WO2021193872A1 - ポリオール組成物を封入した容器、ポリウレタン組成物、及びポリウレタン発泡体 - Google Patents

ポリオール組成物を封入した容器、ポリウレタン組成物、及びポリウレタン発泡体 Download PDF

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WO2021193872A1
WO2021193872A1 PCT/JP2021/012726 JP2021012726W WO2021193872A1 WO 2021193872 A1 WO2021193872 A1 WO 2021193872A1 JP 2021012726 W JP2021012726 W JP 2021012726W WO 2021193872 A1 WO2021193872 A1 WO 2021193872A1
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container
composition
polyol
polyol composition
compound
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PCT/JP2021/012726
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English (en)
French (fr)
Japanese (ja)
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悠 柿本
倫生 梶田
建彦 牛見
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積水化学工業株式会社
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Priority to JP2021520620A priority Critical patent/JPWO2021193872A1/ja
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    • 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

Definitions

  • the present invention relates to a container containing a polyol composition, a polyurethane composition comprising a polyol composition discharged from the container and a polyisocyanate composition, and a polyurethane foam formed from the polyurethane composition.
  • polyurethane foam has been used as a heat insulating material in vehicles such as automobiles, railroad vehicles, and ships, and buildings.
  • polyurethane foam a two-component polyurethane in which a polyol composition and a polyisocyanate composition packed in separate containers are mixed to form a foam is widely used.
  • Two-component polyurethane may be used in an aerosol container because each liquid can be discharged from a container and mixed with a relatively simple structure.
  • one container is filled with a polyol compound and a low boiling point compound
  • the other container is filled with a polyisocyanate compound and a low boiling point compound.
  • a polyurethane foam is formed by discharging a polyol solution and a polyisocyanate solution from each container by the vapor pressure of a low boiling point compound and mixing them.
  • Patent Document 1 describes a two-component aerosol composition for rigid polyurethane foam containing a specific amount of a low boiling point compound, and liquefied petroleum gas (LPG), dimethyl ether (DME), or the like is used as the low boiling point compound. It is stated that this does not adversely affect global warming.
  • the polyurethane foam formed by the above-mentioned conventional two-component aerosol composition tends to shrink easily, and there is room for improvement from the viewpoint of shape stability.
  • a filler to the polyol composition.
  • the amount of the polyol composition discharged from the aerosol container is insufficient, the mixing efficiency of the composition is lowered, the workability is deteriorated, and other problems occur.
  • the present invention is a container containing a polyol composition, which can easily discharge the content polyol composition and can produce a polyurethane foam having a low shrinkage rate, and is discharged from the container. It is an object of the present invention to provide a polyurethane composition comprising a polyol composition, and a polyurethane foam formed from the polyurethane composition.
  • the present inventors have made a polyol composition containing a polyol compound, a filler, a catalyst, and a low boiling point compound, and using a container containing the polyol composition having a low boiling point compound ratio in a certain range. , And found that the above-mentioned problems can be solved, and completed the following invention. That is, the present invention provides the following [1] to [8].
  • C Weight of the container after discharging the polyol composition
  • C Weight after drying the discharged product discharged for 10 seconds at 40 ° C.
  • the filler ratio calculated by the following formula (2) of the polyol composition is 5 to 80%, the above [1].
  • the container described in. Formula (2) Filler ratio (%) (E / D) x 100 D: After keeping the container warm at 35 ° C., the discharge product obtained by discharging the polyol composition from the container in a uniformly mixed state for 10 seconds is dried at 40 ° C. for 30 minutes, and then the weight E: D. The discharged product after drying was diluted with acetone and suction-filtered, and the weight of the obtained agglomerates [3]. Described container. [4] The container according to any one of the above [1] to [3], which is an aerosol container.
  • a polyurethane composition comprising a polyol composition discharged from the container according to any one of the above [1] to [4] and a polyisocyanate composition containing a polyisocyanate compound.
  • the polyurethane composition according to the above [5] which has an isocyanate index of 200 to 1000.
  • the polyurethane foam according to the above [7] which has a shrinkage rate of less than 20%.
  • a container containing a polyol composition which can easily discharge the content polyol composition and can produce a polyurethane foam having a low shrinkage rate, and is discharged from the container.
  • a polyurethane composition comprising a polyol composition and a polyurethane foam formed from the polyurethane composition can be provided.
  • the present invention is a container containing a polyol compound, a filler, a catalyst, and a low boiling point compound, and containing a polyol composition having a low boiling point compound ratio of 5 to 30% calculated by the following formula (1).
  • C Weight of the container after discharging the polyol composition
  • C Weight after drying the discharged product discharged for 10 seconds at 40 ° C. for 30 minutes.
  • the polyol composition encapsulated in the container of the present invention contains a low boiling point compound.
  • the low boiling point compound discharges the polyol composition by its vapor pressure and vaporizes when the polyol composition is discharged to foam the polyol composition and the polyurethane composition described later.
  • the proportion of low boiling point compounds in the polyol composition is 5-30%. If the proportion of the low boiling point compound is less than 5%, the discharge amount of the polyol composition is insufficient, the mixing efficiency with the polyisocyanate composition described later is lowered, the workability is deteriorated, and other problems are likely to occur. Become.
  • the proportion of the low boiling point compound exceeds 30%, the pressure inside the container tends to increase, and the safety tends to decrease.
  • the proportion of the low boiling point compound is preferably 5 to 28%, more preferably 6 to 25%, from the viewpoint of enhancing safety while increasing the discharge amount of the polyol composition.
  • the proportion of low boiling point compounds in the polyol composition is calculated by the following formula (1).
  • Low boiling point compound ratio (%) [(AB) / C-1] ⁇ 100
  • the above formula (1) for calculating the low boiling point compound ratio (%) is synonymous with [(ABC) / C] ⁇ 100, and “C” in the denominator is a polyol excluding low boiling point compounds. Corresponds to the amount of composition and the "ABC" of the molecule corresponds to the amount of low boiling point compound.
  • the operation of keeping the temperature at 35 ° C. is, for example, immersing the container in warm water at 35 ° C. for 60 minutes.
  • each component constituting the polyol composition is discharged in a uniformly mixed state.
  • an unused aerosol container which is a polyol composition sufficiently mixed so as to be uniform and filled with a sufficient amount of the polyol composition so that not all of the polyol composition is discharged within 10 seconds, the above is used.
  • the discharge rate is constant for 10 seconds.
  • the container can be shaken, for example, by holding the container by hand and shaking it up and down.
  • the method for uniformly mixing the polyol composition is not limited to the above-mentioned method.
  • the discharged product When the discharged product is dried at 40 ° C. for 30 minutes in C above, the discharged product is placed in a cylindrical polyethylene container having a diameter of 10 cm and a height of 12 cm, and the upper portion of the container is opened.
  • the type of the low boiling point compound is not particularly limited as long as the polyol composition can be discharged by its vapor pressure, and is hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), hydrofluoroolefin (HFO), hydrocarbon. , Ether compounds, inorganic gases, etc. can be used.
  • HFC hydrofluorocarbon
  • HCFC hydrochlorofluorocarbon
  • HFO hydrofluoroolefin
  • Ether compounds, inorganic gases, etc. can be used.
  • hydrofluoroolefins (HFOs) hydrocarbons having 1 to 5 carbon atoms
  • ether compounds such as dimethyl ether
  • inorganic gases such as nitrogen
  • the low boiling point compound preferably has a boiling point of 0 ° C. or lower at 1 atm, more preferably ⁇ 10 ° C. or lower, and even more preferably ⁇ 15 ° C. or lower, from the viewpoint of increasing the discharge amount of the polyol composition.
  • the boiling point of the low boiling point compound means the boiling point of the low boiling point compound alone, and does not mean the boiling point at which the low boiling point compound azeotropes with another compound, for example.
  • Examples of the low boiling point compound having a boiling point of 0 ° C. or lower include 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,2,3,3,3-pentafluoropropene (HFO-1225ye), and the like.
  • Hydrofluoroolefins such as 1,1,1,3,3-pentafluoropropene (HFO-1225zc), 2,3,3,3-tetrafluoropropene (HFO-1234yf), ethane, propane, isobutane, Examples thereof include hydrocarbons having 1 to 4 carbon atoms such as various butanes such as normal butane, dimethyl ether, and nitrogen.
  • LPG liquefied petroleum gas
  • propane and butanes as main components
  • the low boiling point compounds having a boiling point of 0 ° C. or lower 1,3,3,3-tetrafluoropropene (HFO-1234ze), dimethyl ether, LPG, and nitrogen are preferable, and among them, 1,3,3,3-tetrafluoro Propen (HFO-1234ze), dimethyl ether, and LPG are more preferred.
  • HFO-1234ze 1,3,3,3-tetrafluoropropene
  • dimethyl ether LPG
  • LPG low boiling point compound having a boiling point of 0 ° C. or lower
  • 1,3,3,3-tetrafluoropropene (HFO-1234ze), dimethyl ether, LPG, and nitrogen are preferable, and among them, 1,3,3,3-tetrafluoro Propen (HFO-1234ze), dimethyl ether, and LPG are more preferred.
  • HFO-1234ze 1,3,3,3-tetrafluoropropen
  • the polyol composition in the present invention contains a filler. By containing the filler, the shrinkage of the obtained polyurethane foam can be suppressed.
  • the filler ratio calculated by the formula (2) of the polyol composition is 5 to 80%. When the filler ratio is 5% or more, shrinkage of the obtained polyurethane foam is easily suppressed, and when the filler ratio is 80% or less, the polyol composition is easily discharged from the container.
  • the filler ratio of the polyol composition is preferably 8 to 78%, more preferably 10 to 75%.
  • the filler ratio is calculated by the following formula (2).
  • Formula (2) Filler ratio (%) (E / D) x 100 D: After keeping the container warm at 35 ° C., the discharge product obtained by discharging the polyol composition from the container in a uniformly mixed state for 10 seconds is dried at 40 ° C. for 30 minutes, and then the weight E: D. The discharged product after drying is diluted with acetone and suction-filtered, and the weight of the obtained agglomerates. In the above D, the method of keeping the container at 35 ° C. and discharging the polyol composition for 10 seconds has a low boiling point. The same method as B described above for calculating the compound ratio can be applied.
  • the amount of acetone used is not particularly limited as long as suction filtration can be performed, but for example, it may be 0.1 to 10 mL per 1 mg of the discharged product after drying.
  • the filter paper used for suction filtration is a filter paper capable of filtering fillers, and for example, Advantech's circular quantitative filter paper No. 3 is used.
  • agglomerates acetone insoluble matter
  • the weight is measured, and this value is taken as the weight of the agglomerates in E.
  • the filler examples include a solid flame retardant and an inorganic filler.
  • a solid flame retardant When a solid flame retardant is used as the filler, the flame retardancy of the polyurethane foam can be effectively enhanced. Further, the solid flame retardant is usually in a state of being dispersed in the polyol composition as a powder component.
  • the solid flame retardant is a flame retardant that becomes solid at normal temperature (23 ° C.) and normal pressure (1 atm).
  • Specific examples of the solid flame retardant include a red phosphorus flame retardant, a phosphate-containing flame retardant, a bromine-containing flame retardant, a chlorine-containing flame retardant, an antimony-containing flame retardant, a boron-containing flame retardant, and a metal hydroxide. .. These may be used alone or in combination of two or more.
  • 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 mixed with an oxide or 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.
  • phosphate-containing flame retardant for example, at least selected from various phosphoric acids, metals of Group IA to IVB of the Periodic Table, ammonia, aliphatic amines, aromatic amines, and heterocyclic compounds containing nitrogen in the ring.
  • examples include phosphates consisting of salts with a type of metal or compound.
  • the phosphoric acid is not particularly limited, and examples thereof include monophosphoric acid, pyrophosphoric acid, and polyphosphoric acid.
  • the metals 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 examples include monophosphate, pyrophosphate, polyphosphate and the like.
  • 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 one or more of the above-mentioned ones can be used.
  • the bromine-containing flame retardant is not particularly limited as long as it is a compound containing bromine in its molecular structure and becomes a solid at normal temperature and pressure, and examples thereof include a brominated aromatic ring-containing aromatic compound.
  • 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 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, polychlorinated naphthalene, chlorendic acid, and dodecachlorododecahydrodimethanodibenzocyclo, which is sold under the trade name of "Dechloran Plus". Octene and the like can be mentioned.
  • antimony-containing flame retardant examples include antimony oxide, antimonate, pyroantimonate 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.
  • the antimony-containing flame retardant used in the present invention is preferably antimony oxide.
  • boron-containing flame retardant used in the present invention examples include borax, boron oxide, boric acid, borate and the like.
  • boron oxide examples include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, tetraboron pentoxide and the like.
  • borate examples include alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the periodic table, and ammonium borates.
  • alkali metal borate salts such as lithium borate, sodium borate, potassium borate, and cesium borate
  • alkaline earth metal borate salts such as magnesium borate, calcium borate, and barium borate, and borate. 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.
  • the boron-containing flame retardant used in the present invention is preferably borate, more preferably zinc borate.
  • Metal hydroxide used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydride, titanium hydroxide, zinc hydroxide, and copper hydroxide.
  • Examples include vanadium hydroxide and tin hydroxide.
  • the metal hydroxide may be used alone or in combination of two or more.
  • the content of the solid flame retardant in the polyol composition may be appropriately adjusted so that the filler ratio is within the above range, but is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the polyol compound. It is preferably 10 to 50 parts by mass.
  • the content of the solid flame retardant is at least the above lower limit value, the shrinkage rate of the obtained polyurethane foam can be reduced, and the flame retardancy can be improved.
  • the content of the solid flame retardant is not more than the above upper limit value, the discharge property of the polyol composition becomes good.
  • Inorganic filler examples include silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, and carbon dioxide.
  • inorganic fillers may be used alone or in combination of two or more.
  • the content of the inorganic filler in the polyol composition may be appropriately adjusted so that the filler ratio is within the above range, but is preferably 5 to 150 parts by mass with respect to 100 parts by mass of the polyol compound. It is preferably 10 to 100 parts by mass.
  • the content of the inorganic filler is at least the above lower limit value, the shrinkage rate of the obtained polyurethane foam can be reduced.
  • the content of the inorganic filler is not more than the above upper limit value, the discharge property of the polyol composition becomes good.
  • the polyol composition of the present invention contains a polyol compound as a raw material for a polyurethane foam.
  • the polyol compound include polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.
  • the polyol compound usually becomes a liquid at normal temperature (23 ° C.) and normal pressure (1 atm).
  • polylactone polyol examples include polypropiolactone glycol, polycaprolactone glycol, polyvalerolactone glycol and the like.
  • polycarbonate polyol examples include a polyol obtained by dealcoholization of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with ethylene carbonate, propylene carbonate, and the like. And so on.
  • Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, cresol novolac and the like.
  • Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, and dimethyldicyclohexylmethanediol.
  • Examples of the aliphatic polyol include alkanediols such as ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.
  • 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-hexane glycol, neopentyl glycol and the like.
  • hydroxycarboxylic acid examples include castor oil, a reaction product of castor oil and ethylene glycol, 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 compounds thereof and the like.
  • modified polyol of the polyhydric alcohol examples include those modified by reacting the raw material polyhydric alcohol 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, methyl glucoside and the like.
  • Tetra-octavalent alcohols such as its derivatives, fluoroglycolsinol, 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, (co) polymer of hydroxyalkyl (meth) acrylate and polyfunctional (for example, 2 to 100 functional groups) polyols such as polyvinyl alcohol, condensation of phenol and formaldehyde Things (Novolak) can be mentioned.
  • Novolak formaldehyde Things
  • 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 include AO 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 of these.
  • 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.
  • polyester polyol and polyether polyol are preferable.
  • polybasic acids having an aromatic ring such as isophthalic acid (m-phthalic acid) and terephthalic acid (p-phthalic acid)
  • dihydric alcohols such as bisphenol A, ethylene glycol, and 1,2-propylene glycol.
  • Aromatic polyester polyol obtained by dehydration condensation of the above is more preferable.
  • a polyol having two hydroxyl groups is preferable.
  • the hydroxyl value of the polyol compound is preferably 20 to 300 mgKOH / g, more preferably 30 to 250 mgKOH / g, and even more preferably 50 to 220 mgKOH / g.
  • the hydroxyl value of the polyol compound is not more than the above upper limit value, the viscosity of the polyol composition tends to decrease, which is preferable from the viewpoint of handleability and the like.
  • the hydroxyl value of the polyol compound is at least the above lower limit value, the crosslink density of the polyurethane foam increases and the strength increases.
  • the hydroxyl value of the polyol compound can be measured according to JIS K 1557-1: 2007.
  • the content of the polyol compound in the polyol composition of the present invention is preferably 10 to 80% by mass, more preferably 20 to 75% by mass, and further preferably 25 to 70% by mass.
  • the content of the polyol compound 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 compound is not more than the above upper limit value, the viscosity of the polyol-containing composition does not become too high, which is preferable from the viewpoint of handleability.
  • the polyol composition in the present invention contains a catalyst.
  • the catalyst preferably contains at least one of the trimerization catalyst and the resinification catalyst, and more preferably contains both the trimerization catalyst and the resinification catalyst.
  • a polyol foam produced by using both of these catalysts is preferable because the shrinkage rate tends to be low.
  • the trimerization catalyst is a catalyst that promotes the formation of isocyanurate rings by reacting the isocyanate groups contained in the polyisocyanate compound to trimerize them.
  • 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, tetra
  • quaternary ammonium salt such as a phenylammonium 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 acids. 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 are preferable, and carboxylic acid quaternary ammonium salt is more preferable.
  • the blending amount of the trimerization catalyst is preferably 1 to 25 parts by mass, more preferably 2 to 18 parts by mass, and further preferably 3 to 15 parts by mass with respect to 100 parts by mass of the polyol compound.
  • trimerization of the polyisocyanate compound 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 above upper limit value, the reaction can be easily controlled.
  • the resinification catalyst is a catalyst that promotes the reaction between the polyol compound and the polyisocyanate compound.
  • the resinification 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. Specifically, N-methylimidazole, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-methyl-2-ethylimidazole, 1,2-diethylimidazole, and 1-isobutyl-2-methyl. Examples include imidazole.
  • an imidazole compound in which the secondary amine in the imidazole ring is replaced with a cyanoethyl group may be used.
  • the piperazine compound include tertiary amines such as N-methyl-N'N'-dimethylaminoethylpiperazine and trimethylaminoethylpiperazine.
  • the resinification catalysts include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholinbis (2-dimethylaminoethyl) ether, N, N, N', N ", N"-.
  • Pentamethyldiethylenetriamine N, N, N'-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N, N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine , Various tertiary amines such as tripropylamine and the like.
  • the metal 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 versatate, bismuth trioctate, bismastrioctate (2-ethylhexanoate), tin dioctylate, lead dioctylate and the like can be mentioned, and among them, the organic acid bismuth salt is more preferable. ..
  • the resinification 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 resinification catalyst is preferably 1 to 25 parts by mass, more preferably 2 to 18 parts by mass, and even more preferably 3 to 12 parts by mass with respect to 100 parts by mass of the polyol compound.
  • 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, if it is less than these upper limit values, the reaction rate can be easily controlled.
  • the amount of the resinification catalyst with respect to the trimerization catalyst is the shrinkage rate of the obtained polyurethane foam. From the viewpoint of making it smaller, it is preferably 0.2 to 10, and more preferably 0.5 to 2.
  • the total amount of the catalyst in the polyol composition is not particularly limited, but is preferably 2 to 40 parts by mass, more preferably 4 to 25 parts by mass, and further preferably 5 to 20 parts by mass.
  • the total amount of the catalyst in the polyol composition is not particularly limited, but is preferably 2 to 40 parts by mass, more preferably 4 to 25 parts by mass, and further preferably 5 to 20 parts by mass.
  • the polyol composition in the present invention may contain a liquid flame retardant.
  • the liquid flame retardant is a flame retardant that becomes liquid at normal temperature and pressure.
  • Specific examples of the liquid flame retardant include phosphoric acid ester.
  • the phosphoric acid ester a monophosphate ester, a condensed phosphoric acid ester, or the like can be used.
  • the monophosphate ester is a phosphate ester having one phosphorus atom in the molecule.
  • the monophosphate ester is not limited as long as it is liquid at normal temperature and pressure, but for example, trialkyl phosphate such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, and tris ( ⁇ -chloro).
  • Halogen-containing phosphates such as propyl) phosphate, trialkoxy phosphates such as tributoxyethyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, cresildiphenyl phosphate, diphenyl (2-ethylhexyl) phosphate.
  • alogen-containing phosphates such as propyl) phosphate, trialkoxy phosphates such as tributoxyethyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, cresildiphenyl phosphate, diphenyl (2-ethylhexyl) phosphate.
  • aromatic ring-containing phosphoric acid esters such as, monoisodecyl phosphate, and acidic phosphoric acid esters such as diis
  • 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.
  • commercially available condensed phosphate esters include “CR-733S”, “CR-741", and “CR747” manufactured by Daihachi Chemical Industry Co., Ltd., and "ADEKA STUB PFR" and "FP-600” manufactured by ADEKA. And so on.
  • the liquid flame retardant may be used alone from the above-mentioned ones, or may be used in combination of two or more.
  • monophosphate esters are preferable, and halogen-containing phosphoric acid esters such as tris ( ⁇ -chloropropyl) phosphate are preferable from the viewpoint of facilitating the appropriate viscosity of the polyol compound and improving the flame retardancy of polyurethane foam. More preferred.
  • the blending amount of the liquid flame retardant is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and 20 to 50 parts by mass with respect to 100 parts by mass of the polyol compound.
  • the portion is more preferable.
  • the polyol composition of the present invention may contain a defoaming agent.
  • the defoaming agent improves the foamability of the polyurethane composition obtained from the polyol composition and the polyisocyanate composition.
  • 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 foam stabilizers 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 foam stabilizer is not less than these lower limit values, the polyurethane composition can be easily foamed, and a homogeneous polyurethane foam can be easily obtained. 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 in the present invention may contain water. By containing water, the foamability when forming the polyurethane foam is improved.
  • the blending amount of water is, for example, 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, and more preferably 0.3 to 3 parts by mass with respect to 100 parts by mass of the polyol compound. By setting the blending amount of water within these ranges, the polyurethane composition can be easily foamed appropriately.
  • the polyol composition contains, if necessary, antioxidants such as phenol-based, amine-based, and sulfur-based antioxidants, precipitation inhibitors, heat stabilizers, metal damage inhibitors, and antistatic agents, as long as the object of the present invention is not impaired. , Stabilizers, cross-linking agents, lubricants, softeners, pigments, additives such as antistatic resins, and antistatic agents such as polybutene and petroleum resins.
  • the container of the present invention is a container in which the above-mentioned polyol composition is sealed.
  • the container is not particularly limited as long as the polyol composition can be discharged by the vapor pressure of the low boiling point compound, and an aerosol container is preferable.
  • the aerosol container is provided with, for example, a container body filled with a polyol composition and a cap portion for sealing the upper part of the container body, and when a button or the like provided on the cap portion is pressed, a valve or the like is opened and the internal pressure is released. Then, the polyol composition is discharged from the discharge port provided in the cap portion by the vapor pressure of the low boiling point compound.
  • the method for encapsulating the polyol composition in the container is not particularly limited, but each component other than the low boiling point compound is mixed as necessary using a disper or the like, filled inside the container to seal the container, and then low. Fill with boiling point compound.
  • the filling of the low boiling point compound can be performed, for example, by opening the valve provided in the cap portion of the container and injecting the low boiling point compound into the inside of the container.
  • the container When discharging the polyol composition from the container, discharge it in a state where each component constituting the polyol composition is uniformly mixed. It is advisable to shake the container well before discharging in order to uniformly mix the components constituting the polyol composition.
  • the container can be shaken, for example, by holding the container by hand and shaking it up and down.
  • the method for uniformly mixing the polyol composition is not limited to the above-mentioned method.
  • the temperature of the container at the time of discharging is preferably, for example, 10 ° C. or higher and 40 ° C. or lower. When the temperature is 10 ° C. or higher, the liquid temperature is high to a certain extent, so that the discharge is good, and when the temperature is 40 ° C. or lower, the container is prevented from bursting.
  • the polyurethane composition of the present invention comprises a polyol composition discharged from the above-mentioned container and a polyisocyanate composition containing a polyisocyanate compound. That is, the above-mentioned polyol composition of the present invention is used as a polyol composition of a two-component polyurethane, and is mixed with a polyisocyanate composition containing a polyisocyanate compound and used as a polyurethane composition.
  • the polyol composition and the polyisocyanate composition may be mixed in a mass ratio so that the isocyanate index falls within a predetermined range, as will be described later.
  • the polyurethane composition obtained by mixing the polyol composition and the polyisocyanate composition reacts and is contained in the low boiling point compound contained in the above-mentioned polyol composition or the low boiling point compound contained in the polyisocyanate composition described later. It becomes a polyurethane foam by foaming with a boiling compound or the like.
  • the polyisocyanate composition contains a polyisocyanate compound.
  • a polyisocyanate compound a known polyisocyanate compound used for forming a polyurethane foam can be used.
  • the polyisocyanate compound 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 (polymeric MDI). Be done.
  • Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.
  • Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate and the like.
  • aromatic polyisocyanates are preferable from the viewpoint of ease of use and availability, and diphenylmethane diisocyanate, polypeptide MDI, or a mixture thereof is more preferable.
  • One type of polyisocyanate may be used alone, or two or more types may be mixed and used.
  • Polyisocyanate compositions usually further contain lower boiling point compounds.
  • the low boiling point compound the above-mentioned compounds can be used without particular limitation.
  • the low boiling point compound used in the polyisocyanate composition may be the same as or different from the low boiling point compound used in the polyol composition.
  • the proportion of the low boiling point compound contained in the polyisocyanate composition is preferably 5% by mass or more and less than 20% by mass, and more preferably 7% by mass or more and less than 15% by mass. Sufficient discharge force can be obtained by containing 5% by mass or more of the low boiling point compound. Further, if it is less than 20% by mass, the foaming density obtained does not become too low, and appropriate physical properties can be obtained.
  • a known additive to be blended with polyisocyanate may be appropriately blended in the polyisocyanate composition.
  • the isocyanate index of the polyurethane composition of the present invention is preferably 200 or more.
  • the isocyanate index is 200 or more, the amount of the polyisocyanate compound with respect to the polyol compound becomes excessive, and isocyanurate bonds are easily formed by the trimeric of polyisocyanate, and as a result, the flame retardancy of the polyurethane foam is improved.
  • the isocyanate index is more preferably 250 or more, further preferably 340 or more.
  • the isocyanate index is preferably 1000 or less, more preferably 650 or less, and even more preferably 500 or less. When the isocyanate index is not more than these upper limit values, the balance between the flame retardancy of the obtained polyurethane foam and the manufacturing cost is improved.
  • 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 56100 (mmol).
  • the molecular weight of water is 18 (mol), and the number of OH groups in water is 2.
  • the present invention also provides a mixing system for mixing a polyol composition and a polyisocyanate composition.
  • the mixing system 10 includes a first container 11 in which the polyol composition is encapsulated, and a second container 12 in which the polyisocyanate composition is encapsulated.
  • the first containers 11 and 12 are both aerosol containers (spray cans).
  • the polyol composition sealed in the first container 11 is discharged by the vapor pressure of the low boiling point compound contained in the polyol composition.
  • the polyisocyanate composition sealed in the second container 12 is discharged by the vapor pressure of the low boiling point compound contained in the polyisocyanate composition.
  • the polyol composition and the polyisocyanate composition discharged from the first and second containers 11 and 12 are mixed while being foamed by a low boiling point compound or the like, and the polyisocyanate compound and the polyol compound react with each other to cause polyurethane. Form foam.
  • the mixing system 10 may include a mixer 13.
  • the discharge ports 11A and 12A of the first and second containers 11 and 12, respectively, are connected to the mixer 13 via the supply lines 11B and 12B.
  • the polyol composition and the polyisocyanate composition discharged from the first and second containers 11 and 12 are supplied to the mixer 13 via the supply lines 11B and 12B, respectively, and these are mixed in the mixer 13. .
  • the polyol composition and the polyisocyanate composition mixed in the mixer 13 may be sprayed onto the surface to be constructed by an injector or the like.
  • the mixer 13 is preferably a stationary mixer, which is a so-called static mixer.
  • the stationary mixer is a mixer without a drive unit, and the fluid is mixed by passing the fluid through the inside of the pipe body.
  • Examples of the stationary mixer include a mixer element 13B in which the mixer element 13B is arranged inside the tubular body 13A as shown in FIG.
  • Examples of the mixer element 13B include those formed in a spiral shape and those in which a plurality of baffle plates are formed.
  • the stationary mixer may also have the function of an injector. In this case, as shown in FIG. 1, a mixture of the polyol composition and the polyisocyanate composition mixed inside the tube 13A is mixed at the tip 13C of the tube. It is good to spray from. Note that FIG.
  • a discharge gun, a jig, or the like may be provided.
  • FIG. 2 shows the mixing system 20 as an example of a mode in which a discharge gun is provided before being introduced into the mixer.
  • the mixing system 20 includes a first container 11, a second container 12, supply lines 11B and 12B, a discharge gun 14, and a mixer 13.
  • the first container 11 and the second container 12 are as described above, and contain a polyol composition and a polyisocyanate composition, respectively. From the first and second containers, the polyol composition and the polyisocyanate composition are sent to the discharge gun 14 via the supply lines 11B and 12B, respectively.
  • the discharge gun 14 includes a lever 14A and has an ON-OFF mechanism for feeding liquid.
  • the polyol composition and the polyisocyanate composition are fed to the mixer 13, and when the lever 14A is released, the liquid feeding to the mixer 13 is stopped.
  • the mixing system 20 including the discharge gun 14 the liquid can be fed as needed, so that the workability when forming the polyurethane foam is improved.
  • the polyurethane foam of the present invention is formed from the above-mentioned polyurethane composition. Since the polyurethane foam of the present invention contains the above-mentioned filler, it has a low shrinkage rate and is excellent in shape stability. Specifically, the shrinkage ratio of the polyurethane foam is preferably less than 20%, more preferably less than 10%.
  • the shrinkage rate of the polyurethane foam is determined as follows. Immediately after the completion of foaming (immediately after production), the polyurethane foam is cut into 5 cm squares (length 5 cm, width 5 cm, thickness 5 cm), and the length of each side (length before the test) is measured. In addition, each side means all sides (12 sides) of the cut-out foam.
  • the cut-out foam is left to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, and then the length of each side (length after the test) is measured.
  • Obtain the rate of change in the length of each side [100 x (length before the test-length after the test) / length before the test], and calculate the average value of the rate of change in the length of each side (12 sides).
  • the average value of the rate of change of) is taken as the shrinkage rate.
  • the polyurethane foam formed from the polyurethane composition can be used for various purposes, but it is preferably used as a heat insulating material. Since the polyurethane foam has a large number of bubbles, it has a heat insulating effect. Polyurethane foam is more preferably used as a heat insulating material for vehicles or buildings in particular. Vehicles include railroad vehicles, automobiles, ships, aircraft and the like. Further, in the present invention, a polyurethane foam can be formed with a simple structure by using a container such as an aerosol container. Further, since the foam can be formed by using a container, it is particularly suitable when the surface to be constructed is relatively small.
  • the present invention is not limited to such applications, and may be used to form a newly installed heat-resistant material.
  • the evaluation method is as follows. [Ratio of low boiling point compounds] The proportion of low boiling point compounds in the polyol composition was calculated by the following formula (1).
  • the filler ratio in the polyol composition is calculated by the following formula (2).
  • Formula (2) Filler ratio (%) (E / D) x 100 D: After keeping the container warm at 35 ° C., the discharged product obtained by discharging the polyol composition from the container for 10 seconds is dried at 40 ° C. for 30 minutes, and then the discharged product having a weight E: D after drying is used. Dilute with acetone and perform suction filtration to obtain the weight of the agglomerates.
  • the shrinkage rate of the polyurethane foam was calculated by the following method. Immediately after the completion of foaming (immediately after production), the polyurethane foam is cut into 5 cm squares (length 5 cm, width 5 cm, thickness 5 cm), and the length of each side (length before the test) is measured. Then, the cut-out foam was left to stand at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, and then the length of each side (length after the test) was measured. Obtain the rate of change in the length of each side [100 x (length before the test-length after the test) / length before the test], and use the average value of the rate of change in the length of each side as the shrinkage rate. It was evaluated according to the following criteria. A: Shrinkage rate is less than 10% B: Shrinkage rate is 10% or more and less than 20% C: Shrinkage rate is 20% or more
  • Discharge rate The aerosol container containing the polyol composition was immersed in warm water at 35 ° C. for 60 minutes and then discharged for 5 seconds. The discharge amount was calculated based on the following formula and evaluated based on the following criteria.
  • Discharge amount (g) Weight of aerosol container before discharge-Weight of aerosol container after discharge A: Discharge amount is 15 g or more B: Discharge amount is 10 g or more and less than 15 g C: Discharge amount is less than 10 g
  • the components used in the examples and comparative examples are as follows.
  • the number of copies of each component shown in Table 1 indicates the number of copies of the diluted product as a diluted product.
  • Resinization catalyst Imidazole compound (active ingredient amount 65-75% by mass, diluted with ethylene glycol, manufactured by Tosoh Corporation, product name: TOYOCAT-DM70) Trimerization catalyst: Quaternary ammonium salt of carboxylic acid (active ingredient amount 45-55% by mass, diluted with ethylene glycol) (Evonik Japan Co., Ltd., product name: DABCO TMR-7)
  • Filler 1 Wollastonite (Product name: SH1250 manufactured by Kinsei Matek Co., Ltd.)
  • Filler 2 Red phosphorus flame retardant (manufactured by Rinkagaku Kogyo Co., Ltd., product name: Nova Excel 140, metal hydroxide coating, red phosphorus content 94% by mass or more)
  • Filler 3 Bromine-containing flame retardant, ethylene bis (pentabromophenyl) (manufactured by Albemarle, product name: SAYTEX 8010)
  • Filler 4 Boron-containing flame retardant (Hayakawa Shoji "FIREBREAK ZB")
  • Defoaming agent Polyoxyalkylene-based defoaming agent (manufactured by Toray Dow Corning, product name SH-193)
  • Low boiling point compound 1 DME / LPG A mixture of DME (dimethyl ether) and LPG.
  • Polyisocyanate compound 4,4'-diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Manka Kagaku Japan Co., Ltd., product name: PM200)
  • Example 1 In accordance with the formulation shown in Table 1, components other than the low boiling point compound were measured in a 1000 ml polypropylene beaker, mixed at 1500 rpm for 5 minutes using a disper, transferred to an aerosol container, sealed using a vacuum crimper, and then further lowered. The boiling point compound was filled to obtain a first aerosol container in which the polyol composition was sealed. The amount of the polyol composition to be filled was 460 g for the polyol composition other than the low boiling point compound, and the filling ratio for the low boiling point compound was as shown in Table 1. Using the first aerosol container, the above-mentioned low boiling point compound ratio, filler ratio, and discharge amount were measured.
  • a lower boiling point compound (DME / LPG) is further sealed.
  • the mass ratio of 6/4) was filled to obtain a second aerosol container in which the polyisocyanate composition was sealed.
  • the amount of the low boiling point compound was 65 g with respect to 420 g of the polyisocyanate compound.
  • the polyol composition and the polyisocyanate composition are discharged from the first aerosol container and the second aerosol container described above, respectively, and these are mixed with a static mixer to obtain a polyurethane composition, which is then sprayed from the tip thereof.
  • a polyurethane foam was obtained by spraying on a gypsum board. The results of each evaluation are shown in Table 1.
  • Example 2 to 13 Comparative Examples 1 to 3 A first aerosol container and a second aerosol container were prepared in the same manner as in Example 1 except that the composition of the polyol composition was changed as shown in Table 1, to obtain a polyurethane foam. The results of each evaluation are shown in Table 1.
  • Comparative Example 1 was an example in which a container containing a polyol composition containing no filler was used, and the shrinkage rate of the obtained polyurethane foam was increased.
  • Comparative Example 2 is an example in which a container filled with a polyol composition having a small proportion of low boiling point compounds was used, and the result was that the discharge amount was small.
  • Comparative Example 3 is an example in which a container containing a polyol composition containing no catalyst was used, and the polyurethane foam was not formed and the shrinkage rate could not be evaluated.
  • Mixing system 11 1st container 12 2nd container 11A, 12A Discharge port 11B, 12B Supply line 13 Mixer 13A Tube body 13B Mixer element 13C Tip 14 Discharge gun 14A Lever 20 Mixing system

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