JP2018177891A - Polyol composition and polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyol composition without hard caking (solidification as impossible to re-stirred) when a premix is long term stored for 1 month or longer, polyurethane and polyurethane foam using the same.SOLUTION: There is provided a polyol composition containing a polyol compound, a foam forming agent, a filler, and a metal oxide fine particle, in which the foam forming agent is hydrofluorocarbon, and a hydroxyl group exists on a surface of the oxide metal fine particle.SELECTED DRAWING: None

Description

  The present invention relates to polyol compositions and polyurethane foams.

  Concrete reinforced with reinforcing bars is used as a structural material for enhancing the strength of buildings, such as apartment buildings such as apartments, detached houses, various facilities of schools, outer walls of commercial buildings, etc.

  On the other hand, since concrete has a heat storage property and a cold storage property, the heat stored in the summer heats the inside of the building, and the concrete is cooled in the cold winter season, so that the inside of the building is cooled. In order to reduce the influence of the outside temperature on the interior of the building for a long time through such concrete, the concrete is usually subjected to thermal insulation processing.

  Therefore, a rigid polyurethane foam having fire resistance to fire is used as a heat insulating layer.

  Patent Document 1 discloses a flame retardant composition for polyurethane containing red phosphorus and an antisettling agent.

JP, 2012-219127, A

  An object of the present invention is to provide a polyol composition that does not undergo hard caking (solidification that can not be re-stirred) when storing the premix for a long period of 1 month or more, and a polyurethane foam using it.

The present invention provides the following polyol composition and a polyurethane foam using it.
Item 1. What is claimed is: 1. A polyol composition comprising a polyol compound, a foaming agent, a filler, and metal oxide fine particles, wherein the foaming agent is a hydrofluorocarbon, and a hydroxyl group is present on the surface of the metal oxide fine particles.
Item 2. The polyol composition according to Item 1, further comprising a catalyst and / or a foam stabilizer.
Item 3. The polyol composition according to Item 1 or 2, wherein the filler comprises a flame retardant.
Item 4. The polyol composition according to Item 1, wherein the metal portion of the metal oxide fine particles is aluminum, titanium or silicon.
Item 5. The polyol composition according to Item 1, wherein the water absorption amount of the metal oxide fine particles is 0.2% by mass or more.
Item 6. The polyurethane foam containing the metal oxide fine particle in which the hydroxyl group exists in the surface manufactured by mixing the polyol composition in any one of the said 1-5 with a polyisocyanate compound.

  According to the present invention, the polyol composition can be used if it is re-stirred even when stored for one month or more.

  The polyol composition of the present invention contains a polyol compound, a foaming agent (hydrofluorocarbon), a filler, and metal oxide fine particles having hydroxyl groups on the surface. The polyol composition can be mixed with a polyisocyanate compound to obtain polyurethane and polyurethane foam.

  The polyol composition preferably further contains a catalyst and / or a foam stabilizer.

  Examples of the polyol compound which is a curing agent of the urethane resin include polylactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polymer polyol, polyether polyol and the like.

  Examples of polylactone polyols include polypropiolactone glycol, polycaprolactone glycol and polyvalerolactone glycol.

  Examples of polycarbonate polyols include polyols obtained by the dealcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, nonanediol, etc. with diethylene carbonate, dipropylene carbonate, etc. Etc.

  Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, cresol novolac and the like.

  Examples of alicyclic polyols include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, dimethyldicyclohexylmethanediol and the like.

  As an aliphatic polyol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol etc. are mentioned, for example.

  Examples of polyester polyols include polymers obtained by dehydration condensation of polybasic acids and polyhydric alcohols, polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone, The condensation product of hydroxycarboxylic acid and the above-mentioned polyhydric alcohol etc. is mentioned.

  Specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid. Specific examples of polyhydric alcohols include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, neopentyl glycol and the like. .

  Specific examples of the hydroxycarboxylic acid include castor oil and reaction products of castor oil and ethylene glycol.

  As a polymer polyol, for example, a polymer obtained by graft polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, methacrylate or the like to an aromatic polyol, an alicyclic polyol, an aliphatic polyol, a polyester polyol, etc., polybutadiene Examples thereof include polyols, modified polyols of polyhydric alcohols, and hydrogenated products thereof.

  As the modified polyol of polyhydric alcohol, for example, one obtained by reacting an alkylene oxide with a polyhydric alcohol as a raw material to modify it is mentioned.

  Examples of polyhydric alcohols include glycerin and trihydric alcohols such as trimethylolpropane; pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methyl glucoside and the like Tetrahydric to octahydric alcohols such as derivatives; phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, Phenol polybutadienepolyols such as anthrol, 1,4,5,8-tetrahydroxyanthracene, 1-hydroxypyrene; castor oil polyol; hydroxyalkyl (meth) acrylic Polyfunctional (e.g. functionality 2 to 100) polyol such as (co) polymers and polyvinyl alcohol over preparative include condensates of phenol and formaldehyde (novolac) it is.

  Although the modification | denaturing method of polyhydric alcohol is not specifically limited, The method to which an alkylene oxide (it abbreviates as AO hereafter) is added is used suitably.

  As AO, AO having 2 to 6 carbon atoms, for example, ethylene oxide (hereinafter, abbreviated as EO), 1,2-propylene oxide (hereinafter, abbreviated as PO), 1,3-propylene oxide, 1,2-butylene Oxide, 1,4-butylene oxide and the like can be mentioned.

  Among these, from the viewpoint of properties and reactivity, PO, EO and 1,2-butylene oxide are preferable, and PO and EO are more preferable. When two or more AOs are used (for example, PO and EO), the addition method may be block addition or random addition, or a combination of these.

  As the polyether polyol, for example, ring-opening polymerization of at least one kind of alkylene oxide such as ethylene oxide, propylene oxide, tetrahydrofuran or the like in the presence of at least one kind of low molecular weight active hydrogen compound having two or more active hydrogens. And polymers obtained by

  Examples of low molecular weight active hydrogen compounds having two or more active hydrogens include bisphenol A, ethylene glycol, propylene glycol, butylene glycol, diols such as 1,6-hexanediol, and triols such as glycerin and trimethylolpropane. And amines such as ethylene diamine and butylene diamine.

  As the polyol used in the present invention, it is preferable to use a polyester polyol or a polyether polyol because the effect of reducing the total calorific value upon combustion is large.

  Among them, it is more preferable to use a polyester polyol having a molecular weight of 200 to 800, and it is further preferable to use a polyester polyol having a molecular weight of 300 to 500.

  As a polyisocyanate compound which is a main ingredient of urethane resin, aromatic polyisocyanate, alicyclic polyisocyanate, aliphatic polyisocyanate etc. are mentioned, for example.

  Examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate and the like.

  Examples of the alicyclic polyisocyanate include cyclohexyl diisocyanate, methyl cyclohexyl diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, and dimethyl dicyclohexyl methane diisocyanate.

  Examples of aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate and the like.

  A urethane prepolymer may be used as the polyisocyanate compound. As a urethane prepolymer, what was obtained by making the said polyol compound and excess said polyisocyanate compound react is mentioned.

  The polyisocyanate compound can be used alone or in combination of two or more. The main component of the urethane resin is preferably an aromatic polyisocyanate such as polyphenylpolymethylene polyisocyanate from the viewpoint of ease of use and availability.

  In the composition of the present invention, the isocyanate index is preferably 200 or more, more preferably 260 or more and 700 or less, still more preferably 280 or more and 600 or less, and most preferably 300 or more and 500 or less. .

  The isocyanate index (INDEX) is calculated by the following equation.

INDEX = number of equivalents of isocyanate / (number of equivalents of polyol + number of equivalents of water) x 100
here,
Number of equivalents of isocyanate = number of used polyisocyanates x NCO content (%) / molecular weight of 100 / NCO,
Number of equivalents of polyol = OHV × number of parts used of polyol ÷ molecular weight of KOH, OHV is hydroxyl value of the polyol (mg KOH / g),
The number of equivalents of water = the number of used parts of water × the number of OH groups of water / the molecular weight of water. In the above formula, the unit of usage is mass (g), the molecular weight of NCO group is 42, and the NCO content is the ratio of NCO group in the polyisocyanate compound represented by mass%, and the formula For convenience of unit conversion, the molecular weight of KOH is 56.1, the molecular weight of water is 18, and the number of OH groups in water is 2.

  The catalyst may be contained in a polyol composition, and the polyol composition may be mixed with a polyisocyanate compound and a catalyst to form a polyurethane / polyurethane foam.

As a catalyst, a trimerization catalyst and a urethane catalyst (a resinification catalyst, a foaming catalyst) are mentioned.
The trimerization catalyst promotes the formation of isocyanurate by reacting the isocyanates with each other.

Nitrogen-containing aromatic compounds such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol and 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine as trimerization catalysts ;
Alkali metal salts of carboxylic acids such as potassium acetate, potassium 2-ethylhexanoate and potassium octylate;
Tertiary ammonium salts such as trimethyl ammonium salt, triethyl ammonium salt, triphenyl ammonium salt and the like;
Examples thereof include quaternary ammonium salts such as tetramethyl ammonium salt, tetraethyl ammonium and tetraphenyl ammonium salt.

  The trimerization catalyst is preferably 0.1% by mass to 5% by mass, more preferably 0.1% by mass to 1% by mass, still more preferably 0.5% by mass with respect to the mass of the entire mixture for producing a polyurethane. It is contained in the range of mass%-1 mass%. By adding the trimerization catalyst in the above proportion, the trimerization reaction can be sufficiently caused to form a uniform foam.

  Examples of the urethane catalyst include tertiary amines, tin compounds, metal salts of acetylacetone and the like.

  Examples of the tertiary amine include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N, N ′, N ′ ′, N ′ ′-pentamethyldiethylenetriamine, N, N, N ′ -Trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl-N'N'-dimethylaminoethylpiperazine, an imidazole compound in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group And N, N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine, N-methylimidazole, trimethylaminoethylpiperazine, tripropylamine and the like.

  Examples of the tin compound include dibutyltin diacetate and dibutyltin dilaurate.

  Examples of the metal salts of acetylacetone include aluminum acetylacetone, iron acetylacetone, copper acetylacetone, zinc acetylacetone, acetylacetone beryllium, acetylacetone chromium, acetylacetone indium, acetylacetone manganese, acetylacetone molybdenum, acetylacetone titanium, acetylacetone cobalt, acetylacetone vanadium, acetylacetone zirconium and the like. Be

  In a preferred embodiment, the composition of the present invention comprises a tertiary amine as a urethane catalyst. As the urethane catalyst, one or two or more kinds of tertiary amines alone, or a combination of two or more kinds of tertiary amines and other urethane catalysts can be used.

  The content of the urethane catalyst in the composition of the present invention is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 10% by mass, based on the total mass of the mixture for producing a polyurethane. More preferably, it is in the range of 0.1% by mass to 10% by mass. By using a urethane catalyst, a dimerization reaction sufficiently occurs to generate sufficient heat for causing a trimerization reaction, so that a uniform foam can be formed.

  The foam stabilizer may be contained in a polyol composition, and the polyol composition may be mixed with a polyisocyanate compound and a foam stabilizer to form a polyurethane / polyurethane foam.

  Examples of the foam stabilizer include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, and surfactants such as silicone foam stabilizers such as organopolysiloxanes.

  The content ratio of the foam stabilizer can be preferably in the range of 0.1% by mass to 10% by mass, based on the total mass of the mixture for producing the polyurethane.

  The foam stabilizer may be used alone or in combination of two or more.

  The blowing agent promotes the foaming of the urethane resin. As a foaming agent, it has 3 or 4 carbon atoms such as HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane), etc. Hydrofluorocarbons and water may be mentioned, and only hydrofluorocarbons may be used, but the combination of hydrofluorocarbons and water is preferred.

  The content ratio of the foaming agent can be preferably in the range of 0.1% by mass to 30% by mass, relative to the mass of the whole mixture for producing a polyurethane, 0.1% by mass to 18% by mass Is more preferably in the range of 0.5% by mass to 18% by mass, and most preferably in the range of 1% by mass to 10% by mass.

  When the range of the blowing agent is in the above range, foaming is promoted, and the density of the resulting molded article can be reduced.

  The blowing agent can be used alone or in combination of two or more.

  When the polyol composition of the present invention contains a tertiary amine, a carboxylic acid can be further blended in order to adjust the reaction rate.

  As carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthate, caprylic acid, pelargonic acid, capric acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid Aliphatic monocarboxylic acids such as linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid; fatty acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid Polyvalent carboxylic acids; hydroxy acids such as lactic acid, malic acid and citric acid; aromatic monocarboxylic acids such as benzoic acid, salicylic acid, gallic acid and cinnamic acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyrolic acid Merlitic acid, mellitic acid, biphenyl dicarboxylic acid, biphenyl tetracarboxylic acid, Oxo carboxylic acids, such as pyruvate; data range aromatic polycarboxylic acids such as carboxylic acids and their anhydrides or mixtures thereof.

  When a carboxylic acid is used, the content ratio of the carboxylic acid in the composition of the present invention is preferably 0.01% by mass to 6% by mass, more preferably 0 based on the mass of the entire mixture for producing a polyurethane. It is from 0.55% by mass to 1% by mass, more preferably from 0.1% by mass to 1% by mass.

  Examples of the filler include pigments, powder flame retardants and inorganic fillers. A filler can select and use a commercial item suitably.

  As the pigment, either an inorganic pigment or an organic pigment can be used, and it is not particularly limited. Specifically, white pigments such as titanium oxide; carbon black, graphite (graphite), iron black Black pigments such as (iron black); blue pigments such as bituminous blue, ultramarine blue, cobalt blue, copper phthalocyanine blue, and indanthrone blue; synthetic yellow iron oxide, transparent iron oxide (yellow), bismuth vanadate, titanium yellow Yellow pigments such as monoazo yellow, disazo yellow, isoindolinone yellow, metal complex salts azo yellow, quinophthalone yellow, benzimidazolone yellow, etc .; red iron oxide, transparent red iron oxide (red), monoazo red, monoazo red, unsubstituted quinacridone red, Azo Lake (Mn salt), quinacridone mazenda, ansanthrone Red pigments such as dianthraquinonil red, perylene maroon, perylene red and diketopyrrolopyrrole chromium vermilion; green pigments such as chlorinated phthalocyanine green and brominated phthalocyanine green; pyrazolone orange, benzimidazolone Other pigments such as orange, dioxazine violet, perylene violet and the like can be mentioned. These pigments can be used alone or in combination of two or more.

  The content ratio of the pigment used in the present invention is preferably 1.5% by mass to 70% by mass, more preferably 4.5% by mass to 40% by mass, based on the total mass of the mixture for producing a polyurethane. More preferably, it is 2% by mass to 15% by mass, and most preferably 4.5% by mass to 30% by mass.

  The powder flame retardant is selected from the group consisting of red phosphorus, boron-containing flame retardant, needle-like filler, phosphate-containing flame retardant, bromine-containing flame retardant, nitrogen-based flame retardant, antimony-containing flame retardant and metal hydroxide It is preferable to contain one or more of the following.

  There is no limitation on the red phosphorus used in the present invention, and a commercially available product can be appropriately selected and used.

  When red phosphorus is used as the filler, the content of red phosphorus is preferably 1.5% by mass to 52% by mass, more preferably 1.5% by mass, based on the mass of the entire mixture for producing a polyurethane. It is in the range of -20% by mass, more preferably 2.0% by mass to 15% by mass, and most preferably 2.0% by mass to 10% by mass.

  Boron-containing flame retardants include borax, boron oxide, boric acid, borate and the like.

  Examples of 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, borates of elements of Groups 4, 12 and 13 of the periodic table and ammonium. Specifically, alkali metal salts of borates such as lithium borate, sodium borate, potassium borate and cesium borate, alkaline earth metal borates such as magnesium borate, calcium borate and barium borate, and borates Acid zirconium, aluminum borate, ammonium borate and the like.

  The boron-containing flame retardant is preferably a borate.

The boron-containing flame retardant can use one or two or more kinds When using a boron-containing flame retardant as a filler, its content ratio is preferably 1 with respect to the mass of the whole mixture for producing a polyurethane. .5% by mass to 52% by mass, more preferably 1.5% by mass to 20% by mass, still more preferably 2.0% by mass to 15% by mass, most preferably 2.0% by mass to 10% by mass %.

  The acicular fillers may be organic fillers or inorganic fillers, but are preferably inorganic fillers. The aspect ratio of the needle-like filler is 5 to 50, preferably 8 to 40, more preferably 10 to 40, still more preferably 10 to 35, and most preferably 8 to 25. Here, the aspect ratio of the filler as referred to in the present specification means the minimum thickness of the maximum length of the filler confirmed in the image obtained by observing the needle-like filler with a scanning electron microscope (with respect to the maximum length). Ratio (also referred to as diameter / thickness ratio) to vertical direction), a sufficient number of fillers, an average of 250 or more.

  The average particle diameter of the acicular fillers is 0.1 μm to less than 15 μm, preferably 0.1 μm to 14 μm, and more preferably 0.3 to 10 μm. The average particle size is determined by an X-ray transmission sedimentation particle size distribution measuring apparatus. The melting point of the needle-like filler is 750 ° C. or more, preferably 800 ° C. or more, and more preferably 1,000 ° C. or more.

  Needle-like inorganic fillers include basic magnesium sulfate, aluminum borate, wollastonite (wollastonite), zonotolite, dawsonite, elastadite, boehmite, rod-like hydroxyapatite, potassium titanate whisker, aluminum borate whisker, magnesium based whisker, Silicon-based whisker, needle-like alumina, needle-like ceramic, asbestos, needle-like calcium carbonate, gypsum fiber, glass fiber, asbestos fiber, silica fiber, silica fiber, alumina fiber, silica / alumina fiber, zirconia fiber, carbon fiber (fibers such as carbon nanotubes) , Needle-like or spherical new carbon such as fullerene), graphite fiber, boron nitride fiber, boron fiber, metal fiber and the like are exemplified.

  The acicular fillers prevent at least one of shrinkage and deformation. In this specification, “shrinkage” refers to a change in length including the length in the length direction, the length in the width direction, and the length in the thickness direction, and “deformation” refers to a shape such as warpage It refers to change, in particular, change in shape in the thickness direction. Needle-like means that the major axis is three or more times the minor axis, and includes not only so-called needle-like but also spindle-like, cylindrical and the like.

  In a preferred embodiment, the needle-like filler is a needle-like inorganic filler having an aspect ratio of 5 to 50 and an average particle diameter of 0.1 μm to less than 15 μm. Preferred needle fillers are wollastonite or potassium titanate whiskers.

  When a needle-like filler is used as the filler, its content is preferably 1 to 30% by mass, more preferably 1 to 25% by mass, and further preferably, based on the mass of the entire mixture for producing a polyurethane. Is 2% by mass to 18% by mass.

  The phosphate-containing flame retardant is, for example, a phosphorus comprising a salt of various phosphoric acids and at least one metal or compound selected from metals of Groups IA to IVB of the periodic table, ammonia, aliphatic amines and aromatic amines. An acid salt can be mentioned. Examples of metals of Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), aluminum and the like.

  Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine and the like.

  As aromatic amines, pyridine, triazine, melamine, ammonium and the like can be mentioned.

  The above-mentioned phosphate-containing flame retardant may be subjected to known water resistance improvement treatment such as treatment with a silane coupling agent or coating with a melamine resin, and a known foaming aid such as melamine or pentaerythritol is added. It is good.

  Specific examples of the phosphate-containing flame retardant include, for example, monophosphate, pyrophosphate, polyphosphate and the like.

  The monophosphate is not particularly limited. For example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, phosphorous acid Monosodium, disodium phosphite, sodium salts such as sodium hypophosphite, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, hypophosphorous acid Potassium salts such as potassium, monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, lithium salts such as lithium hypophosphite, barium dihydrogenphosphate, phosphorus Barium hydrogen oxide, barium triphosphate, barium salts such as barium hypophosphite, magnesium monohydrogen phosphate, hydrogen phosphate Magnesium, trimagnesium phosphate, magnesium salts such as magnesium hypophosphite, calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium salts such as calcium hypophosphite, and the like.

  The polyphosphate is not particularly limited, and examples thereof include ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate ammonium amide, aluminum polyphosphate and the like.

  The phosphate-containing flame retardant can be used alone or in combination of two or more.

  When using a phosphate-containing flame retardant as a filler, its content is preferably 1.5% by mass to 52% by mass, more preferably 1.5% by mass, based on the mass of the entire mixture for producing a polyurethane. % By mass to 20% by mass, more preferably 2.0% by mass to 15% by mass, and most preferably 2.0% by mass to 10% by mass.

  The bromine-containing flame retardant is not particularly limited as long as it is a compound containing bromine in the molecular structure, and examples thereof include aromatic brominated compounds and the like.

  Specific examples of the aromatic brominated compound include, for example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromo) Monomer organic bromine compounds such as phenoxy) ethane, ethylene-bis (tetrabromophthalimide), tetrabromobisphenol A; polycarbonate oligomers manufactured from brominated bisphenol A as a raw material, copolymer of polycarbonate oligomer and bisphenol A, etc. Brominated polycarbonates; diepoxy compounds produced by the reaction of brominated bisphenol A with epichlorohydrin, brominated phenols and epichlorohydrin Brominated epoxy compounds such as monoepoxy compounds obtained by the reaction with: poly (brominated benzyl acrylate); brominated polyphenylene ether; brominated bisphenol A, condensate of cyanuric chloride and brominated phenol; brominated (polystyrene), Brominated polystyrenes such as poly (brominated styrene), cross-linked brominated polystyrene, etc .; halogenated bromine compound polymers such as cross-linked or non-cross-linked brominated poly (-methylstyrene).

  From the viewpoint of controlling the calorific value at the initial stage of combustion, brominated polystyrene, hexabromobenzene and the like are preferable, and hexabromobenzene is more preferable.

  The bromine-containing flame retardant can be used alone or in combination of two or more.

  When a bromine-containing flame retardant is used as the filler, the content is preferably 1.5% by mass to 52% by mass, more preferably 1.5% by mass, based on the mass of the entire mixture for producing a polyurethane. It is preferably 20% by mass, more preferably 2.0% by mass to 15% by mass, and most preferably 2.0% by mass to 10% by mass.

  As a nitrogen-containing flame retardant, melamine derivatives such as melamine, butylmelamine, trimethylolmelamine, hexamethylolmelamine, hexamethoxymethylmelamine, melamine phosphate, cyanuric acid, methyl cyanurate, diethyl cyanurate, trimethyl cyanurate, triethylsiar Cyanuric acid derivatives such as nurate, isocyanuric acid, methyl isocyanurate, N, N'-diethyl isocyanurate, tris methyl isocyanurate, tris ethyl isocyanurate, bis (2-carboxyethyl) isocyanurate, 1,3,5-tris (2-Carboxyethyl) isocyanurate, isocyanuric acid derivatives such as tris (2,3-epoxypropyl) isocyanurate, melamine cyanurate, melamine isocyanurate, ammonium carbonate And the like.

  The nitrogen-containing flame retardant can be used alone or in combination of two or more.

  When a nitrogen-containing flame retardant is used as the filler, its content is preferably 1.5% by mass to 52% by mass, more preferably 1.5% by mass, based on the total mass of the mixture for producing a polyurethane. It is preferably 20% by mass, more preferably 2.0% by mass to 15% by mass, and most preferably 2.0% by mass to 10% by mass.

  As an antimony containing flame retardant, an antimony oxide, an antimonate, a pyroantimonate etc. are mentioned, for example.

  Examples of antimony oxide include antimony trioxide and antimony pentoxide.

  Examples of the antimonate salt include sodium antimonate, potassium antimonate and the like.

  As a pyroantimonate, for example, sodium pyroantimonate, potassium pyroantimonate and the like can be mentioned.

  The antimony-containing flame retardant is preferably antimony oxide.

  The antimony-containing flame retardant may be used alone or in combination of two or more.

  When an antimony-containing flame retardant is used as a filler, its content is preferably 1.5% by mass to 52% by mass, more preferably 1.5% by mass, based on the mass of the entire mixture for producing a polyurethane. It is preferably 20% by mass, more preferably 2.0% by mass to 15% by mass, and most preferably 2.0% by mass to 10% by mass.

  The metal hydroxides used in the present invention include, for example, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, copper hydroxide, vanadium hydroxide And tin hydroxide.

  One or two or more metal hydroxides can be used.

  The content of the metal hydroxide is preferably 1.5% by mass to 52% by mass, more preferably 1.5% by mass to 20% by mass, further preferably, based on the mass of the entire mixture for producing a polyurethane. Is 2.0% by mass to 15% by mass, most preferably 2.0% by mass to 10% by mass.

  When the filler contains a powder flame retardant, the total content of the powder flame retardant is preferably 4.5% by mass to 70% by mass, more preferably 4 with respect to the mass of the whole mixture for producing a polyurethane. 0.5 mass% to 40 mass%, more preferably 4.5 mass% to 30 mass%.

  If the flame retardant is in the above-mentioned range, the molded article can be prevented from cracking the fine residue formed by the heat of fire, and the foaming of the composition is not inhibited.

  The inorganic filler is not particularly limited. For example, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, carbonate Magnesium, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salts such as calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber , Glass beads, Silica parn, Aluminum nitride, Boron nitride, Silicon nitride, Carbon black, Graphite, Carbon fiber, Carbon parn, Charcoal powder, Various metal powders, Potassium titanate, Magnesium sulfate, Lead zirconate titanate, Miniumuporeto, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powder, slag fibers, fly ash, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber, and the like.

  The inorganic filler may be used alone or in combination of two or more.

  The content ratio of the inorganic filler used in the present invention is preferably 1.5% by mass to 70% by mass, more preferably 4.5% by mass to 40% by mass with respect to the total mass of the mixture for producing a polyurethane. %, More preferably 2% by mass to 15% by mass, and most preferably 4.5% by mass to 30% by mass.

  The polyol composition of the present invention can contain phosphoric acid ester as a liquid flame retardant. The phosphoric acid ester is not particularly limited, but it is preferable to use monophosphoric acid ester, condensed phosphoric acid ester and the like.

  The monophosphate ester is not particularly limited, and, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixyl phosphate, Tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthylphosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphe Nyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenyl phosphine oxide, tricresyl phosphine oxide, diphenyl methane phosphonate, diethyl phenyl phosphonate, Examples include lysylsinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphafaenansene, tris (β-chloropropyl) phosphate and the like.

  The condensed phosphoric acid ester is not particularly limited. For example, trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name PX-200) And hydroquinone poly (2,6-xylyl) phosphates and condensed phosphoric esters such as condensates thereof.

  Examples of commercially available condensed phosphoric acid esters include resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade name CR-741), aromatic condensed phosphate ester (trade name CR747), resorcinol Polyphenyl phosphate (made by ADEKA, trade name Adekastab PFR), bisphenol A polycresyl phosphate (trade name FP-600, FP-700) etc. can be mentioned.

  Among the above, it is preferable to use a monophosphate because the effect of reducing the viscosity in the composition before curing and the effect of reducing the initial calorific value are high, and tris (β-chloropropyl) phosphate is used. Is more preferred.

  One or two or more kinds of phosphoric acid esters can be used.

  When using phosphoric ester as a liquid flame retardant, the content rate is preferably 1.5% by mass to 52% by mass, more preferably 1.5% by mass with respect to the mass of the whole mixture for producing a polyurethane. % To 20% by mass, more preferably 2.0% to 15% by mass, and most preferably 2.0% to 10% by mass.

  Examples of the metal oxide fine particles include silicon oxide, aluminum oxide, titanium oxide and zirconium oxide, and the surface of these metal oxide fine particles is subjected to a hydrophobizing treatment. The hydrophobization treatment can be carried out according to a conventional method, for example, hydrophobization of hydroxyl groups of hydrophilic metal oxide fine particles having hydroxyl groups on the surface, such as halogenated aliphatic hydrocarbon, monochlorosilane, dichlorosilane, octylsilane, silicone oil, etc. The thing hydrophobized by the agent is mentioned. The average primary particle size of the metal oxide fine particles is preferably 3 nm to 60 nm, more preferably 5 nm to 50 nm, and still more preferably 5 nm to 40 nm.

  The water absorption amount of the metal oxide fine particles is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more.

  The content ratio of the metal oxide fine particles is preferably 0.1% by mass to 5% by mass, more preferably 0.3% by mass to 4% by mass, still more preferably, based on the mass of the entire mixture for producing a polyurethane. It is 0.5% by mass to 3% by mass, most preferably 0.5% by mass to 2% by mass.

  The composition of the present invention may be, if necessary, an antioxidant such as phenol, amine or sulfur, a heat stabilizer, a metal damage inhibitor, an antistatic agent, as long as the object of the present invention is not impaired. Auxiliary components such as stabilizers, crosslinking agents, lubricants, softeners, pigments, tackifying resins and the like, and tackifiers such as polybutene and petroleum resins can be included.

  In one preferable embodiment of the present invention, when the total content of the urethane catalyst is X mass% and the content of the carboxylic acid is Y mass%, X> Y, and the content of the urethane catalyst is the above It is more than the content of carboxylic acid. By setting the content as such, the reaction rate can be expected to be improved because the reaction is not suppressed excessively.

  In a preferred embodiment of the present invention, the catalyst, foam stabilizer, blowing agent, filler and metal oxide fine particles are provided as a polyol composition comprising a polyol and these components (reacted with a polyisocyanate compound to produce a polyurethane foam Polyol solution composition to obtain

  The polyol composition can be obtained by kneading the respective components using a known device such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a lice machine, a planetary stirrer and the like. .

  Next, the method for curing the polyol composition according to the present invention will be described.

  When the polyol composition and the polyisocyanate compound are mixed, the viscosity increases with time and the flowability is lost.

  For example, polyurethane can be obtained as a foam by injecting a mixture of a polyol composition and a polyisocyanate compound (hereinafter referred to as "foamed urethane composition") into a container such as a mold and curing the mixture. . Alternatively, polyurethane can be obtained as a foam by spraying a urethane foam composition onto a structure to be coated and curing it.

  The viscosity of the polyol composition is preferably 100 to 3000 mPas, more preferably 300 to 2000 mPas, and still more preferably 500 to 1500 mPas.

  When obtaining a polyurethane foam, heat or pressure can be applied.

Although the thickness of the polyurethane foam is not particularly limited, it is, for example, 1 to 50 mm. In particular, in the case of 20 mm or more, the effect of suppressing deformation during the heat generation test is exhibited, which is advantageous. In one embodiment, the polyurethane foam of the present invention is a 100 mm × 100 mm × 20 mm (length direction × width direction × thickness direction) molded body heated at a radiant heat intensity of 50 kW / m ^{2 for} 20 minutes according to the ISO-5660 test method. The dimensions in the length direction and the width direction of the molded product after heating with respect to the time before heating are greater than 95 mm, and the deformation in the thickness direction is less than 10 mm.

  The polyurethane foam of the present invention preferably has a specific gravity in the range of 0.020 to 0.130 from the viewpoint of easy handling, more preferably in the range of 0.020 to 0.100, and more preferably 0.030 to 0. The range of 080 is more preferable, and the range of 0.030 to 0.060 is most preferable.

  The polyurethane foam of the present invention is preferably heated under temperature conditions of 30 ° C. to 900 ° C. at a rate of 10 ° C./min, and the measurement atmosphere is an air flow of 100 mL / min under air conditions. The mass reduction rate (1-sample mass after heating / sample mass before heating) x 100 (%) in TG / DTA measurement is 5% or less. Therefore, the foam can maintain high shape retention even after heating.

  Next, applications of the polyurethane foam according to the present invention will be described.

  The polyurethane foam can be molded into thin panels and placed in structures such as buildings, furniture, cars, trains, ships and the like. Alternatively, a polyurethane foam layer can be formed on the surface of the structure by spraying a urethane foam composition onto the structure.

The fire resistance of the foamed urethane composition and polyurethane foam of the present invention can be evaluated by a corn calorimeter test according to the test method of ISO-5660. Specifically, in this fire resistance test, a polyurethane foam is cut into a length of 10 cm, a width of 10 cm and a thickness of 5 cm to prepare a sample for corn calorimeter test. Next, using a sample for corn calorimeter test, the total calorific value when heated at a radiant heat intensity of 50 kW / m ^{2 for} 20 minutes is measured with a corn calorimeter according to the test method of ISO-5660.

By "nonflammable" herein, (1) the total amount of heat generated by the heating start after 20 minutes at the radiant heat intensity 50 kW / m ² is 8 MJ / ^{m 2} or less, (2) heating starts after 20 min Heating conditions exceeding 200 kW / m ² do not continue for more than 10 seconds, (3) Conditions of (1) to (3) that deformation such as cracks or holes harmful to fire protection does not occur in 20 minutes after the start of heating Say what has all.

  EXAMPLES Although an Example is given to the following and this invention is more concretely demonstrated to it, this invention is not limited to these.

Examples 1 to 10 and Comparative Examples 1 to 5 Production of polyurethane foam and evaluation of its performance 1. Production of Polyurethane Foam Molding Each component used in this example is shown in Table 1, and the blending amount of each component and the evaluation result are shown in Table 2.

2. Performance evaluation The performance evaluation of the obtained polyurethane foam molded body was performed on the following reference | standard. The results are shown in Table 2.
(1) Caking A material other than the foaming agent shown in Table 2 was put into a 500 ml plastic container, and stirred with a small stirrer at 3000 rpm for 5 minutes. Thereafter, a foaming agent was charged and stirred at 3000 rpm for 1 minute. The obtained sample (polyol composition) was charged into a 300 ml mayonnaise bottle manufactured by Tokyo Glass Instruments Co., Ltd., and 200 g was stored in a 40 ° C. oven.
After one month, the sample was taken out, the spoon was dropped gently, and if it reached the bottom of the container by its own weight, it was ○, and if it hit a hard layer on the way, it was ×.

(2) Viscosity Measured with a spindle BM3, rotation speed 60 rpm, temperature 25 ° C. using a viscosity BM type viscometer.

(3) 1 g of water absorption sample was put into an oven at 20 ° C. and 85%, and the increase in weight after 60 minutes was measured to calculate the weight increase rate.
In addition, since 0.01% or less has a large measurement error, it describes as <0.01.

Claims (6)

What is claimed is: 1. A polyol composition comprising a polyol compound, a foaming agent, a filler, and metal oxide fine particles, wherein the foaming agent is a hydrofluorocarbon, and a hydroxyl group is present on the surface of the metal oxide fine particles. The polyol composition according to claim 1, further comprising a catalyst and / or a foam stabilizer. The polyol composition according to claim 1, wherein the filler comprises a flame retardant. The polyol composition according to claim 1, wherein the metal portion of the metal oxide fine particles is aluminum, titanium or silicon. The polyol composition according to claim 1, wherein the water absorption amount of the metal oxide fine particles is 0.2% by mass or more. The polyurethane foam containing the metal oxide fine particle in which the hydroxyl group exists in the surface manufactured by mixing the polyol composition in any one of the said Claims 1-5 with a polyisocyanate compound.