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WO2022059566A1 - Composition de polyol, composition de polyuréthane expansible et mousse de polyuréthane - Google Patents

Composition de polyol, composition de polyuréthane expansible et mousse de polyuréthane Download PDF

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Publication number
WO2022059566A1
WO2022059566A1 PCT/JP2021/032890 JP2021032890W WO2022059566A1 WO 2022059566 A1 WO2022059566 A1 WO 2022059566A1 JP 2021032890 W JP2021032890 W JP 2021032890W WO 2022059566 A1 WO2022059566 A1 WO 2022059566A1
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WO
WIPO (PCT)
Prior art keywords
polyol
polyol composition
phosphoric acid
acid ester
phosphate
Prior art date
Application number
PCT/JP2021/032890
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English (en)
Japanese (ja)
Inventor
広晃 名藤
建彦 牛見
Original Assignee
積水化学工業株式会社
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Publication of WO2022059566A1 publication Critical patent/WO2022059566A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products

Definitions

  • the present invention relates to a polyol composition, an effervescent polyurethane composition and a polyurethane foam.
  • Polyurethane foam is used as a heat insulating material for buildings such as condominiums and other condominiums, detached houses, various school facilities, and commercial buildings because of its excellent heat insulating properties and adhesiveness.
  • the polyurethane foam is obtained by foaming an effervescent polyurethane composition containing a polyol composition and a polyisocyanate.
  • the polyol composition generally contains a polyol and a foaming agent, and may further contain a filler such as a flame retardant or an inorganic filler, if necessary. These fillers are blended for the purpose of improving the flame retardancy of the obtained polyurethane foam, coloring, or improving the mechanical strength.
  • Patent Document 1 describes an invention relating to a polyol composition in which a polyol and a specific flame retardant are blended in a certain amount, and is described to be excellent in flame retardancy, low smoke emission and the like.
  • a method for constructing a polyurethane foam for example, as described in Patent Document 2, a method such as mixing a polyol composition and a polyisocyanate, reacting them, foaming them, and spraying them at a construction site may be used. Taken. Therefore, the polyol composition and the polyisocyanate are mixed immediately before construction.
  • the filler will settle over time during storage. Therefore, it is necessary to stir the polyol composition to disperse the filler before mixing it with polyisocyanate to produce a polyurethane foam.
  • problems in terms of operability and safety such as the liquid boiling up and overflowing from the container due to the foaming agent contained in the polyol composition during stirring.
  • the problem of liquid boiling rapid rise in liquid level
  • an odor may be generated when the polyurethane foam is formed, which may cause a problem in the working environment.
  • the present invention provides a polyol composition containing a polyol, a foaming agent, and a filler, which can suppress boiling during stirring and can suppress the generation of odor during the formation of polyurethane foam. Make it an issue.
  • the gist of the present invention is the following [1] to [9].
  • a polyol composition for on-site spraying which comprises a polyol, a foaming agent, a filler, a catalyst, and a phosphoric acid ester compound.
  • the foaming agent contains a hydrofluoroolefin having a boiling point of 40 ° C. or lower.
  • the phosphoric acid ester compound contains at least one selected from a condensed phosphoric acid ester and a monophosphoric acid ester.
  • a polyol composition which can suppress the boiling of the liquid at the time of stirring when dispersing the filler and also can suppress the odor at the time of spraying on site. be able to.
  • the polyol composition of the present invention contains a polyol, a foaming agent, a filler, a catalyst, and a phosphate ester compound.
  • the polyol composition of the present invention is characterized by containing a phosphoric acid ester compound.
  • the solubility of the foaming agent in the polyol is improved, so that it becomes easy to suppress the boiling of the liquid during stirring. That is, the phosphoric acid ester compound has a function as a compatibilizer between the polyol and the foaming agent.
  • the odor when forming the polyurethane foam can be suppressed. As a result, bad odor can be suppressed during the on-site spraying work, and the working environment becomes good.
  • the flame retardancy of the polyurethane foam can be improved by blending the phosphoric acid ester compound.
  • Examples of the phosphoric acid ester compound include monophosphoric acid ester and condensed phosphoric acid ester.
  • the monophosphate ester is a phosphate ester having one phosphorus atom in the molecule.
  • Examples of the monophosphate ester include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate and tri (2-ethylhexyl) phosphate, halogen-containing phosphate esters such as tris ( ⁇ -chloropropyl) phosphate, and tributoxyethyl phosphate.
  • Arocyclic-containing phosphates such as trialkoxy phosphate, tricresyl phosphate, trixilenyl phosphate, tris (isopropylphenyl) phosphate, cresyldiphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, monoisodecyl phosphate, diisodecyl
  • acidic phosphoric acid esters such as phosphate.
  • a phosphite ester or the like may be used in addition to the above.
  • phosphite ester examples include triphenylphosphine, tricresylphosphine, trisnonylphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite and the like.
  • One type of monophosphate ester may be used alone, or two or more types may be used in combination.
  • condensed phosphate ester examples include aromatic condensed phosphate esters such as trialkylpolyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate.
  • aromatic condensed phosphate esters such as trialkylpolyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, and bisphenol A polyphenyl phosphate.
  • One type of condensed phosphoric acid ester may be used alone, or two or more types may be used in combination. Further, the condensed phosphoric acid ester and the monophosphoric acid ester may be used in combination.
  • the phosphoric acid ester compound it is preferable to include a phosphoric acid ester compound containing no chlorine in the structure from the viewpoint of easily suppressing boiling during stirring and reducing the environmental load. Further, from the viewpoint of easily suppressing boiling during stirring and suppressing the odor during spraying work, it is preferable to include a phosphoric acid ester compound containing no aromatic ring in the structure.
  • trialkyl phosphate is preferable from the viewpoint of easily suppressing boiling during stirring and easily suppressing odor during work.
  • at least one of the phosphate ester compounds selected from trimethyl phosphate and triethyl phosphate is preferable.
  • the halogen-containing phosphoric acid ester tris ( ⁇ -chloropropyl) phosphate is preferable.
  • trialkyl phosphate and a halogen-containing phosphoric acid ester in combination. Therefore, as the phosphoric acid ester, it is more preferable to use tris ( ⁇ -chloropropyl) phosphate in combination with at least one selected from trimethyl phosphate and triethyl phosphate.
  • the polyol composition of the present invention may contain a compatibilizer other than the phosphoric acid ester, but from the viewpoint of preventing malodor, the content of the phosphoric acid ester compound with respect to the total amount of the compatibilizer is preferably 50% by mass or more. It is more preferably 80% by mass or more, and further preferably 100% by mass. Therefore, it is more preferable not to contain a compatibilizer other than the phosphoric acid ester.
  • the compatibilizer other than the phosphoric acid ester examples include ester compounds other than the phosphoric acid ester compound (hereinafter, also referred to as non-phosphate ester compound).
  • ester compounds other than the phosphoric acid ester compound hereinafter, also referred to as non-phosphate ester compound.
  • low molecular weight alcohols such as dipropylene glycol and the like.
  • a carboxylic acid compound such as 2-ethylhexanoic acid, an imidazole compound having an imidazole ring, and the like can also be used.
  • the small molecule alcohol means an alcohol having a molecular weight of 200 or less.
  • non-phosphate ester compound examples include chain ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate and ethylene glycol acetate, ⁇ -acetlactone, ⁇ -propion lactone and ⁇ .
  • chain ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate and ethylene glycol acetate, ⁇ -acetlactone, ⁇ -propion lactone and ⁇ .
  • cyclic ester compounds such as-butyrolactone and ⁇ -valerolactone.
  • the content of the phosphoric acid ester in the polyol composition of the present invention is not particularly limited, but is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and further preferably 40 parts by mass or more with respect to 100 parts by mass of the polyol. Yes, and preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less.
  • the content of the phosphoric acid ester is at least these lower limit values, it becomes easy to suppress boiling during stirring, and odor can be suppressed. Further, when it is not more than the upper limit value, the decrease in the mechanical strength of the polyurethane foam can be suppressed.
  • the polyol composition of the present invention contains a polyol as a raw material for polyurethane foam.
  • the polyol used in the present invention is not particularly limited, and examples thereof include polylactone polyols, polycarbonate polyols, polyester polyols, polyether polyols, and polymer polyols.
  • polylactone polyol examples include polypropiolactone glycol, polycaprolactone glycol, polyvalerolactone glycol and the like.
  • polycarbonate polyol examples include a polyol obtained by a dealcohol reaction between a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butane diol, pentan diol, hexane diol, octane diol, and nonane diol and ethylene carbonate, propylene carbonate, or the like. And so on.
  • polyester polyol for example, a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, a polymer obtained by ring-opening polymerization of a lactone such as ⁇ -caprolactone and ⁇ -methyl- ⁇ -caprolactone. , And a condensate of hydroxycarboxylic acid and the polyhydric alcohol or the like.
  • the polybasic acid include adipic acid, azelaic acid, sebacic acid, isophthalic acid (m-phthalic acid), terephthalic acid (p-phthalic acid), succinic acid and the like.
  • polyhydric alcohol examples include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexaneglycol, neopentyl glycol and the like.
  • hydroxycarboxylic acid examples include castor oil, a reaction product of castor oil and ethylene glycol, and the like.
  • the polyether polymer for example, at least one kind of alkylene oxide such as ethylene oxide, propylene oxide and tetrahydrofuran is ring-opened in the presence of at least one kind such as a low molecular weight active hydrogen compound having two or more active hydrogens.
  • a low molecular weight active hydrogen compound having two or more active hydrogens examples include a polymer obtained by polymerization.
  • the low molecular weight active hydrogen compound having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol and 1,6-hexanediol, and triols such as glycerin and trimethylolpropane. , Ethylenediamine, amines such as butylene diamine, and the like.
  • polymer polyol examples include a polymer obtained by graft-polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate with an aromatic polyol, an alicyclic polyol, an aliphatic polyol, a polyester polyol, or the like. , Polybutadiene polyols, modified polyols of polyhydric alcohols, hydrogenated additives thereof and the like.
  • aromatic polyol used for producing the polymer polyol include bisphenol A, bisphenol F, phenol novolak, and cresol novolak.
  • Examples of the alicyclic polyol used for producing the polymer polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.
  • Examples of the aliphatic polyol used for producing the polymer polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.
  • modified polyol of the polyhydric alcohol examples include those modified by reacting the polyhydric alcohol as a raw material with an alkylene oxide.
  • polyhydric alcohol examples include trihydric alcohols such as glycerin and trimethylolpropane, pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol and the like, sucrose, glucose, mannose, fructose, methylglucoside and the like.
  • Tetra-octavalent alcohols such as its derivatives, fluoroglucolsinol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, and 1,4. , 5,8-Tetrahydroxyanthracene and other polyols, castor oil polyol, hydroxyalkyl (meth) acrylate (co) polymer and polyfunctional (eg, functional group number 2-100) polyols such as polyvinyl alcohol, condensation of phenol and formaldehyde. Things (Novolak) can be mentioned.
  • the method for modifying the polyhydric alcohol is not particularly limited, but a method for adding an alkylene oxide (hereinafter, also referred to as “AO”) is preferably used.
  • AO alkylene oxide
  • examples of AO include AOs having 2 to 6 carbon atoms, for example, ethylene oxide (hereinafter, also referred to as “EO”), 1,2-propylene oxide (hereinafter, also referred to as “PO”), 1,3-propyleneoxide, and the like.
  • Examples thereof include 1,2-butylene oxide and 1,4-butylene oxide.
  • PO, EO and 1,2-butylene oxide are preferable, and PO and EO are more preferable, from the viewpoint of properties and reactivity.
  • the addition method may be block addition, random addition, or a combination thereof.
  • the polyol used in the present invention is preferably at least one selected from the group consisting of polyester polyols and polyether polyols. Further, a polyol having two hydroxyl groups is preferable.
  • aromatic polyester polyols which are polyester polyols having an aromatic ring, are preferable from the viewpoint of enhancing flame retardancy.
  • the aromatic polyester polyol include polybasic acids having an aromatic ring such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid), bisphenol A, ethylene glycol, 1,2-propylene glycol and the like. The one obtained by dehydration condensation with the dihydric alcohol of No. 1 is more preferable.
  • the weight average molecular weight of the polyol is preferably more than 300, more preferably 400 or more, still more preferably 430 or more, and preferably 20,000 or less, more preferably 10,000 or less.
  • the weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).
  • the hydroxyl value of the polyol is preferably 20 to 300 mgKOH / g, more preferably 40 to 280 mgKOH / g, even more preferably 100 to 250 mgKOH / g, and particularly preferably 120 to 210 mgKOH / g.
  • the hydroxyl value of the polyol is not more than the upper limit, it is easy to suppress boiling of the polyol composition during stirring, and the viscosity of the polyol composition is likely to decrease, which is preferable from the viewpoint of handleability and the like.
  • the hydroxyl value of the polyol is at least the above lower limit value, the crosslink density of the polyurethane foam is increased and the strength is increased.
  • the hydroxyl value of the polyol can be measured according to JIS K 1557-1: 2007.
  • the content of the polyol in the polyol composition of the present invention is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and further preferably 30 to 50% by mass.
  • the content of the polyol is at least the above lower limit value, the polyol and the polyisocyanate are likely to react with each other, which is preferable.
  • the content of the polyol is not more than the upper limit, the viscosity of the polyol composition does not become too high, which is preferable from the viewpoint of handleability.
  • the polyol composition of the present invention contains a foaming agent.
  • a polyurethane foam can be obtained by foaming a polyol composition containing the foaming agent and a foamable polyurethane composition containing a polyisocyanate.
  • the foaming agent preferably contains a foaming agent having a boiling point of 40 ° C. or lower (hereinafter, also referred to as a low boiling point foaming agent) from the viewpoint of improving the foamability when forming the polyurethane foam.
  • the boiling point of the low boiling point foaming agent is more preferably 20 ° C. or lower.
  • the boiling point means the boiling point at 1 atm.
  • the content of the low boiling point foaming agent in the foaming agent is preferably 50% by mass or more, more preferably 80% by mass or more, and further preferably 100% by mass based on the total amount of the foaming agent.
  • the foaming agent is not particularly limited, but preferably contains a fluorocarbon-based foaming agent such as a fluorine compound, hydrochlorofluorocarbon, hydrofluorocarbon, and hydrofluoroolefin.
  • a fluorocarbon-based foaming agent such as a fluorine compound, hydrochlorofluorocarbon, hydrofluorocarbon, and hydrofluoroolefin.
  • the foaming agent contains a hydrofluoroolefin (hereinafter, may be referred to as “HFO”) because the foaming agent has high stability, the catalytic activity does not easily decrease, and the environmental load is also low. Is more preferable, and it is further preferable that it consists of only a hydrofluoroolefin.
  • the HFO which is a suitable foaming agent is not particularly limited as long as it has a boiling point of 40 ° C. or lower, and examples thereof include fluoroalkenes having about 3 to 6 carbon atoms. Further, the HFO may be a hydrochlorofluoroolefin having a chlorine atom, and therefore may be a chlorofluoroalkene having about 3 to 6 carbon atoms.
  • HFOs having a boiling point of 40 ° C. or lower examples include trifluoropropene, tetrafluoropropene such as HFO-1234, pentafluoropropene such as HFO-1225, chlorodifluoropropene, chlorotrifluoropropene such as HFO-1233, and chloro.
  • examples thereof include tetrafluoropropene. More specifically, 3,3,3-trifluoropropene (HFO-1243zf, boiling point: -18 ° C.), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E), boiling point: -18 ° C.).
  • HFO-1234ze Z
  • boiling point 10 ° C.
  • 2,3,3,3-tetrafluoropropene HFO-1234yf, boiling point: 10 ° C.) ⁇ 29 ° C.
  • 1,1,3,3-tetrafluoropropene boiling point: 4 ° C.
  • trans-1,2,3,3,3-pentafluoropropene HFO-1225ye (E), boiling point: -10).
  • HFO-1225ye (Z) cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye (Z), boiling point: -19 ° C.), 1,1,3,3,3-pentafluoropropene (HFO-1225zc).
  • HFO-1233zd (E), HFO-1336mzz (z), and HFO-1224yd (Z) are preferable, and HFO-1233zd (E) is more preferable.
  • HFOs may be used alone or in combination of two or more.
  • the lower limit of the boiling point of HFO is not particularly limited, but is preferably 0 ° C. or higher from the viewpoint of easy handling. Therefore, the HFO according to the present invention preferably has a boiling point of 0 to 40 ° C. Further, the boiling point of the HFO is more preferably in the range of 10 to 20 ° C. from the viewpoint of suppressing boiling of the polyol composition and having good handleability.
  • the content of the fluorocarbon-based foaming agent contained in the foaming agent is preferably 80% by mass or more, more preferably 95% by mass or more, and preferably 100% by mass with respect to the total amount of foaming agent. More preferred.
  • the polyol composition of the present invention may contain a foaming agent other than the chlorofluorocarbon-based foaming agent.
  • the foaming agent other than the chlorofluorocarbon-based foaming agent include water, nitrogen gas, oxygen gas, argon gas, carbon dioxide gas and the like. Among these, water, oxygen gas, and carbon dioxide gas are preferable from the viewpoint of handleability, and water is more preferable from the viewpoint of adjusting the isocyanate index and from the viewpoint of ease of handling.
  • the content of the foaming agent other than the chlorofluorocarbon-based foaming agent contained in the foaming agent is preferably 20% by mass or less, more preferably 5% by mass or less, based on the total amount of the foaming agent.
  • the blending amount of the foaming agent is preferably 10 to 80 parts by mass, more preferably 15 to 70 parts by mass, and even more preferably 20 to 60 parts by mass with respect to 100 parts by mass of the polyol.
  • the blending amount of the foaming agent is at least the above lower limit value, foaming is promoted, foamability is improved, and the density of the obtained polyurethane foam can be reduced.
  • the blending amount of the foaming agent is not more than the upper limit value, it is possible to suppress excessive progress of foaming.
  • the polyol composition of the present invention contains a filler.
  • the polyurethane foam can be imparted with properties according to the type of the filler, and for example, flame retardancy, mechanical strength can be improved, and coloring can be performed.
  • the filler include flame retardants, inorganic fillers other than flame retardants, and the like.
  • the polyol composition of the present invention may contain a flame retardant as a filler.
  • a flame retardant By containing the flame retardant, the flame retardancy of the formed polyurethane foam can be effectively enhanced.
  • the flame retardant include red phosphorus flame retardants, phosphate-containing flame retardants, bromine-containing flame retardants, chlorine-containing flame retardants, antimony-containing flame retardants, boron-containing flame retardants, and solid flame retardants such as metal hydroxides. Be done.
  • the red phosphorus flame retardant may be composed of red phosphorus alone, may be a red phosphorus coated with a resin, a metal hydroxide, a metal oxide, or the like, or may be a red phosphorus coated with a resin, a metal hydroxide, or a metal. It may be a mixture of oxides and the like.
  • the resin coated with red phosphorus or mixed with red phosphorus is not particularly limited, and examples thereof include thermosetting resins such as phenol resin, epoxy resin, unsaturated polyester resin, melamine resin, urea resin, aniline resin, and silicone resin. Be done.
  • a metal hydroxide is preferable from the viewpoint of flame retardancy.
  • the metal hydroxide those described later may be appropriately selected and used.
  • the phosphate-containing flame retardant is selected from, for example, various phosphoric acids, metals of the Group IA to IVB of the Periodic Table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring. Included are phosphates consisting of salts with at least one metal or compound.
  • the phosphoric acid is not particularly limited, and examples thereof include monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid.
  • Examples of the metal of Group IA to 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.
  • Examples of the aromatic amine include aniline, o-triidin, 2,4,6-trimethylaniline, anicidin, 3- (trifluoromethyl) aniline and the like.
  • Examples of the heterocyclic compound containing nitrogen in the ring include pyridine, triazine, melamine and the like.
  • the phosphate-containing flame retardant include monophosphate, polyphosphate and the like.
  • the monophosphate is not particularly limited, but for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, and phosphite.
  • Sodium salts such as monosodium, disodium phosphite, sodium hypophosphite, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, hypophosphite
  • Potassium salts such as potassium, monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphate, dilithium phosphate, lithium salts such as lithium hypophosphite, barium dihydrogen phosphate, phosphorus
  • 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, calcium dihydrogen phosphate , Calcium hydrogen phosphate, tricalcium phosphate, calcium salts such as calcium hypophosphite,
  • the polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate, aluminum polyphosphate, and the like.
  • the phosphate-containing flame retardant may be used alone from the above-mentioned ones, or may be used in combination of two or more.
  • the brominated flame retardant is not particularly limited as long as it is a compound containing bromine in its molecular structure and becomes solid at normal temperature and pressure, and examples thereof include brominated aromatic ring-containing aromatic compounds.
  • examples of the brominated aromatic ring-containing aromatic compound include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, and ethylenebis (pentabromophenoxy).
  • Examples thereof include monomer-based organic bromine compounds such as pentabromophenyl), ethylene bis (tetrabromophthalimide), and tetrabromobisphenol A.
  • the brominated aromatic ring-containing aromatic compound may be a bromine compound polymer.
  • a polycarbonate oligomer produced from brominated bisphenol A as a raw material a brominated polycarbonate such as a copolymer of this polycarbonate oligomer and bisphenol A, and a diepoxy compound produced by the reaction of brominated bisphenol A with epichlorohydrin.
  • brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin, poly (bromineed benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, and brominated phenol of cyanur chloride.
  • chlorine-containing flame retardant examples include those commonly used in flame-retardant resin compositions, for example, polynaphthalene chloride, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclo sold under the trade name of "Dechloran Plus". Octene and the like can be mentioned.
  • antimony-containing flame retardant examples include antimony oxide, antimony acid salt, pyroantimony acid salt and the like.
  • antimony oxide examples include antimony trioxide and antimony pentoxide.
  • antimonate examples include sodium antimonate, potassium antimonate and the like.
  • pyroantimonate examples include sodium pyroantimonate, potassium pyroantimonate and the like.
  • the antimony-containing flame retardant may be used alone or in combination of two or more.
  • boron-containing flame retardant examples include borax, boron oxide, boric acid, borate and the like.
  • examples of the boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, tetraboron pentoxide and the like.
  • Examples of the borate include alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the Periodic Table, and ammonium borates.
  • an alkali metal borate salt such as lithium borate, sodium borate, potassium borate, and cesium borate
  • an alkaline earth metal salt borate such as magnesium borate, calcium borate, and barium borate
  • boro Examples thereof include zirconium acid, zinc borate, aluminum borate, and ammonium borate.
  • the boron-containing flame retardant may be used alone or in combination of two or more.
  • Metal hydroxide examples include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, zinc hydroxide, copper hydroxide, vanadium hydroxide, and water. Examples include tin oxide.
  • the metal hydroxide may be used alone or in combination of two or more.
  • the polyol composition of the present invention may contain an inorganic filler other than the above-mentioned flame retardant as a filler.
  • Inorganic fillers 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, graphite fiber, metal.
  • Needle-shaped fillers such as fibers, slag fibers, gypsum fibers, silica fibers, alumina fibers, silica alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, stainless steel fibers, carbon black, alumina, titanium oxide, calcium oxide, magnesium oxide, Iron oxide, tin oxide, antimony 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, Bentnite, Activated clay, Sebiolite, Imogolite, Celicite, Glass beads, Silica balun, Aluminum nitride, Boron nitride, Silicon nitride, Graphite, Carbon balun, Charcoal powder, Various metal powders, Potassium titanate, Magnesium
  • the inorganic filler is a solid component that becomes solid at normal temperature and pressure.
  • needle-like fillers typified by silicon-based needle-like fillers such as wollastonite, carbon black, calcium carbonate and the like are preferable.
  • the inorganic filler may be used alone or in combination of two or more.
  • the content of the filler in the polyol composition is not particularly limited, but is preferably 1 to 150 parts by mass, more preferably 10 to 120 parts by mass, and further preferably 30 to 80 parts by mass with respect to 100 parts by mass of the polyol. ..
  • the polyol composition of the present invention preferably contains a catalyst from the viewpoint of promoting the reaction between the polyol and the polyisocyanate and improving the flame retardancy of the polyurethane foam to be formed.
  • the catalyst contains a trimerization catalyst, a urethanization catalyst, and the like, and it is also preferable that the catalyst contains both a trimerization catalyst and a urethanization catalyst.
  • trimerization catalyst is a catalyst that promotes the formation of an isocyanurate ring by reacting an isocyanate group contained in a polyisocyanate, which will be described later, with a trimerization.
  • 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, A quaternary ammonium salt such as a tetraphenylammonium salt or a triethylmonomethylammonium salt can be used.
  • ammonium salts examples include ammonium salts of carboxylic acids such as 2,2-dimethylpropanoic acid, and more specifically, quaternary ammonium salts of carboxylic acid. These may be used alone or in combination of two or more. Among these, one or more selected from carboxylic acid alkali metal salt and carboxylic acid quaternary ammonium salt is preferable, and an embodiment using both of them is also preferable.
  • the blending amount of the trimerization catalyst is preferably 0.1 to 25 parts by mass, more preferably 0.3 to 20 parts by mass, still more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the polyol.
  • trimerization of polyisocyanate is likely to occur, and the flame retardancy of the obtained polyurethane foam is improved.
  • the blending amount of the trimerization catalyst is not more than the upper limit value, the reaction can be easily controlled.
  • the urethanization catalyst is a catalyst that promotes the reaction between the polyol and polyisocyanate.
  • the urethanization catalyst include amine-based catalysts such as imidazole compounds and piperazine compounds, and metal-based catalysts.
  • the imidazole compound include a tertiary amine in which the secondary amine at the 1-position of the imidazole ring is replaced with an alkyl group, an alkenyl group or the like.
  • N-methylimidazole 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methyl.
  • imidazole Further, an imidazole compound in which the secondary amine in the imidazole ring is substituted with a cyanoethyl group may be used.
  • the piperazine compound include tertiary amines such as N-methyl-N'N'-dimethylaminoethylpiperazine and trimethylaminoethylpiperazine.
  • amine-based catalysts include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinbis (2-dimethylaminoethyl) ether, N, N, N', N ", N"-.
  • Various tertiary amines such as tripropylamine and the like.
  • the metal-based catalyst examples include metal salts composed of lead, tin, bismuth, copper, zinc, cobalt, nickel and the like, and preferably organic acid metal salts composed of lead, tin, bismuth, copper, zinc, cobalt, nickel and the like. Is. More preferably, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin versatetate, bismuth trioctate, bismuth tris (2-ethylhexanoate), tin dioctylate, lead dioctylate and the like are mentioned, and among them, the organic acid bismuth salt is further preferable. ..
  • the urethanization catalyst may be used alone or in combination of two or more. Further, among the above, it is preferable to use one or more selected from the imidazole compound and the organic acid bismuth salt, and it is also preferable to use both of them.
  • the blending amount of the urethanization catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, still more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polyol.
  • the blending amount of the resinification catalyst is at least these lower limit values, urethane bonds are likely to be formed, and the reaction proceeds rapidly. On the other hand, when it is not more than these upper limit values, it becomes easy to control the reaction rate.
  • the total amount of the catalyst in the polyol composition is not particularly limited, but is preferably 0.2 to 30 parts by mass, more preferably 0.6 to 20 parts by mass, and further preferably 1 to 10 parts by mass.
  • the total amount of the catalyst in the polyol composition is not particularly limited, but is preferably 0.2 to 30 parts by mass, more preferably 0.6 to 20 parts by mass, and further preferably 1 to 10 parts by mass.
  • the polyol composition of the present invention may contain a defoaming agent.
  • the defoaming agent improves the foamability of the effervescent polyurethane composition containing the polyol composition and the polyisocyanate.
  • the defoaming agent include a polyoxyalkylene-based defoaming agent such as polyoxyalkylene alkyl ether and a surfactant such as a silicone-based defoaming agent such as organopolysiloxane. These defoaming agents may be used alone or in combination of two or more.
  • the blending amount of the foam stabilizer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, still more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the polyol compound.
  • the blending amount of the defoaming agent is not less than these lower limit values, it becomes easy to foam the polyurethane composition, and it becomes easy to obtain a homogeneous polyurethane foam. Further, when the blending amount of the defoaming agent is not more than these upper limit values, the balance between the manufacturing cost and the obtained effect becomes good.
  • the polyol composition may be a phenol-based, amine-based, sulfur-based or other antioxidant, heat stabilizer, metal damage inhibitor, antistatic agent, stabilizer, or cross-linking, if necessary, as long as the object of the present invention is not impaired. It can contain one or more selected from agents, lubricants, softeners, pigments and the like.
  • the method for producing the polyol composition of the present invention is not particularly limited, and for example, each component can be produced by stirring at about 20 to 40 ° C. using a homodisper or the like for about 30 seconds to 20 minutes.
  • the effervescent polyurethane composition of the present invention contains the polyol composition of the present invention and polyisocyanate, and is obtained by mixing these.
  • the polyurethane foam of the present invention comprises a foamable polyurethane composition, specifically, a reaction product obtained by reacting and foaming a foamable polyurethane composition.
  • polyisocyanate examples include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.
  • aromatic polyisocyanate examples include phenylenediocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate.
  • alicyclic polyisocyanate examples include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.
  • aliphatic polyisocyanate examples include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate and the like.
  • aromatic polyisocyanates are preferable, and diphenylmethane diisocyanates are more preferable, from the viewpoint of ease of use and availability.
  • the polyisocyanate one type may be used alone, or two or more types may be mixed and used. Further, the polyisocyanate may be appropriately blended with a known additive to be blended with the polyisocyanate before being mixed with the polyol composition.
  • the isocyanate index of the effervescent polyurethane composition of the present invention is not particularly limited, but is preferably 150 or more.
  • the isocyanate index is at least the above lower limit value, the amount of polyisocyanate with respect to the polyol becomes excessive, and isocyanurate bonds are easily generated by the trimeric body of polyisocyanate, and as a result, the flame retardancy of the polyurethane foam is improved.
  • the isocyanate index is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more.
  • the isocyanate index is preferably 800 or less, more preferably 600 or less, and even more preferably 400 or less.
  • Equivalent number of water molecular weight of water (g) / molecular weight of water (mol) x number of OH groups of water
  • the molecular weight of NCO is 42 (mol) and the molecular weight of KOH is 56,100 (mmol).
  • the molecular weight of water is 18 (mol)
  • the number of OH groups in water is 2.
  • the polyol composition of the present invention is used for in-situ spraying.
  • the polyol composition may be mixed with the polyisocyanate at the work site, and the mixture may be sprayed onto the spray target surface to form a polyurethane foam on the spray target surface.
  • the polyol composition filled in a container or the like brought to the work site and the isocyanate filled in the container or the like are sent to a foaming machine, and the polyol composition and isocyanate are mixed by the foaming machine. May be mixed and the mixture (foamable polyurethane composition) may be sprayed onto the surface to be sprayed.
  • the spraying may be performed by a spray gun attached to the foaming machine or the like.
  • the surface to be sprayed is not particularly limited, but a building such as a wall, ceiling, roof, or floor of the building is suitable.
  • the polyol composition filled in a container or the like may be stirred at the work site before being mixed with isocyanate.
  • the boiling of the liquid during stirring of the polyol composition can be suppressed, it is possible to prevent the polyol composition from overflowing from the container even when the outside air temperature is relatively high in summer or the like. Further, by using the phosphoric acid ester compound as a phase solvent, it is possible to prevent the generation of a foul odor even when the polyol composition is stirred at the construction site, sent into liquid, and further mixed with polyisocyanate.
  • the height of the highest point after stirring was measured, and the difference from the height before stirring was calculated and evaluated as the boiling height.
  • the height of the highest point after stirring means the height from the bottom surface of the screw pipe to the highest point of the liquid (polypoly composition), and the height before stirring means the height from the bottom surface of the screw pipe to the liquid (polyol composition).
  • Object It means the height to the surface.
  • a polyol composition (total 300 g) is prepared by mixing and stirring from the components described in each Example and Comparative Example, and the polyol composition immediately after preparation is smelled from a distance of 15 cm in height for 5 seconds, and the stink felt is 6 levels. Evaluation was made based on the odor intensity display method. The evaluation criteria and judgment were as follows. (Evaluation criteria) 0 ... Odorless 1 ... Smell that can be finally detected (detection threshold) 2 ... A weak odor that tells you what the odor is (cognitive threshold) 3 ... Smell that can be easily perceived 4 ... Strong odor 5 ... Strong odor (judgment) A ... 3 or less B ... 4 or more
  • Table 1 shows the polyols, fillers, foaming agents, phosphoric acid esters, urethanization catalysts, and foam stabilizers used in each Example and Comparative Example.
  • the compatibilizer used in place of the phosphoric acid ester is described as another compatibilizer.
  • the polyol, filler, foaming agent, phosphoric acid ester (other compatibilizer), urethanization catalyst, and defoaming agent are mixed in the blending amounts shown in Table 2 to obtain a polyol composition, which has the above-mentioned boiling height and boiling height. The odor was evaluated. The results are shown in Table 2.
  • the polyol composition of the present invention containing a polyol, a foaming agent, a filler, a catalyst, and a phosphoric acid ester has a low boiling height at the time of stirring, and is suitable for operability and safety. It turned out to be excellent. It was also found that the odor intensity was low and good results were obtained in the odor evaluation. On the other hand, as shown in Comparative Example 1, it was found that the polyol composition containing no phosphoric acid ester and compatibilizer had a high boiling height at the time of stirring and was inferior in operability and safety. Further, as shown in Comparative Examples 2 and 3, it was found that the polyol composition using a compatibilizer other than the phosphoric acid ester had a strong malodor and was unsuitable for use for spraying in the field.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette composition de polyol pour pulvérisation sur site contient un polyol, un agent moussant, une charge, un catalyseur et un composé de phosphate.　L'invention concerne une composition de polyol qui peut supprimer le phénomène d'ébullition d'un liquide pendant l'agitation lors de la dispersion d'une charge, et peut supprimer l'apparition d'une odeur lors de la formation d'une mousse de polyuréthane.
PCT/JP2021/032890 2020-09-18 2021-09-07 Composition de polyol, composition de polyuréthane expansible et mousse de polyuréthane WO2022059566A1 (fr)

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JP2016145360A (ja) * 2010-08-18 2016-08-12 ハネウェル・インターナショナル・インコーポレーテッド 発泡剤、発泡性組成物、及びフォーム
JP2018080328A (ja) * 2016-11-04 2018-05-24 積水化学工業株式会社 現場吹き付け用発泡性ポリウレタン組成物
JP2018188597A (ja) * 2017-05-11 2018-11-29 積水化学工業株式会社 輸送機器内装材用難燃性ウレタン樹脂組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016145360A (ja) * 2010-08-18 2016-08-12 ハネウェル・インターナショナル・インコーポレーテッド 発泡剤、発泡性組成物、及びフォーム
JP2018080328A (ja) * 2016-11-04 2018-05-24 積水化学工業株式会社 現場吹き付け用発泡性ポリウレタン組成物
JP2018188597A (ja) * 2017-05-11 2018-11-29 積水化学工業株式会社 輸送機器内装材用難燃性ウレタン樹脂組成物

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