JP7029338B2 - Polyol composition and polyurethane foam - Google Patents

Description

The present invention relates to polyol compositions and polyurethane foams.

Concrete reinforced with reinforcing bars is used as a structural material to increase the strength of buildings in apartment houses such as condominiums, detached houses, various school facilities, and outer walls of commercial buildings.

On the other hand, since concrete has heat storage and cold storage properties, there are disadvantages that the inside of the building is heated by the heat accumulated in the summer, and the inside of the building is cooled as a result of cooling the concrete in the cold season in the winter. In order to reduce the influence of the outside temperature on the inside of the building for a long time through such concrete, the concrete is usually heat-insulated.

Therefore, as a heat insulating layer, a rigid polyurethane foam having flame retardancy against fire is used.

Patent Document 1 discloses a flame retardant composition for polyurethane containing red phosphorus and an anti-sedimentant.

Japanese Unexamined Patent Publication No. 2012-219127

An object of the present invention is to provide a polyol composition that does not hard cake (solidify to the extent that it cannot be re-stirred) when the premix is stored for a long period of time for one month or longer, and a polyurethane foam using the same.

The present invention provides the following polyol composition and a polyurethane foam using the same.
Item 1. A polyol composition containing a polyol compound, a foaming agent, a filler, and metal oxide fine particles, wherein the foaming agent is a hydrofluoroolefin, and the surface of the metal oxide fine particles is hydrophobized.
Item 2. Item 2. The polyol composition according to Item 1, which comprises a catalyst and / or a defoaming agent.
Item 3. Item 2. The polyol composition according to Item 1 or 2, wherein the filler contains a powder flame retardant.
Item 4. Item 2. The polyol composition according to Item 1 or 2, wherein the filler contains an inorganic filler.
Item 5. Item 2. The polyol composition according to Item 1 or 2, wherein the filler contains a pigment.
Item 6. Item 6. The polyol composition according to any one of Items 1 to 5, wherein the metal portion of the metal oxide fine particles is aluminum, titanium, or silicon.
Item 7. Item 2. The polyol composition according to any one of Items 1 to 6, wherein the water absorption of the metal oxide fine particles is 0.5% by mass or less.
Item 8. A polyurethane foam containing metal oxide fine particles whose surface has been hydrophobized, which is produced by mixing the polyol composition according to any one of Items 1 to 7 with a polyisocyanate compound.

According to the present invention, the polyol composition can be used by re-stirring even after storage for 1 month or longer.

The polyol composition of the present invention contains a polyol compound, a foaming agent (hydrofluoroolefin), a filler, and metal oxide fine particles whose surface has been hydrophobized. This polyol composition can be mixed with a polyisocyanate compound to obtain a polyurethane foam.

The polyol composition preferably further contains a catalyst and / or a defoaming agent.

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

Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, polyvalerolactone glycol and the like.

Examples of the polycarbonate polyol include a polyol obtained by dealcoholization of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentandiol, hexanediol, octanediol, and nonanediol with diethylene carbonate, dipropylene carbonate, and the like. And so on.

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

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

Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

Examples of the polyester polyol include 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 ε-caprolactone and α-methyl-ε-caprolactone. Examples thereof include a condensate of hydroxycarboxylic acid and the above-mentioned polyhydric alcohol and the like.

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

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

Examples of the polymer polyol include polybutadiene, which is 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. Examples thereof include polyols, modified polyols of polyhydric alcohols, and hydrogenated products thereof.

Examples of the modified polyol of the polyhydric alcohol include those modified by reacting the polyhydric alcohol as a raw material with an alkylene oxide.

Polyhydric alcohols include, for example, trihydric alcohols such as glycerin and trimethylolpropane; pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methyl glucoside and the like. Tetra-octavalent alcohols such as derivatives; phenol, fluoroglycercin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene, Phenolic polybutadiene polyols such as anthrol, 1,4,5,8-tetrahydroxyanthracene, 1-hydroxypyrene; castor oil polyols; (co) polymers of hydroxyalkyl (meth) acrylates and polyfunctional (eg functional) such as polyvinyl alcohols. Examples thereof include polyols (groups 2 to 100) and condensates (novolak) of phenol and formaldehyde.

The method for modifying the polyhydric alcohol is not particularly limited, but a method for adding an alkylene oxide (hereinafter abbreviated as AO) is preferably used.

The AO includes 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. Examples thereof include oxide, 1,4-butylene oxide and the like.

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

As the polyether polymer, for example, at least one kind of alkylene oxide such as ethylene oxide, propylene oxide and tetrahydrofuran is ring-opened polymerized in the presence of at least one kind such as a low molecular weight active hydrogen compound having two or more active hydrogens. Examples thereof include the polymer obtained by subjecting the mixture.

Examples of 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.

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

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.

Examples of the polyisocyanate compound as the main agent of the urethane resin include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.

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

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.

Urethane prepolymer may be used as the polyisocyanate compound. Examples of the urethane prepolymer include those obtained by reacting the above-mentioned polyol compound with the above-mentioned polyisocyanate compound in excess.

One or more polyisocyanate compounds can be used. The main agent of the urethane resin is preferably an aromatic polyisocyanate such as polyphenylpolymethylene polyisocyanate because it is easy to use and easily available.

In the composition of the present invention, the isocyanate index is preferably 200 or more, more preferably 260 or more and 700 or less, further 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 formula.

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

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

Examples of the catalyst include a trimerization catalyst and a urethane catalyst (resinification catalyst, foaming catalyst). The trimerization catalyst promotes the production of isocyanurates by reacting isocyanates with each other.

As the trimerization catalyst, nitrogen-containing aromatic compounds such as tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, and 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine ;
Carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate, potassium octylate, etc.
Tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt;
Examples thereof include quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt and tetraphenylammonium 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, based on the total mass of the mixture for producing polyurethane. It is contained in the range of 1% by mass to 1% by mass. By adding the quantification catalyst at the above ratio, the quantification reaction can be sufficiently carried out and a uniform foam can be formed.

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

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

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

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

In a preferred embodiment, the composition of the invention comprises a tertiary amine as a urethane catalyst. As the urethane catalyst, only one or two or more kinds of tertiary amines can be used, or a combination of two or more kinds composed 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 polyurethane. , More preferably in the range of 0.1% by mass to 10% by mass. By using the urethane catalyst, the dimerization reaction is sufficiently generated and sufficient heat is generated to cause the trimerization reaction, so that a uniform foam can be formed.

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

Examples of the defoaming agent include a polyoxyalkylene defoaming agent such as polyoxyalkylene alkyl ether and a surfactant such as a silicone defoaming agent such as organopolysiloxane.

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

One type or two or more types of foam stabilizers can be used.

The foaming agent promotes the foaming of the urethane resin. Examples of the foaming agent include hydrofluoroolefins having 3 or 4 carbon atoms such as trans-1-chloro-3,3,3-trifluoropropene and water, and hydrofluoroolefins alone may be used, but hydrofluoroolefins and water. Is preferable in combination with.

The content ratio of the foaming agent can be preferably in the range of 0.1% by mass to 30% by mass, and 0.1% by mass to 18% by mass, based on the total mass of the mixture for producing polyurethane. It is more preferably in the range of 0.5% by mass to 18% by mass, more preferably in the range of 1% by mass to 10% by mass, and most preferably in the range of 1% by mass to 10% by mass.

When the range of the foaming agent is within the above range, foaming is promoted and the density of the obtained molded product can be reduced.

One type or two or more types of foaming agents can be used.

When the polyol composition of the present invention contains a tertiary amine, a carboxylic acid can be further added for the purpose of adjusting the reaction rate.

Carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid and linoleic acid. , Linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid and other aliphatic monocarboxylic acids; Group polycarboxylic acids; hydroxy acids such as lactic acid, malic acid, citric acid; aromatic monocarboxylic acids such as benzoic acid, salicylic acid, gallic acid, cinnamic acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyro Aromatic polyvalent carboxylic acids such as merit acids, melitonic acids, biphenyldicarboxylic acids, biphenyltetracarboxylic acids, naphthalenedicarboxylic acids; oxocarboxylic acids such as pyruvate; and anhydrides or mixtures thereof.

When a carboxylic acid is used, the content 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 total mass of the mixture for producing polyurethane. It is 0.05% by mass to 1% by mass, more preferably 0.1% by mass to 1% by mass.

Examples of the filler include pigments, powder flame retardants, and inorganic fillers. As the filler, a commercially available product can be appropriately selected and used.

As the pigment, both an inorganic pigment and an organic pigment can be used, and the pigment is not particularly limited, but specifically, a white pigment such as titanium oxide; carbon black, graphite (graphite), iron black. Black pigments such as (iron black); blue pigments such as dark blue, ultramarine, cobalt blue, copper phthalocyanine blue, and indanslon blue; synthetic yellow iron oxide, transparent red iron oxide (yellow), bismus vanadate, titanium yellow , Monoazo Yellow, Disazo Yellow, Isodolinone Yellow, Metallic Salt Azo Yellow, Kinoftalone Yellow, Benz Imidazolone Yellow, etc. Yellow pigments; Red pigments such as azolake (Mn salt), quinacridone magenta, anthronthron orange, dianthraquinonyl red, perylene maroon, perylene red, diketopyrrolopyrrole chrome vermilion; chlorinated phthalocyanine green, brominated phthalocyanine green, etc. Green pigments; other pigments such as pyrazolone orange, benzimidazolone orange, dioxazine violet, perylene violet and the like. These pigments can be used alone or in combination of two or more.

The content of the pigment used in the present invention is preferably 1% by mass to 70% by mass, more preferably 1.5% by mass to 50% by mass, still more preferably, with respect to the total mass of the mixture for producing polyurethane. Is 2% by mass to 40% by mass, 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 above.

The red phosphorus used in the present invention is not limited, 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 total mass of the mixture for producing polyurethane. It is in the range of about 20% by mass, more preferably 2.0% by mass to 15% by mass, and most preferably 2.0% by mass to 10% by mass.

Examples of the boron-containing flame retardant include borax, boron oxide, boric acid, borate and the like.

Examples of the boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, tetraboron pentoxide and the like.

Examples of the borate include alkali metals, alkaline earth metals, elements of Groups 4, 12, and 13 of the Periodic Table, and ammonium borates. Specifically, an alkali metal borate salt such as lithium borate, sodium borate, potassium borate, and cesium borate, an alkaline earth metal salt borate such as magnesium borate, calcium borate, and barium borate, boro Examples thereof include zirconium acid, aluminum borate, and ammonium borate.

The boron-containing flame retardant is preferably borate.

One or more of the boron-containing flame retardants can be used. When the boron-containing flame retardant is used as a filler, the content ratio thereof is preferably 1 with respect to the total mass of the mixture for producing polyurethane. It is in the range of 5.5% by mass to 52% by mass, more preferably 1.5% by mass to 20% by mass, further preferably 2.0% by mass to 15% by mass, and most preferably 2.0% by mass to 10% by mass. %.

The needle-shaped filler may be an organic filler or an inorganic filler, but is preferably an inorganic filler. The aspect ratio of the needle-shaped 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 referred to in the present specification is the minimum thickness (relative to the maximum length) of the maximum length of the filler confirmed in the image obtained by observing the needle-shaped filler with a scanning electron microscope. Ratio (also referred to as diameter / thickness ratio) to (vertical), sufficient number of fillers, average of 250 or more.

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

Needle-shaped inorganic fillers include basic magnesium sulfate, aluminum borate, wollastonite (silica ashstone), zonotrite, dosonite, elestadite, boehmite, rod-shaped hydroxyapatite, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, etc. Silicon-based whisker, acicular alumina, acicular ceramic, asbestos, acicular calcium carbonate, gypsum fiber, glass fiber, asbestos fiber, silica fiber, alumina fiber, silica-alumina fiber, zirconia fiber, carbon fiber (fiber such as carbon nanotube) (Including spherical new carbon such as shape, needle shape or fullerene), graphite fiber, boron nitride fiber, boron fiber, metal fiber and the like are exemplified.

The needle-like filler prevents at least one of shrinkage and deformation. As used herein, "shrinkage" refers to a change in length including length in the length direction, length in the width direction, and length in the thickness direction, and "deformation" refers to a shape such as warpage. It refers to a change, especially a change in shape in the thickness direction. The needle shape means that the major axis is three times or more the minor axis, and includes not only the so-called needle shape but also the spindle shape, the cylindrical shape and the like.

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

When a needle-shaped filler is used as the filler, the content ratio thereof is preferably 1 to 30% by mass, more preferably 1% by mass to 25% by mass, still more preferably, with respect to the total mass of the mixture for producing polyurethane. Is 2% by mass to 18% by mass.

The phosphate-containing flame retardant is, for example, phosphorus composed of a salt of various phosphates and at least one metal or compound selected from the metals of the Periodic Table IA to IVB, ammonia, aliphatic amines, and aromatic amines. Phosphate can be mentioned. Examples of the metal of Group IA to IVB of the Periodic Table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.

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

Examples of the aromatic amine include pyridine, triazine, melamine and the like.

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

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

The monophosphate is not particularly limited, but for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, and phosphite. Sodium salts such as monosodium, disodium phosphite, sodium hypophosphite, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, hypophosphite Potassium salts such as potassium, monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphate, dilithium phosphate, lithium salts such as lithium hypophosphite, barium dihydrogen phosphate, phosphorus Barium salts such as barium hydrogen phosphate, tribarium phosphate, barium hypophosphite, magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium salts such as magnesium hypophosphite, calcium dihydrogen phosphate , Calcium hydrogen phosphate, tricalcium phosphate, calcium salts such as calcium hypophosphite, and the like.

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

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

When a phosphate-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 polyurethane. It is 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 its molecular structure, and examples thereof include aromatic brominated compounds.

Specific examples of the aromatic brominated compound include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, and bis (pentabromo). Fenoxy) Ethane, ethylene-bis (tetrabromophthalimide), tetrabromobisphenol A and other monomer organic bromine compounds; polycarbonate oligomers produced from brominated bisphenol A as a raw material, copolymers of polycarbonate oligomers and bisphenol A, etc. Bromineed polycarbonate; diepoxy compounds 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; Condensate of brominated bisphenol A, cyanur chloride and brominated phenol; brominated polystyrene such as brominated (polystyrene), poly (brominated styrene), cross-broken brominated polystyrene; cross-linked or non-cross-linked brominated Examples thereof include halogenated bromine compound polymers such as 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.

One or more kinds of bromine-containing flame retardants can be used.

When a bromine-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 polyurethane. It is about 20% by mass, more preferably 2.0% by mass to 15% by mass, and most preferably 2.0% by mass to 10% by mass.

Examples of nitrogen-based flame retardants include melamine derivatives such as melamine, butyl melamine, trimethylol melamine, hexamethylol melamine, hexamethoxymethyl melamine, and melamine phosphate, cyanuric acid, methyl cyanurate, diethyl cyanurate, trimethyl cyanurate, and triethyl cyanurate. Cyanuric acid derivatives such as nurate, isocyanuric acid, methyl isocyanurate, N, N'-diethyl isocyanurate, trismethyl isocyanurate, trisethyl isocyanurate, bis (2-carboxyethyl) isocyanurate, 1,3,5-tris Examples thereof include isocyanuric acid derivatives such as (2-carboxyethyl) isocyanurate and tris (2,3-epoxypropyl) isocyanurate, melamine cyanurate, melamine isocyanurate, and ammonium carbonate.

One or more nitrogen-based flame retardants can be used.

When a nitrogen-based 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 polyurethane. It is about 20% by mass, more preferably 2.0% by mass to 15% by mass, and most preferably 2.0% by mass to 10% by mass.

Examples of the antimony-containing flame retardant include antimony oxide, antimony acid salt, pyroantimony acid salt and the like.

Examples of antimony oxide include antimony trioxide and antimony pentoxide.

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

Examples of the pyroantimonate include sodium pyroantimonate, potassium pyroantimonate and the like.

The antimony-containing flame retardant is preferably antimony oxide.

As the antimony-containing flame retardant, one kind or two or more kinds can be used.

When an antimony-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 polyurethane. It is about 20% by mass, more preferably 2.0% by mass to 15% by mass, and most preferably 2.0% by mass to 10% by mass.

Examples of the metal hydroxide used in the present invention include magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, nickel hydroxide, zirconium hydroxide, titanium hydroxide, copper hydroxide, and vanadium hydroxide. , Tin hydroxide and the like.

As the metal hydroxide, one kind or two or more kinds can be used.

The content ratio of the metal hydroxide is preferably 1.5% by mass to 52% by mass, more preferably 1.5% by mass to 20% by mass, still more preferably, with respect to the total mass of the mixture for producing 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 total mass of the mixture for producing polyurethane. It is 5.5% by mass to 40% by mass, more preferably 4.5% by mass to 30% by mass.

If the flame retardant is in the above range, the compact residue formed by the heat of the fire in the molded product can be prevented from cracking, and the foaming of the composition is not hindered.

The inorganic filler is not particularly limited, but for example, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, and carbon dioxide. Magnesium, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salts such as calcium silicate, talc, clay, mica, montmorillonite, bentonite, active white clay, sepiolite, imogolite, sericite, glass fiber , Glass beads, silica parun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon parun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum pollate, sulfurized Examples thereof include molybdenum, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber and the like.

As the inorganic filler, one kind or two or more kinds can be used.

The content of the inorganic filler used in the present invention is preferably 1% by mass to 70% by mass, more preferably 1.5% by mass to 50% by mass, based on the total mass of the mixture for producing polyurethane. It is more preferably 2% by mass to 40% by mass, and most preferably 4.5% by mass to 30% by mass.

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

The monophosphoric acid ester is not particularly limited, but for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, etc. Tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyldiphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-Acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, Examples thereof include tricresylphosphinoxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resylsinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, tris (β-chloropropyl) phosphate and the like.

The condensed phosphate ester is not particularly limited, but for example, trialkylpolyphosphate, resorcinolpolyphenyl phosphate, resorcinolpoly (di-2,6-kisilyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name PX-200). ), Hydroquinonepoly (2,6-xylyl) phosphate and condensed phosphate esters such as condensates thereof.

Examples of commercially available condensed phosphate esters include resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade name CR-741), aromatic condensed phosphate ester (trade name CR747), and resorcinol. Examples thereof include polyphenyl phosphate (manufactured by ADEKA, trade name Adecastab PFR), bisphenol A polycresyl phosphate (trade names FP-600, FP-700) and the like.

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

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

When a phosphoric acid ester is used as a liquid flame retardant, 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 polyurethane. It is in the range of% 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.

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 hydrophobized. The hydrophobization treatment can be carried out according to a conventional method. For example, the hydroxyl group of hydrophilic metal oxide fine particles having a hydroxyl group on the surface is hydrophobized with a halogenated aliphatic hydrocarbon, monochlorosilane, dichlorosilane, octylsilane, silicone oil or the like. Examples thereof include those that have been hydrophobized with an agent. Hydrophobic groups such as dimethylsilyl, trimethylsilyl, dimethylpolysiloxane, dimethylsiloxane, alkylsilyl, aminoalkylsilyl, and methacrylsilyl are present on the surface of the metal oxide fine particles by the hydrophobic treatment. 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 further preferably 5 nm to 40 nm.

The water absorption of the metal oxide fine particles is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.2% by mass or less.

The content 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, with respect to the total mass of the mixture for producing polyurethane. It is 0.5% by mass to 3% by mass, most preferably 0.5% by mass to 2% by mass.

The compositions of the present invention contain, as necessary, phenol-based, amine-based, sulfur-based and other antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, as long as they do not impair the object of the present invention. It can contain auxiliary components such as stabilizers, cross-linking agents, lubricants, softeners, pigments and tackifier resins, and antistatic agents such as polybutene and petroleum resins.

In one of the preferred embodiments of the present invention, when the total content of the urethane catalyst is X% by mass and the content of the carboxylic acid is Y% by mass, X> Y, and the content of the urethane catalyst is the above-mentioned. It is equal to or higher than the content of carboxylic acid. By setting such a content, the reaction is not excessively suppressed, so that the reaction rate can be expected to be improved.

In a preferred embodiment of the present invention, the catalyst, foam stabilizer, foaming agent, filler and metal oxide fine particles are provided as a polyol composition containing a polyol and these components (polyurethane foam by reacting with a polyisocyanate compound). Polyol solution composition for obtaining).

The polyol composition can be obtained by kneading each component using a known device such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a Raikai machine, and a planetary stirrer.

Next, a 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 the passage of time and the fluidity is lost.

For example, polyurethane can be obtained as a foam by injecting a mixture of a polyol composition and a polyisocyanate compound (hereinafter, abbreviated as "urethane foam composition") into a container such as a mold and curing it. .. Alternatively, polyurethane can be obtained as a foam by spraying the urethane foam composition onto the 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 even more preferably 500 to 1500 mPas.

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

The thickness of the polyurethane foam is not particularly limited, but is, for example, 1 to 50 mm. In particular, when it is 20 mm or more, the effect of suppressing deformation during the heat generation test is exhibited, which is advantageous. In one embodiment, in the polyurethane foam of the present invention, a 100 mm × 100 mm × 20 mm (length direction × width direction × thickness direction) molded body was 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 body after heating with respect to those before heating are larger 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 because it is easy to handle, more preferably in the range of 0.020 to 0.100, and 0.030 to 0. It is more preferably in the range of 080, and most preferably in the range of 0.030 to 0.060.

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

Next, an application example of the polyurethane foam according to the present invention will be described.

The polyurethane foam can be formed into a thin panel and placed in a structure such as a building, furniture, an automobile, a train, or a ship. Alternatively, the polyurethane foam layer can be formed on the surface of the structure by spraying the urethane foam composition onto the structure.

The fire resistance of the urethane foam composition and the polyurethane foam of the present invention can be evaluated by a cone calorimeter test based on 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 a cone calorimeter test. Next, using the corn calorimeter test sample, the total calorific value when heated for 20 minutes at a radiant heat intensity of 50 kW / m ² is measured by the corn calorimeter according to the test method of ISO-5660.

In the present specification, "nonflammable" means (1) a total calorific value of 8 MJ / m ² or less for 20 minutes after the start of heating at a radiant heat intensity of 50 kW / m ² , and (2) 20 minutes after the start of heating. Conditions (1) to (3) that the heat generation rate exceeding 200 kW / m ² does not continue for more than 10 seconds, and (3) no deformation such as cracks or holes harmful to fire prevention occurs within 20 minutes after the start of heating. It means the one that has all of.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Examples 1 to 11 and Comparative Examples 1 to 4
Table 1 shows each component used in Examples and Comparative Examples, and Table 2 shows the blending amount of each component.

The performance of the obtained polyol composition and metal oxide fine particles was evaluated according to the following criteria. The results are shown in Table 2.
(1) With respect to the caking polyol composition, materials other than the foaming agent shown in Table 2 were put into a 500 ml plastic container, and the mixture was stirred with a small stirrer at 3000 rpm for 5 minutes. Then, the foaming agent was added, and the mixture was stirred at 3000 rpm for 1 minute. 200 g of the obtained sample (polypoly composition) was put into a 300 ml mayonnaise bottle manufactured by Tokyo Glass Instruments Co., Ltd. and stored in an oven at 40 ° C. One month later, the sample was taken out, the spatula was gently lowered, and if it reached the bottom of the container by its own weight, it was marked as ○, and if it did not hit the hard layer on the way, it was marked as ×.
(2) Viscosity The polyol composition was measured with a BM type viscometer at a spindle BM3, a rotation speed of 60 rpm, and a temperature of 25 ° C.
(3) Amount of water absorption For the metal oxide fine particles, 1 g of a sample was put into an oven at 20 ° C. and 85%, and the weight increase after 60 minutes was measured to calculate the weight increase rate. Since the measurement error is large when it is 0.01% or less, it is described as <0.01.

Claims (8)

The foaming agent contains a polyol compound, a foaming agent, a filler, and metal oxide fine particles, and the metal oxide fine particles have a dimethylsilyl group, a trimethylsilyl group, a dimethylpolysiloxane group, and a dimethylsiloxane group on the surface thereof. , A polyol composition comprising one or more hydrophobic groups selected from an alkylsilyl group, an aminoalkylsilyl group, and a methacrylicsilyl group . The polyol composition according to claim 1, which comprises a catalyst and / or a defoaming agent. The polyol composition according to claim 1 or 2, wherein the filler contains a powder flame retardant. The polyol composition according to claim 1 or 2, wherein the filler contains an inorganic filler. The polyol composition according to claim 1 or 2, wherein the filler contains a pigment. The polyol composition according to any one of claims 1 to 5, wherein the metal portion of the metal oxide fine particles is aluminum, titanium, or silicon. The polyol composition according to any one of claims 1 to 6, wherein the water absorption of the metal oxide fine particles is 0.5% by mass or less. A polyurethane foam containing metal oxide fine particles whose surface has been hydrophobized, which is produced by mixing the polyol composition according to any one of claims 1 to 7 with a polyisocyanate compound.