JP2022057750A - Flame-retardant urethane resin composition - Google Patents

Abstract

To provide a flame-retardant urethane resin composition which enables formation of a polyurethane foam excellent in flame retardance while setting a volume ratio of a mixture of a polyol composition and a polyisocyanate composition in a specific range.SOLUTION: A flame-retardant urethane resin composition is a mixed liquid obtained by mixing a polyol composition containing a polyol compound, a flame retardant, a catalyst, and a foaming agent with a polyisocyanate composition containing a polyisocyanate compound, in which a volume ratio (polyisocyanate composition/polyol composition) of the polyisocyanate composition to the polyol composition is 0.8-1.2, and an isocyanate index is 250 or more.SELECTED DRAWING: None

Description

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

Polyurethane foam is practically used for heat insulation and dew condensation prevention of each structure such as ceilings, roofs, walls of buildings such as condominiums, detached houses, and commercial buildings by utilizing its excellent heat insulating properties. 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.

Although polyurethane foam is lightweight, it is easy to burn because it is an organic substance. In order to improve this, a highly flame-retardant polyurethane foam is required.
For example, Patent Document 1 comprises 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, and the amount of the polyester polyol and water. The present invention describes an invention relating to a sprayed heat insulating material, which comprises a specific range and uses a specific amount of a powder having a certain particle size. The sprayed heat insulating material has been shown to be excellent in flame retardancy and dimensional stability.

Japanese Unexamined Patent Publication No. 2010-270877

In general, it is known that the use of a composition having a high isocyanate index is suitable for forming a highly flame-retardant polyurethane foam. However, when the polyurethane foam is formed by spraying, since the pump of the spraying device has a specific structure, the mixture of the polyol composition and the polyisocyanate composition can be adjusted only to a volume ratio of about 1: 1 and poly. It is difficult to increase the isocyanate index by relatively increasing the volume of the isocyanate composition.
Therefore, the present invention is a flame-retardant urethane resin composition in which the volume ratio of the mixture of the polyol composition and the polyisocyanate composition is in a specific range, and is flame-retardant capable of forming a polyurethane foam having excellent flame retardancy. It is an object of the present invention to provide a urethane resin composition.

As a result of diligent studies, the present inventor has found that the above-mentioned problems can be solved by a flame-retardant urethane resin composition in which the volume ratio of the polyisocyanate composition to the polyol composition and the isocyanate index are in a specific range, and completed the present invention. I let you. That is, the present invention provides the following [1] to [7].
[1] A flame-retardant urethane resin composition which is a mixed solution of a polyol composition containing a polyol compound, a flame-retardant agent, a catalyst, and a foaming agent and a polyisocyanate composition containing a polyisocyanate compound, and is a polyol. A flame-retardant urethane resin composition having a volume ratio of the polyisocyanate composition to the composition (polyisocyanate composition / polyol composition) of 0.8 to 1.2 and an isocyanate index of 250 or more.
[2] The flame-retardant urethane resin composition according to the above [1], wherein the weighted average hydroxyl value of the polyol compound in the mixed solution is more than 200 mgKOH / g.
[3] The flame-retardant urethane resin composition according to the above [1] or [2], wherein the water content of the polyol composition measured by the Karl Fischer method is 2% by mass or less.
[4] The flame-retardant urethane resin composition according to any one of the above [1] to [3], which further contains a filler and the content of the filler is 20 parts by mass or more with respect to 100 parts by mass of the polyol compound. ..
[5] The above [1] to [4], wherein the flame retardant contains a phosphoric acid ester flame retardant, and the content of the phosphoric acid ester flame retardant is 40 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.
[6] The flame-retardant urethane resin composition according to any one of [1] to [5] above, wherein the catalyst contains a bismuth compound.
[7] The flame-retardant urethane resin composition according to any one of the above [1] to [6], which is used for spraying.

According to the present invention, it is possible to provide a flame-retardant urethane resin composition capable of forming a polyurethane foam having excellent flame retardancy while keeping the volume ratio of the polyisocyanate composition to the polyol composition within a certain range.

The present invention relates to a flame-retardant urethane resin composition which is a mixed solution of a polyol composition containing a polyol compound, a flame retardant, a catalyst and a foaming agent and a polyisocyanate composition containing a polyisocyanate compound. The flame-retardant urethane resin composition has a volume ratio (polyisocyanate composition / polyol composition) of the polyisocyanate composition to the polyol composition of 0.8 to 1.2, and an isocyanate index of 250 or more.
Since the flame-retardant urethane resin composition of the present invention is a mixed solution of the polyol composition and the polyisocyanate composition as described above, at least the polyol compound, the polyisocyanate compound, the flame retardant, the catalyst, and the foaming agent are used. It is a composition containing.

The flame-retardant urethane resin composition of the present invention is preferably used for spraying as described later. In that case, the flame-retardant urethane resin composition of the present invention comprises a polyol composition containing a polyol compound, a flame retardant, a catalyst, and a foaming agent, and a polyisocyanate composition containing a polyisocyanate compound by a spraying device or the like. Is prepared as a mixed solution. Due to the pump structure of the spraying device, the volume ratio of the polyisocyanate composition to the polyol composition (polyisocyanate composition / polyol composition) in the mixture is usually 0.8 to 1.2, which is more general. Is 0.9 to 1.1. The volume ratio means a volume ratio. INDUSTRIAL APPLICABILITY The present invention can provide a polyurethane foam having excellent flame retardancy even in a flame-retardant urethane resin composition in which the volume ratio of the polyol composition and the polyisocyanate composition is within a certain range.

[Isocyanate index]
The isocyanate index of the flame-retardant urethane resin composition of the present invention is 250 or more. If the isocyanate index is less than 250, a polyurethane foam having the desired flame retardancy cannot be obtained. Further, the flame-retardant urethane resin composition of the present invention can have an isocyanate index of 250 or more even when a polyol compound having a hydroxyl value of a certain value or more is used, so that the obtained polyurethane foam machine can be used. It is possible to improve flame retardancy while maintaining the target strength. The isocyanate index of the flame-retardant urethane resin composition is preferably 300 or more, more preferably 350 or more. Further, from the viewpoint of improving the foamability at the time of forming the foam, the isocyanate index is preferably 600 or less.
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 hydroxyl groups of the polyol and active hydrogen groups of water used as 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 in 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.

[Moisture percentage]
The water content of the polyol composition measured by the Karl Fischer method is preferably 2% by mass or less. When the water content is 2% by mass or less, the isocyanate index of the flame-retardant urethane resin composition becomes high, and the flame-retardant property of the obtained polyurethane foam is improved. From the viewpoint of improving the flame retardancy of the polyurethane foam, the water content of the polyol composition measured by the Karl Fischer method is preferably 1.5% by mass or less, more preferably 1% by mass or less.

[Polyol compound]
The polyol compound contained in the polyol composition in the present invention may be one kind of polyol or two or more kinds of polyols.
The weighted average hydroxyl value of the polyol compound in the mixed solution is preferably more than 200 mgKOH / g. When the weighted average hydroxyl value is more than 200 mgKOH / g, the mechanical strength of the formed polyurethane foam is likely to be improved, and the workability at the time of spraying is improved. Therefore, from the viewpoint of increasing the mechanical strength of the obtained polyurethane foam and improving the workability at the time of spraying, the weighted average hydroxyl value of the polyol compound is preferably 205 mgKOH / g or more, more preferably. It is 210 mgKOH / g or more, more preferably 220 mgKOH / g or more. On the other hand, from the viewpoint of enhancing the flame retardancy of the obtained polyurethane foam, the weighted average hydroxyl value of the polyol compound is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, still more preferably 270 mgKOH / g. It is as follows.

Here, the weighted average hydroxyl value of the polyol compound is determined by the sum of the product of the hydroxyl values of the individual polyols constituting the polyol compound and the weight fraction of the individual polyols in 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 amount is m ₁ , and the hydroxyl value of the polyol (d2) is X ₂ . Assuming that the blending amount is m ₂ , the weighted average hydroxyl value is expressed by the following formula. The blending amounts m ₁ and m ₂ are the number of parts by mass in 100 parts by mass of the polyol compound.
Weighted average hydroxyl value (mgKOH / g) = X ₁ x (m ₁ / (m ₁ + m ₂ )) + X ₂ x (m ₂ / (m ₁ + m ₂ ))

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, and more preferably contains a phthalic acid-based 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.

<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.
From the viewpoint of enhancing the flame retardancy of the polyurethane foam, the content of the p-phthalic acid-based polyester polyol is preferably 50 parts by mass or more, more preferably 80 parts by mass or more in 100 parts by mass of the polyol compound. , 100 parts by mass is even more preferred.

<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 diol, neopentyl glycol, cyclohexylene glycol, cyclohexanedimethanol, triols such as trimethylolpropane and glycerin, tetrafunctional alcohols such as pentaerythritol, polyfunctionals such as sucrose and sorbitol), Aliper amines (eg, alkylene diamines such as ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, neopentyl diamine, alkanol amines such as monoethanolamine, diethanolamine), aromatic amines (eg, aniline, tolylene diamine, xiri). 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 condensation obtained by the Mannich reaction of formaldehyde and alkanolamine, or at least one of ethylene oxide and propylene oxide is subjected to ring-opening addition polymerization of this compound. It is a polyether polyol obtained by making it.

Further, from the viewpoint of improving the flame retardancy of the polyurethane foam, the polyol compound preferably contains a polyol having an aromatic ring, and more preferably contains a polyester polyol having an aromatic ring.
From the viewpoint of improving the flame retardancy of the obtained polyurethane foam, the content of the polyol having an aromatic ring is preferably 50 parts by mass or more, and more preferably 80 parts by mass or more out of 100 parts by mass of the polyol compound. It is preferably 100 parts by mass, and more preferably 100 parts by mass.

[Flame retardants]
The polyol composition in the present invention preferably contains a flame retardant from the viewpoint of improving the flame retardancy of the obtained polyurethane foam. The flame retardant is a liquid flame retardant, and it is particularly preferable to contain a phosphoric acid ester-based flame retardant. The phosphoric acid ester flame retardant is a liquid flame retardant, and can improve the flame retardancy of the polyurethane foam, and can appropriately control the viscosity of the polyol composition even when a filler described later is used. .. Here, the liquid flame retardant is a flame retardant that is liquid at 23 ° C.

<Phosphoric acid ester flame retardant>
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 phosphoric acid ester flame retardant is preferably 40 parts by mass or more, more preferably 43 parts by mass or more, and further preferably 45 parts by mass or more with respect to 100 parts by mass of the polyol compound. When the content of the phosphoric acid ester flame retardant is equal to or higher than these lower limit values, the concentration of the polyol compound in the polyol composition decreases. Therefore, the polyol composition and the polyisocyanate composition are separated by a constant volume ratio as described above. When mixed, the isocyanate index tends to increase, and the flame retardancy of the obtained polyurethane foam is improved. The content of the phosphoric acid ester flame retardant is preferably 100 parts by mass or less, and more preferably 80 parts by mass or less with respect to 100 parts by mass of the polyol compound. When the content of the phosphoric acid ester flame retardant is not more than these upper limit values, the concentration of the polyol compound is secured to a certain level or more, and the mechanical strength of the polyurethane foam can be improved.

<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.

As the filler, it is preferable to use 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, boron-based flame retardants, brominated flame retardants, phosphate-containing flame retardants and the like are preferable as fillers from the viewpoint of improving the flame retardancy of the polyurethane foam while improving the sprayability. , Boron flame retardants are more preferred.

(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, and for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and 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, activated 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 20 parts by mass or more, more preferably 25 parts by mass or more, and further preferably 30 parts by mass or more with respect to 100 parts by mass of the polyol compound. If the content of the filler is at least these lower limit values, the concentration of the polyol compound in the polyol composition decreases. Therefore, when the polyol composition and the polyisocyanate composition are mixed at a constant volume ratio as described above, etc. , The isocyanate index tends to increase, and therefore the flame retardancy of the obtained polyurethane foam is improved. Further, when the above-mentioned solid flame retardant is used as the filler, the flame retardancy can be improved by the function of the solid flame retardant itself.
The content of the filler is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and further preferably 50 parts by mass or less with respect to 100 parts by mass of the polyol compound. 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.

[Polyisocyanate compound]
As the polyisocyanate compound contained in the polyisocyanate composition, 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 Cobestrourethane 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.

[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. Therefore, the polyol composition of the present invention preferably contains a trimerization catalyst from the viewpoint of improving the flame retardancy of the polyurethane foam.

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 , Carboxylic acid 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 3 to 20 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. Specific examples thereof include amino compounds, tin compounds, bismuth compounds, and acetylacetone metal salts.
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, and acid blocks thereof. Among the amino compounds, imidazole compounds are preferable.

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 beryllium, 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 improving the foamability when forming the polyurethane foam by spraying the flame-retardant urethane resin composition. The content of the bismuth compound is preferably 0.1 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polyol compound.
Further, as the urethanization catalyst, the combined use of a bismuth compound and an amino compound is preferable, and the combined use of a bismuth compound and an imidazole compound is more preferable.
When the bismuth compound and the amino compound are used in combination, the mass ratio of the amino compound to the bismuth compound (mass of the amino compound / mass of the bismuth compound) is preferably 0.1 to 10, and more preferably 0.3 to 5. It is more preferably 0.5 to 3.

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 8 to 45 parts by mass with respect to 100 parts by mass of the polyol compound.

[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 foaming agent include organic physical foaming agents such as a mixture of these compounds, and inorganic physical foaming 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 1 part by mass.

[Foam control agent]
The polyol composition may contain a defoaming agent. As the defoaming agent, a compound having a polar portion and a non-polar portion in the molecule and having a surface-active effect can be preferably used. Examples of the defoaming agent include silicone defoaming agents such as organopolysiloxane. Further, the silicone foam stabilizer may contain a graft copolymer of polydimethylsiloxane and polyethylene glycol.
The content of the foam stabilizer is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the polyol compound. It is more preferably a part. The foam stabilizer may be used alone or in combination of two or more.

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, as described above, the polyol composition and the polyisocyanate composition are mixed so that the volume ratio (polyisocyanate composition / polyol composition) is 0.8 to 1.2, and the flame-retardant urethane resin is mixed. The composition is prepared.

[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 foam of the present invention is not particularly limited, but when it is divided into two or more, for example, a two-component flame-retardant urethane resin composition, it is prepared by mixing each component in advance. It can be obtained by preparing two or more divided parts such as a polyol composition and a polyisocyanate composition, mixing them, and foaming them. 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. Further, in the case of the one-component type, a method of foaming the flame-retardant urethane resin composition obtained by mixing each component constituting the flame-retardant urethane resin composition by a known method can be mentioned.

(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 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 usually 0.8 to 1.2, and more generally 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>
(I) Polyester polyol / p-phthalic acid-based polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: RLK-087, hydroxyl value 200 mgKOH / g)
-P-Phthalic acid polyester polyol (manufactured by Kawasaki Kasei Co., Ltd., product name: RFK-505, hydroxyl value = 250 mgKOH / g)
(Ii) Polyether polyol / Mannich-based polyether polyol (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., product name: DK3776, hydroxyl value = 350 mgKOH / g)
-Ethylenediamine-based polyether polyol (manufactured by AGC Inc., product name: Exenol 750ED, hydroxyl value = 750 mgKOH / g)

<Catalyst>
(I) Trimerization catalyst: Carboxylic acid quaternary ammonium salt (DABCO TMR-7 manufactured by Evonik Japan Co., Ltd.), concentration 45-55% by mass
(Ii) Triquantization catalyst: 2-ethylhexanoic acid potassium salt (manufactured by Air Products and Chemicals, product name: DABCO K-15), concentration 70 to 80% 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

<Flame retardant>
-Liquid flame retardant Phosphoric acid ester flame retardant Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)
<Filler>
-Filler wollastonite (SiO2 · CaO) (manufactured by Kinsei Matek, product name: SH-1250), solid flame retardant-Filler zinc borate (manufactured by Borax, product name firebrake ZB), solid flame retardant

<Effervescent agent>
-Water-HFO-1233zd <hydrofluoroolefin> (manufactured by Honeywell, product name: Solstice LBA)

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

[Moisture percentage]
The amount of water contained in the polyol composition was measured by a Karl Fischer water measuring device (manufactured by Kyoto Electronics Industry Co., Ltd., product name: MKV-710).

[Flame retardancy evaluation (heat steel ball evaluation)]
For the polyurethane foams produced in each Example and Comparative Example, the subduction distance of the steel ball was measured by the following procedures (1) to (3).
(1) A polyurethane foam was cut into a cube having a side of 50 mm and used as a test body.
(2) A steel ball (SUS304) having a diameter of 10.0 mm and a weight of 4.15 g was placed inside an electric furnace in which the temperature inside the furnace was set to 800 ° C. and heated for 15 minutes.
(3) In an atmosphere of 23 ° C., the steel ball heated in (2) above was immediately placed on the center of the upper part of the test piece of (1) above, and left to stand until the subduction of the steel ball was completed. Then, the cross section of the test piece sufficiently cooled by leaving it at 23 ° C. for 30 minutes was cut, and the subduction distance of the steel ball was measured. The subduction distance of the steel ball means the maximum distance of the cavity in the direction perpendicular to the upper surface of the test piece.

In the evaluation of the hot steel ball, a small program electric furnace (MMF-1) having internal dimensions of 120 mm × 150 mm × 100 mm was used as the electric furnace of (2) above, and SUS304 was used as the steel ball. Further, immediately after heating the steel ball, the steel ball is placed on the test piece. Therefore, the temperature inside the electric furnace (800 ° C.) can be regarded as the temperature of the steel ball when the steel ball is placed on the test piece.
From the subduction distance of the obtained steel balls, the flame retardancy was judged according to the following criteria.
(standard)
〇 ・ ・ The subduction distance of the steel ball was 10 mm or less.
× ... The subduction distance of the steel ball was more than 10 mm.

[Evaluation of spraying device suitability]
When the polyol composition and the polyisocyanate composition produced in each Example and Comparative Example were evaluated by a spraying device, the ease of clogging of the strainer mesh (60 mesh) on the polyol side installed inside the main body device was evaluated. ..
⊚: There is almost no clogging.
○: Slightly clogged, but operational level ×: Highly clogged, machine load is high and cannot be operated

[Examples 1 to 6, Comparative Examples 1 to 2]
According to the formulation shown in Table 1, a polyol composition consisting of a polyol compound, a quantification catalyst, a urethanization catalyst, a flame retardant, a filler and a foaming agent, and a polyisocyanate composition consisting of MDI were prepared, and the respective compositions were sprayed. Introduced in 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). Polyurethane foam was formed by spraying onto gypsum board. The volume ratio of the polyol composition to the polyisonate composition in the flame-retardant urethane resin composition (mixed solution) was 1: 1. The isocyanate index of the flame-retardant urethane resin composition (mixed solution) was as shown in Table 1. The evaluation results are shown in Table 1.

The mass part of each catalyst is the mass part as a product.
The numerical value in parentheses of the polyol compound is the hydroxyl value (mgKOH / g) of each polyol compound.

In each example, the volume ratio of the polyol composition to the polyisocyanate composition is 1: 1, but the isocyanate index of the flame-retardant urethane resin composition is high, and the flame-retardant property of the polyurethane foam formed by spraying is high. It was excellent.
On the other hand, the isocyanate index of the flame-retardant urethane resin composition used in each comparative example was low, and the flame-retardant property of the polyurethane foam was inferior to that of the examples.

Claims (7)

A flame-retardant urethane resin composition which is a mixed solution of a polyol composition containing a polyol compound, a flame-retardant agent, a catalyst, and a foaming agent and a polyisocyanate composition containing a polyisocyanate compound. A flame-retardant urethane resin composition having a volume ratio (polyisocyanate composition / polyol composition) of 0.8 to 1.2 and an isocyanate index of 250 or more. The flame-retardant urethane resin composition according to claim 1, wherein the weighted average hydroxyl value of the polyol compound in the mixed solution is more than 200 mgKOH / g. The flame-retardant urethane resin composition according to claim 1 or 2, wherein the water content of the polyol composition measured by the Karl Fischer method is 2% by mass or less. The flame-retardant urethane resin composition according to any one of claims 1 to 3, further comprising a filler, wherein the content of the filler is 20 parts by mass or more with respect to 100 parts by mass of the polyol compound. The invention according to any one of claims 1 to 4, wherein the flame retardant contains a phosphoric acid ester-based flame retardant, and the content of the phosphoric acid ester-based flame retardant is 40 parts by mass or more with respect to 100 parts by mass of the polyol compound. Flame retardant urethane resin composition. The flame-retardant urethane resin composition according to any one of claims 1 to 5, wherein the catalyst contains a bismuth compound. The flame-retardant urethane resin composition according to any one of claims 1 to 6, which is used for spraying.