was defined as the measurement start time (0 seconds), and the time (seconds) until the foam began to pull a string on the rod pierced by the foaming foam was measured, and this was defined as the gel time.

[Cream time]
The liquid temperatures of the polyol composition having the composition shown in Table 1 and the polyisocyanate composition composed of the polyisocyanate compound (MDI) were adjusted to 10 ° C., respectively. Then, in a room at 23 ° C., the above-mentioned polyol composition and polyisocyanate composition adjusted to 10 ° C. are put into a 500 mL cup so as to be a mixed solution having a total amount of 60 g at the mixing ratio as shown in the table. did. Then, the mixed solution was immediately stirred at 8000 rpm for 2 seconds at Labody Spa (High-speed disperser Homo Disper 2.5 type manufactured by PRIMIX Corporation). The time at which stirring was started was defined as the measurement start time (0 seconds), and the time (seconds) until the mixture discolored and the liquid level started to rise due to foaming was measured, and this was defined as the cream time.

[Observation of cell condition of polyurethane foam]
By visually observing the polyurethane foams produced in each Example and Comparative Example, the case where the cell state is fine and there is no conspicuous bubble rupture is "○", and the case where the cell is cracked and is in a rough state is "". It was evaluated as "x".

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

[External pollution (bleed)]
Draw a line on the surface of the polyurethane foam produced in each example and comparative example with magic (ZEBRA, "McKee extra-fine" oil-based black), and "○" for those that do not repel magic ink and "×" for those that repel magic ink. I evaluated it. When the magic ink is repelled, it means that the foam stabilizer or the like is bleeding out on the surface of the polyurethane foam, indicating that the object to be used is easily contaminated.

[Combustion quality]
The polyurethane foam produced in each Example and Comparative Example was cut into a length of 10 cm, a width of 10 cm, and a thickness of 3.25 cm (inner gypsum board 12.5 mm) to prepare a sample for a corn calorimeter test. When the test sample was heated at a radiant heat intensity of 50 kW / m ² in accordance with the ISO-5660 test method, the combustion duration after the sample was ignited was measured. Those having a combustion duration of 100 seconds or less were evaluated as "◯", and those having a combustion duration of more than 100 seconds were evaluated as "x".

[Examples 1 to 7, Comparative Examples 1 to 4]
Polyol compositions were prepared according to the formulations shown in Table 1. Further, a polyisocyanate composition composed of MDI was prepared. Each composition was introduced into a spraying device (GRACO: A-25). A flame-retardant urethane resin composition consisting of a mixed solution of a polyol composition and a polyisocyanate composition is prepared into a flame-retardant urethane resin composition having a thickness of 12.5 mm by adjusting the temperature in the apparatus and using a spray gun (manufactured by GRACO: AP gun). A polyurethane foam was formed by spraying onto a gypsum board. With respect to the polyurethane foam thus formed, the above-mentioned "observation of the cell state of the polyurethane foam" and "thermal conductivity" were evaluated, and the evaluation results are shown in Table 1.

A flame-retardant urethane resin composition obtained by stirring the polyol composition obtained by the formulation shown in Table 1 and the polyisocyanate composition composed of the polyisocyanate compound at a liquid temperature of 10 ° C. and 8000 rpm for 2 seconds so as to have a total of 200 g. Got Then, the flame-retardant urethane resin composition was sprayed into a box having a size of 180 mm × 180 mm and a depth of 100 mm to form a polyurethane foam. The polyurethane foam thus formed was evaluated for the above-mentioned "external contamination (bleed)".
In the evaluation of "combustibility", a polyurethane foam formed by spraying a flame-retardant urethane resin composition in a box using a box having a gypsum board having a thickness of 12.5 mm set as a base on the bottom of the box. The body was used as a sample.

The mass part of each catalyst is the mass part as a product.

Since the flame-retardant urethane resin composition in each example did not contain a foam stabilizer, the obtained polyurethane foam had few bleeds on the surface and was difficult to burn. In addition, although it did not contain a defoaming agent, the cell condition was good, the thermal conductivity was low, and the heat insulating property was excellent.
On the other hand, since the flame-retardant urethane resin composition of Comparative Example 1 contains a defoaming agent, many of the obtained polyurethane foams bleed on the surface and are more easily burned. Although the flame-retardant urethane resin compositions of Comparative Examples 2 to 4 did not contain a defoaming agent, they had a large gel time value, so that the cell state was rough, and therefore the thermal conductivity was high and the heat insulating property was inferior.

Claims (7)

A flame-retardant urethane resin composition containing 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, and does not contain a foam stabilizer. , A flame-retardant urethane resin composition having a gel time of 20 seconds or less. The flame-retardant urethane resin composition according to claim 1, wherein the cream time is 8 seconds or less. The flame-retardant urethane resin composition according to claim 1 or 2, wherein the catalyst contains a metallic urethanization catalyst. The flame-retardant urethane resin composition according to any one of claims 1 to 3, wherein the polyol composition further contains a filler. The flame-retardant urethane resin composition according to any one of claims 1 to 4, wherein the catalyst contains a quantification catalyst. 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 with respect to 100 parts by mass of the polyol compound. The flame-retardant urethane resin composition according to any one of claims 1 to 6, which is used for spraying.