JP7221580B2 - Expandable polyurethane composition and polyurethane foam - Google Patents

Description

The present invention relates to expandable polyurethane compositions and polyurethane foams.

Foamed polyurethane resin is used as a heat insulating material for buildings such as collective housing such as condominiums, detached houses, various facilities of schools, and commercial buildings. Since urethane resins have low flame retardancy, it is known that increasing the ratio of isocyanurate in the resin is effective in improving this. However, if the isocyanurate ratio is too high, the flyability (brittleness) deteriorates, so it was necessary to optimize the isocyanurate ratio in order to achieve both high flame retardancy and flyability.

For example, Patent Documents 1-3 describe rigid polyurethane foams with high flame retardancy and low flyability and methods for making them.

JP 2000-230028 JP 2004-339269 JP 2010-24247

However, none of the rigid polyurethane foams of Patent Documents 1 to 3 has been confirmed to satisfy high flame retardancy. Furthermore, for excellent flame retardancy, it is important that the rigid polyurethane foam does not collapse easily after burning, that is, the flyability after burning is important. No mention is made of improving the

An object of the present invention is to provide a foamable polyurethane composition and a polyurethane foam having high flame retardancy and improved flyability after combustion.

The inventors of the present application conducted various studies to achieve the above object, and found that high flame retardancy and improved post-combustion flyability can be achieved by controlling the peak intensity of a specific wavelength in IR measurement within a specific range. The inventors have found that a foamable polyurethane composition and a polyurethane foam having both properties can be obtained, and have completed the present invention.

That is, the present invention is as follows.

Section 1. A foamable polyurethane composition obtained by reacting a polyol with an aromatic polyisocyanate, said foamable polyurethane composition comprising a foam stabilizer, a catalyst, a blowing agent, and a flame retardant, said cured foamable polyurethane. In the IR measurement at a position 5 mm to 10 mm from the surface layer of the composition, the maximum value in the range of 1390 to 1430 cm ^-1 is 1500 to 1520 cm when the average value in the range of 1900 to 2000 cm ^-1 is set to zero. A foaming composition characterized by being 1.5 times or more and 2.0 times or less the maximum value in the range of ^-1 .

Section 2. Item 2. The foamable polyurethane composition according to Item 1, wherein the foamable polyurethane composition is a reaction mixture of a polyol premix containing a polyol, a foam stabilizer, a catalyst, a blowing agent, and a flame retardant, and an aromatic isocyanate. Polyurethane composition.

Item 3. Item 3. A polyurethane foam obtained by curing the foamable polyurethane composition according to Item 1 or 2.

Section 4. Item 4. The polyurethane foam according to item 3, which is a molded article.

The expandable polyurethane compositions of the present invention combine excellent flame retardancy with improved flyability.

Graph of IR measurement results for samples of cured foamable polyurethane compositions of Examples 1-2 and Comparative Examples 1-2.

SUMMARY OF THE INVENTION The present invention is a foamable polyurethane composition obtained by reacting a polyol with an aromatic polyisocyanate, the foamable polyurethane composition comprising a foam stabilizer, a catalyst, a blowing agent, and a flame retardant to produce a cured foam. In the IR measurement at a position 5 mm to 10 mm from the surface layer of the polyurethane composition, the maximum value in the range of 1390 to 1430 cm ^-1 is 1500 to 1500 when the average value in the range of 1900 to 2000 cm ^-1 is set to zero. It includes a foamable polyurethane composition characterized by being 1.5 times or more and 2.0 times or less the maximum value in the range of 1520 cm ^-1 . As used herein, the term "cured" refers to the state after the components of the foamable polyurethane composition are mixed, foamed and cured to complete the reaction.

Foamable polyurethane compositions contain polyols, aromatic polyisocyanates, foam stabilizers, catalysts, blowing agents, flame retardants and optionally other ingredients. Aromatic polyisocyanate as the main ingredient of the urethane resin and polyol as the curing agent of the urethane resin are cured by a chemical reaction to form the urethane resin. Each component will be described below.

1. Aromatic polyisocyanate Aromatic polyisocyanate, which is the main ingredient of urethane resin, includes, for example, phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and the like.

One or more aromatic polyisocyanates can be used. Diphenylmethane diisocyanate is preferable as the main component of the urethane resin because of its ease of use and availability.

2. Polyol Polyols that are curing agents for urethane resins include, for example, polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, and polyether polyols.

Polylactone polyols include, for example, polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.

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

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

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

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

Polyester polyols include, for example, 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, Examples include condensates of hydroxycarboxylic acids and the above polyhydric alcohols.

Specific examples of polybasic acids 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, and neopentyl glycol. .

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

Examples of polymer polyols include polymers obtained by graft-polymerizing ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate to aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, and polybutadiene. Examples include polyols, modified polyols of polyhydric alcohols, and hydrogenated products thereof.

Modified polyols of polyhydric alcohols include, for example, polyhydric alcohols that have been modified by reacting them with alkylene oxide.

Examples of polyhydric alcohols include trihydric alcohols such as glycerin and trimethylolpropane; pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc.; Tetra- to octahydric alcohols such as derivatives thereof; phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene , anthrol, 1,4,5,8-tetrahydroxyanthracene, 1-hydroxypyrene, and other phenolic polybutadiene polyols; castor oil polyols; hydroxyalkyl (meth)acrylate (co)polymers and polyfunctionals such as polyvinyl alcohol (for example Polyols having a functional group number of 2 to 100) and condensates (novolacs) of phenol and formaldehyde can be mentioned.

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

AO includes AO having 2 to 6 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propyroxide, 1,2- butylene oxide, 1,4-butylene oxide and the like.

Among these, PO, EO and 1,2-butylene oxide are preferred, and PO and EO are more preferred, 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 polyol, for example, in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogens, at least one alkylene oxide such as ethylene oxide, propylene oxide and tetrahydrofuran is subjected to ring-opening polymerization. The polymer obtained is mentioned.

Low-molecular-weight active hydrogen compounds having two or more active hydrogens include, for example, bisphenol A, ethylene glycol, propylene glycol, butylene glycol, diols such as 1,6-hexanediol, and triols such as glycerin and trimethylolpropane. , ethylenediamine, butylenediamine and the like.

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

Among them, polyester polyols having a molecular weight of 200 to 800 are more preferably used, and polyester polyols having a molecular weight of 300 to 500 are more preferably used.

The isocyanate index is the equivalent ratio of the isocyanate groups of the polyisocyanate to the hydroxyl groups of the polyol expressed as a percentage. If the value exceeds 100, it means that the isocyanate groups are in excess of the hydroxyl groups.
The range of the isocyanate index of the urethane resin used in the present invention is not particularly limited, but it is preferably in the range of 150 to 1000, more preferably in the range of 200 to 800, and even more in the range of 250 to 700. preferable. The isocyanate index (INDEX) is calculated by the following method.

INDEX = number of equivalents of isocyanate / (number of equivalents of polyol + number of equivalents of water) x 100

Here, the number of equivalents of isocyanate = number of parts of polyisocyanate used × NCO content (%) ÷ 100/molecular weight of NCO,
Equivalent number of polyol = OHV x number of parts of polyol used / molecular weight of KOH, OHV is hydroxyl value of polyol (mg KOH / g),
Equivalent number of water=number of parts of water used×number of OH groups of water/molecular weight of water. In the above formula, the unit used is weight (g), the molecular weight of NCO is 42, the molecular weight of KOH is 56,100, the molecular weight of water is 18, and the number of OH groups in water is 2.

3. Foam Stabilizer Examples of foam stabilizers include polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ethers, surfactants such as silicone foam stabilizers such as organopolysiloxane, and the like. The blending amount of the foam stabilizer is appropriately set according to the urethane resin. preferred.

One or two or more foam stabilizers can be used.

4. catalyst
Catalysts include, for example, trimerization catalysts.

The trimerization catalyst reacts and trimerizes the isocyanate groups contained in the aromatic polyisocyanate, which is the main ingredient of the polyurethane resin, and promotes the formation of isocyanurate rings.

In order to promote the formation of isocyanurate rings, for example, tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tris(dialkylaminoalkyl) as a trimerization catalyst Nitrogen-containing aromatic compounds such as hexahydro-S-triazine; carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate and potassium octerate; tertiary compounds such as trimethylammonium salts, triethylammonium salts and triphenylammonium salts Ammonium salts; quaternary ammonium salts such as tetramethylammonium salts, tetraethylammonium salts, tetraphenylammonium salts and the like can be used.

The amount of the trimerization catalyst is preferably in the range of 0.6 parts by weight to 10 parts by weight, more preferably in the range of 0.6 parts by weight to 8 parts by weight, with respect to 100 parts by weight of the urethane resin. It is more preferably in the range of 0.6 to 6 parts by weight, most preferably in the range of 0.6 to 3.0 parts by weight. When the amount is 0.6 parts by weight or more, the problem of inhibition of trimerization of the aromatic polyisocyanate does not occur.

In addition to the trimerization catalyst, examples of the catalyst include the following catalysts: alkylated polyalkylenepolyamine, triethylamine, N″,N″-pentamethyldiethylenetriamine, N,N,N′-trimethylaminoethyl-ethanolamine, etc. Amine-based urethanization catalyst; N-methylmorpholinebis(2-dimethylaminoethyl)ether, N,N,N',bis(2-dimethylaminoethyl)ether, N-methyl,N'-dimethylaminoethylpiperazine, Nitrogen atom-containing catalysts such as imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group.
The amount of the urethanization catalyst added is not limited, but it is preferably in the range of 0 to 10 parts by weight, more preferably in the range of 0.05 to 10 parts by weight, with respect to 100 parts by weight of the urethane resin. .1 to 7 parts by weight is more preferred.

The total amount of the trimerization catalyst and the catalyst other than the trimerization catalyst, when contained in the foamable polyurethane composition, is 0.6 weight parts per 100 parts by weight of the urethane resin. parts by weight to 10 parts by weight, more preferably 0.6 parts by weight to 8 parts by weight, still more preferably 0.6 parts by weight to 6 parts by weight, and 0.2 parts by weight. Most preferably, it ranges from 6 parts by weight to 3.0 parts by weight.

When the amount is 0.6 parts by weight or more, the problem of inhibition of formation of urethane bonds does not occur, and when the amount is 10 parts by weight or less, an appropriate foaming speed can be maintained and handling is easy.

One or two or more catalysts can be used.

5. Foaming Agent The foaming agent promotes foaming of the urethane resin. Examples of foaming agents include water; low-boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane; dichloroethane, propyl chloride, isopropyl chloride, butyl chloride; chlorinated aliphatic hydrocarbon compounds such as isobutyl chloride, pentyl chloride and isopentyl chloride; fluorine compounds such _{as CHF3} , _CH2F2 , _CH3F ; trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane, (For example, hydrochlorofluorocarbon compounds such as HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)); HFC-245fa (1, 1,1,3,3-pentafluoropropane), hydrofluorocarbons such as HFC-365mfc (1,1,1,3,3-pentafluorobutane); ether compounds such as diisopropyl ether, or mixtures of these compounds, etc. and inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas and carbon dioxide gas.

Although the amount of the foaming agent to be blended is not particularly limited, it is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the urethane resin. The foaming agent is more preferably in the range of 0.1 to 18 parts by weight, more preferably in the range of 0.5 to 18 parts by weight, with respect to 100 parts by weight of the urethane resin. Most preferably it ranges from parts by weight to 10 parts by weight.

When the amount of water is 0.1 parts by weight or more, foaming is promoted, and the density of the resulting molded article can be reduced. can be prevented.

One or two or more foaming agents can be used.

6. Flame Retardant The flame retardant comprises at least one selected from red phosphorus, phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, boron -containing flame retardants, antimony-containing flame retardants, and metal hydroxides. Preferably, the flame retardant comprises red phosphorus and at least one selected from phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, boron -containing flame retardants, antimony-containing flame retardants, and metal hydroxides. include.

Commercially available flame retardants can be appropriately selected and used.
The red phosphorus used in the present invention is not limited, and commercially available products can be appropriately selected and used.
The amount of red phosphorus to be added is preferably in the range of 3 to 18 parts by weight, more preferably in the range of 3 to 10 parts by weight, per 100 parts by weight of the urethane resin.

Although the phosphate used in the present invention is not particularly limited, it is preferable to use a monophosphate, a condensed phosphate, or the like.

Monophosphates are not particularly limited, but examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, tris(phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl 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, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resircinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), phosphaphenanthrene, tris(β-chloropropyl) phosphate and the like.

The condensed phosphate is not particularly limited, but examples include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly(di-2,6-xylyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name PX-200 ), hydroquinone poly(2,6-xylyl) phosphate, and condensed phosphates such as these condensates.

Commercially available condensed phosphates include, for example, resorcinol polyphenyl phosphate (trade name CR-733S), bisphenol A polycresyl phosphate (trade name CR-741), aromatic condensed phosphate (trade name CR747), and resorcinol. Polyphenyl phosphate (manufactured by ADEKA, trade name ADEKA STAB PFR), bisphenol A polycresyl phosphate (trade names FP-600, FP-700) and the like can be mentioned.

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 heat generation amount, and tris(β-chloropropyl) phosphate is used. is more preferred.

Phosphate ester can be used alone or in combination of two or more.

The amount of the phosphate ester added is preferably in the range of 1.5 parts by weight to 52 parts by weight, more preferably in the range of 1.5 parts by weight to 20 parts by weight, with respect to 100 parts by weight of the urethane resin. It is preferably in the range of 2.0 to 15 parts by weight, most preferably in the range of 2.0 to 10 parts by weight.

When the range of the phosphate ester is 1.5 parts by weight or more, it is possible to prevent cracking of the dense residue formed when the foamed polyurethane composition is exposed to fire. Foaming of the foamable polyurethane composition is not inhibited.

Also, the phosphate-containing flame retardant used in the present invention contains phosphoric acid. The phosphoric acid used in the phosphate-containing flame retardant is not particularly limited, but includes various phosphoric acids such as monophosphoric acid, pyrophosphoric acid, polyphosphoric acid, and combinations thereof.

Phosphate-containing flame retardants include, for example, phosphoric acid 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. Acid salts may be mentioned. Examples of metals of Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum.

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

Aromatic amines include pyridine, triazine, melamine, and ammonium.

The above phosphate-containing flame retardant may be treated with a silane coupling agent, coated with a melamine resin, or otherwise subjected to a known water resistance improvement treatment. can be

Specific examples of phosphate-containing flame retardants include monophosphates, pyrophosphates, polyphosphates, and the like.

Although the monophosphate is not particularly limited, for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate, disodium phosphate, trisodium phosphate, phosphorous acid - sodium salts such as sodium, disodium phosphite, sodium hypophosphite, monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, hypophosphorous acid Potassium salts such as potassium, lithium phosphate, dilithium phosphate, trilithium phosphate, lithium phosphite, dilithium phosphite, lithium hypophosphite and other lithium salts, barium dihydrogen phosphate, phosphorus Barium salts such as barium hydrogen oxyphosphate, tribarium phosphate, barium hypophosphite, magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium hypophosphite, etc., calcium dihydrogen phosphate , calcium hydrogen phosphate, tricalcium phosphate, and calcium hypophosphite, and zinc salts such as zinc phosphate, zinc phosphite, and zinc hypophosphite.

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

Among these, it is preferable to use a monophosphate, and it is more preferable to use ammonium dihydrogen phosphate, since the self-extinguishing property of the phosphate-containing flame retardant is improved.

One or more phosphate-containing flame retardants can be used.

The amount of the phosphate-containing flame retardant used in the present invention is preferably in the range of 1.5 parts by weight to 52 parts by weight, more preferably 1.5 parts by weight to 20 parts by weight, with respect to 100 parts by weight of the urethane resin. parts by weight, more preferably 2.0 to 15 parts by weight, most preferably 2.0 to 10 parts by weight.

The bromine-containing flame retardant used in the present invention 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 aromatic brominated compounds include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromo Monomeric organic bromine compounds such as phenoxy)ethane, ethylene-bis(tetrabromophthalimide), tetrabromobisphenol A; polycarbonate oligomers produced from brominated bisphenol A, copolymers of polycarbonate oligomers and bisphenol A, etc. brominated epoxy compounds such as diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin, and monoepoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin; poly(brominated benzyl acrylate) brominated polyphenylene ethers; condensates of brominated bisphenol A, cyanuric chloride and brominated phenols; brominated polystyrenes such as brominated (polystyrene), poly(brominated styrene), cross-linked brominated polystyrene; Examples include halogenated bromide 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 preferred, and hexabromobenzene is more preferred.

Bromine-containing flame retardants can be used alone or in combination of two or more.

The amount of the bromine-containing flame retardant used in the present invention is preferably in the range of 1.5 parts by weight to 52 parts by weight with respect to 100 parts by weight of the urethane resin, and 1.5 parts by weight to 20 parts by weight. It is more preferably in the range of 2.0 parts by weight to 15 parts by weight, and most preferably in the range of 2.0 parts by weight to 10 parts by weight.

The boron-containing flame retardant used in the present invention includes borax, boron oxide, boric acid, borates, and the like.

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

Examples of borates include borates of alkali metals, alkaline earth metals, elements of Groups 4, 12 and 13 of the periodic table, and ammonium.

Specifically, 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; Zirconium borate, zinc borate, aluminum borate, ammonium borate and the like.

The boron-containing flame retardant used in the present invention is preferably borate, more preferably zinc borate.

One or more boron-containing flame retardants can be used.
The addition amount of the boron-containing flame retardant used in the present invention is preferably in the range of 1.5 parts by weight to 52 parts by weight with respect to 100 parts by weight of the urethane resin, and 1.5 parts by weight to 20 parts by weight. It is more preferably in the range of 2.0 parts by weight to 15 parts by weight, and most preferably in the range of 2.0 parts by weight to 10 parts by weight.

Antimony-containing flame retardants used in the present invention include, for example, antimony oxide, antimonate, pyroantimonate and the like.

Examples of antimony oxide include antimony trioxide and antimony pentoxide.

Examples of antimonates include sodium antimonate and potassium antimonate.

Examples of pyroantimonate include sodium pyroantimonate and potassium pyroantimonate.

The antimony-containing flame retardant used in the present invention is preferably antimony oxide.

One or more antimony-containing flame retardants can be used.

The amount of the antimony-containing flame retardant added is preferably in the range of 1.5 to 52 parts by weight, more preferably in the range of 1.5 to 20 parts by weight, with respect to 100 parts by weight of the urethane resin. It is more preferably in the range of 2.0 to 15 parts by weight, and most preferably in the range of 2.0 to 10 parts by weight.

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

1 type, or 2 or more types can be used for a metal hydroxide.

The amount of metal hydroxide added is preferably in the range of 1.5 to 52 parts by weight, more preferably in the range of 1.5 to 20 parts by weight, with respect to 100 parts by weight of the urethane resin. It is more preferably in the range of 2.0 to 15 parts by weight, and most preferably in the range of 2.0 to 10 parts by weight.

The total amount of the flame retardant used in the present invention is preferably in the range of 4.5 to 70 parts by weight, more preferably in the range of 4.5 to 40 parts by weight, per 100 parts by weight of the urethane resin. is more preferable, and the range of 4.5 to 30 parts by weight is even more preferable.

When the flame retardant is in the range of 4.5 parts by weight or more, it is possible to prevent cracking of the dense residue formed by the heat of a fire in a molded article made of the foamable polyurethane composition, and when it is 70 parts by weight or less, foaming can be prevented. foaming of the elastic polyurethane composition is not inhibited.

In a preferred embodiment, the foamable polyurethane composition contains 50 to 85 parts by weight of the aromatic polyisocyanate and 0.0 parts by weight of the foam stabilizer based on 100 parts by weight of the urethane resin composed of the aromatic polyisocyanate and the polyol. 1 to 10 parts by weight, 3.5 to 10 parts by weight of a catalyst, 0.1 to 30 parts by weight of a blowing agent, and 4.5 to 70 parts by weight of a flame retardant. Phosphorus is in the range of 3 parts by weight to 18 parts by weight, and at least one selected from phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, and metal hydroxides One is from 1.5 parts by weight to 52 parts by weight. In this case, the flame retardant is preferably 4.5 to 52 parts by weight, more preferably 4.5 to 30 parts by weight. At least one selected from phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, boron-containing flame retardants, antimony-containing flame retardants, and metal hydroxides is a boron-containing flame retardant, and the preferred range is 1. It ranges from 5 parts by weight to 9 parts by weight.

7. Other Ingredients The foamable polyurethane composition may further contain an inorganic filler. The inorganic filler is not particularly limited, but examples include silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, and carbonate. Magnesium, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salts such as calcium silicate, talc, clay, mica, wollastonite, montmorillonite, bentonite, activated clay, sepiolite, Imogolite, sericite, glass fiber, glass beads, silica palun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon palun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, zirconium titanate Acid lead, aluminum porate, molybdenum sulfide, silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber, and the like.

One or two or more inorganic fillers can be used.

The foamable polyurethane composition may contain antioxidants such as phenolic, amine and sulfur antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, Auxiliary ingredients such as stabilizers, crosslinkers, lubricants, softeners, pigments, tackifying resins, tackifiers such as polybutenes, petroleum resins, etc. may be included.

1 above. ~7. As the components of are mixed and the foamable polyurethane composition reacts and cures, its viscosity changes over time. Therefore, before using the foamable polyurethane composition, the foamable polyurethane composition is divided into two or more parts to prevent the foamable polyurethane composition from reacting and hardening. When using the foamable polyurethane composition, the foamable polyurethane composition can be obtained by putting together the foamable polyurethane composition that has been divided into two or more pieces.

When dividing the foamable polyurethane composition into two or more parts, each component of the foamable polyurethane composition divided into two or more parts does not start to cure independently, and after mixing each component of the foamable polyurethane composition, Each component may be divided so that the curing reaction begins.

Mixing and curing of the foamable polyurethane composition may be carried out at room temperature, or each component may be preheated. At low temperatures, the reaction does not proceed sufficiently and flame retardancy is not exhibited, so the temperature for mixing and curing is preferably 0° C. or higher, more preferably 5° C. or higher.

The above foam stabilizers, catalysts, blowing agents and flame retardants may be mixed with either the polyol or the aromatic polyisocyanate, or may be provided separately from the polyol and the aromatic polyisocyanate, but are preferably Foaming agents, catalysts, blowing agents, and flame retardants are provided as polyol premixes comprising polyols and these ingredients. In addition, the above 7. Other components of may also be mixed with either the polyol or the aromatic polyisocyanate, or may be provided separately from the polyol and aromatic polyisocyanate, but are preferably included in the polyol premix.

A polyol, an aromatic polyisocyanate, a foam stabilizer, a catalyst, a blowing agent, and a flame retardant, preferably an aromatic polyisocyanate, and a polyol premix containing the polyol, a foam stabilizer, a catalyst, a blowing agent, and a flame retardant. The resulting foamable polyurethane composition upon mixing is expanded and cured to form a polyurethane foam. The present invention also includes polyurethane foams formed from foamable polyurethane compositions containing the above components.

The foamable urethane composition of the present invention has an IR (infrared absorption analysis) measurement at a position 5 mm to 10 mm from the surface layer of the cured foamable polyurethane composition, and the average value in the range of 1900 to 2000 cm ^-1 is zero. The maximum value in the range of 1390 to 1430 cm ^-1 is 1.5 times or more and 2.0 times or less than the maximum value in the range of 1500 to 1520 cm ^-1 when adjusted to the values. The reason for measuring the IR at a position 5 mm to 10 mm from the surface layer of the foamable polyurethane composition (or polyurethane foam) is that the surface layer, which easily dissipates heat, was avoided and the position where the composition was stable was measured. The peak maximum in the range 1390-1430 cm ^-1 represents the nurate and the peak maximum in the range 1500-1520 cm ^-1 represents the aromatic ring.

In this specification, the ratio of the maximum value in the range of 1390 to 1430 cm to the maximum value in the range of 1500 to 1520 cm ^-1 (maximum value in ^the range of 1390 to 1430 ^cm / 1500 to 1520 cm ^-1 range maximum) is referred to as the isocyanurate ratio. Unexpectedly, this isocyanurate ratio can be used as an index for evaluating compatibility between flame retardancy and flyability of a foamable urethane composition. When the isocyanurate ratio is 1.5 times or more and 2.0 times or less, the expandable urethane composition and the molded article formed therefrom have both excellent flame retardancy and low flyability after combustion.

If the isocyanurate ratio is less than 1.5, the flame retardancy will be poor, and if the isocyanurate ratio exceeds 2.0, the flyability of the foamable urethane composition will be deteriorated.

The flame retardancy of the urethane foam composition and polyurethane foam of the present invention can be evaluated by a cone calorimeter test in accordance with the test method of ISO-5660. Specifically, in this flame retardancy test, a polyurethane foam made of an expandable polyurethane composition is cut into a length of 10 cm, a width of 10 cm and a thickness of 5 cm to prepare a cone calorimeter test sample. Next, using a cone calorimeter test sample, the total calorific value is measured by a cone calorimeter when heated for 20 minutes at a radiant heat intensity of 50 kW/m ² in accordance with the test method of ISO-5660.

As used herein, "flyability" refers to the flyability after combustion, in particular the flyability of a cured expandable polyurethane composition or polyurethane foam after flame retardancy testing. Flyability after burning is evaluated whether or not the cured foamable polyurethane composition or polyurethane foam sample crumbles into powder and does not stick to the finger when touched with a finger.

The use of the foamable polyurethane composition and polyurethane foam of the present invention is not particularly limited, but they are usually used to fill openings or gaps in buildings. Here, the term “building” includes any structure that constitutes a building, and includes not only building structural materials such as walls, ceilings, roofs, and floors, but also windows (double sliding windows, casement windows, double-hung windows). etc.), shoji, doors (that is, doors), doors, sliding doors, and fittings such as ranma are also included. An “opening” refers to any opening in a building, including joints between structural members of a building and holes in a single structural member. Between two facing members or parts, especially between structural members, between structural members and fittings, between fittings and fittings, or between structural members or fittings and furniture (such as a kitchen sink) Refers to the resulting opening.

Moreover, the foamable polyurethane composition is not only directly filled into the openings or gaps of the building, but is also poured into a mold or the like and has dimensions (length, width, and thickness) that are suitable for the openings or gaps of the building. or cut to desired dimensions (length, width, and thickness) as a polyurethane foam by discharging it from the mixing vessel to another location, then inserting the polyurethane foam into an opening or crevice in a building. May be worn.

Polyisocyanurate foam obtained by foaming and curing a foamable polyurethane composition has excellent waterproof, airtight, and fireproof properties. It is possible to effectively block the intrusion of gas and the like generated by combustion. EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these.

Production Example 1 Production of Foamable Polyurethane Composition and Its Foam According to the formulation shown in Table 1, the foamable polyurethane compositions according to Examples 1 and 2 and Comparative Examples 1 and 2 were prepared by (1) a polyol premix and ( 2) Aromatic polyisocyanate was prepared in two portions. The details of each component in the table are as follows.

(1) Polyol premix polyol p-phthalate polyester polyol (manufactured by Kawasaki Chemical Industries, product name: Maximol RLK-087, hydroxyl value = 200 mgKOH/g)
・Foam stabilizer Polyalkylene glycol-based foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193)
・ Catalyst trimerization catalyst (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-TRX)
Trimerization catalyst (manufactured by San-Apro Co., Ltd., product name: U-CAT 18X)
Urethane catalyst (alkylated polyalkylene polyamine) (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-TT)
Urethane catalyst (manufactured by San-Apro Co., Ltd., product name: U-CAT 202)
A mixture of a urethanization catalyst (tertiary amine) and ethylene glycol (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-DM70)
・Blowing agent Water HFC HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Central Glass Co., Ltd.) and HFC-245fa (1,1,1,3,3-pentafluoropropane, Nippon Solvay Co., Ltd.) ), mixing ratio HFC-365mfc:HFC-245fa = 7:3, hereinafter referred to as “HFC”)
・ Flame retardant tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)
Red phosphorus (manufactured by Rin Kagaku Kogyo, product name: Nova Excel 140)
Zinc borate (manufactured by Hayakawa Trading Co., Ltd., product name: Firebrake ZB)
・ Inorganic filler wollastonite (SiO ₂ · CaO) (manufactured by Kinseimatec, product name: SH-1250)

(2) Aromatic polyisocyanate
4,4'-diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Wanhua Chemical Japan Co., Ltd., product name: PM200)
According to the formulation shown in Table 1 below, the components of (1) polyol premix were weighed into a 1,000 mL polypropylene beaker and hand-stirred at 25° C. for 1 minute. (2) Aromatic polyisocyanate was added to the kneaded mixture of (1) polyol premix components after stirring, and the mixture was stirred with a hand mixer for about 10 seconds to prepare an expandable polyurethane resin composition. The obtained foamable polyurethane resin composition lost its fluidity over time, and a foam of the foamable polyurethane resin composition was obtained. The foam was evaluated according to the following criteria, and the results are shown in Table 1 (ratio of each component is shown in parts by weight per 100 parts by weight of urethane resin).

Test Example 1 IR measurement
Measurement was performed by the total reflection (ATR) method using an IR measuring instrument (FT-IR Microscope 600 UMA manufactured by Varian).

IR was measured at positions 5 mm to 10 mm from the surface layer of the cured foamable polyurethane compositions of Examples 1 and 2 and Comparative Examples 1 and 2. A graph of the IR measurement is shown in FIG.

As shown in Table 1, the isocyanurate ratios of Examples 1 and 2 were 1.58 and 1.72, respectively, and the isocyanurate ratios of Comparative Examples 1 and 2 were 1.49 and 2.02, respectively.

Test Example 2 Flame Retardancy Test A cone calorimeter test sample of 10 cm x 10 cm x 5 cm was cut out from the cured foam of the foamable polyurethane resin composition, and conformed to ISO-5660 with a radiant heat intensity of 50 kW/m ^{2 .} The maximum heat release rate and the total heat release amount were measured when heating for 20 minutes at .

This measurement method is a test method stipulated by the General Building Research Institute, a public institution stipulated in Article 108-2 of the Enforcement Ordinance of the Building Standards Act, as a test method that corresponds to the standard by the cone calorimeter method. It conforms to the test method of ISO-5660.

If the total calorific value of the cone calorimeter after heating for 20 minutes is 8 MJ/m ² or ^less , it passes the test. was marked as ○. As shown in Table 1, Examples 1 and 2 and Comparative Example 2 passed, and Comparative Example 1 failed.

Test Example 3 Flyability Test The cured foam after the flame retardancy test in Test Example 2 was touched with a finger, and the sample crumbled into powder and was rated x when the powder stuck to the finger, and ○ when the powder did not stick. As shown in Table 1, Examples 1 and 2 and Comparative Example 1 were good, and Comparative Example 2 was poor.

Claims (3)

A foamable polyurethane composition used to form a polyurethane foam, comprising:
The foamable polyurethane composition comprises an aromatic polyisocyanate, a polyol, a foam stabilizer, a catalyst, a blowing agent, and a flame retardant;
The flame retardant includes red phosphorus, a phosphate ester, and a boron-containing flame retardant,
The catalyst includes a trimerization catalyst and a urethanization catalyst,
The trimerization catalyst comprises a quaternary ammonium salt,
The urethanization catalyst contains an imidazole compound,
The foaming agent contains an organic physical foaming agent,
With respect to 100 parts by weight of the total amount of the aromatic polyisocyanate and the polyol,
Containing the red phosphorus in the range of 3 to 18 parts by weight,
Containing the phosphoric acid ester in the range of 1.5 to 52 parts by weight,
containing the boron-containing flame retardant in the range of 1.5 to 52 parts by weight,
containing the trimerization catalyst in the range of 0.6 to 10 parts by weight,
containing the urethanization catalyst in the range of 0.05 to 10 parts by weight,
The isocyanate index of the urethane resin composed of the aromatic polyisocyanate and the polyol is in the range of 150 to 1000,
In IR measurement at a position 5 mm to 10 mm from the surface of a polyurethane foam obtained by curing a foamable polyurethane composition, the average value in the range of 1900 to 2000 cm ^-1 is adjusted to zero value, and the average value is 1390 to 1430 cm ^-1 . The maximum value of the range is 1.5 times or more and 2.0 times or less than the maximum value of the range of 1500 to 1520 cm ^-1 when the average value of the range of 1900 to 2000 cm ^-1 is adjusted to zero. A foamable polyurethane composition. A polyurethane foam obtained by curing the foamable polyurethane composition of claim 1 . 3. The polyurethane foam according to claim 2 , which is a molded article.

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