JP6450115B2 - Urethane resin composition - Google Patents

Description

  The present invention relates to a urethane resin composition.

A polyurethane foam can be obtained by curing the urethane resin composition. Since this polyurethane foam has moderate flexibility, it is widely used for cushions for supporting human bodies, as well as cushioning materials, heat insulating materials, and sound insulation materials for vehicles, home appliances, electronic devices and the like.
However, although the polyurethane foam is excellent in flexibility, it has a drawback that it is easy to burn. For this reason, examination which makes the said polyurethane foam hard to burn is performed.

Regarding the flame retardancy of polyurethane foam, a resin composition containing a polyether polyol, isocyanate, a foaming agent and a flame retardant, wherein the flame retardant includes a thermally expandable graphite, a phosphorus flame retardant and a melamine flame retardant. One urethane resin composition has been proposed (Patent Document 1).
This first urethane resin composition contains thermally expandable graphite. This thermally expandable graphite expands by heat from a fire or the like to form a nonflammable expansion residue.
However, in the case of the polyurethane foam obtained from the first urethane resin composition, until the combustible component in the polyurethane foam is not burned out, the expansion residue is formed by the thermally expandable graphite contained in the combustible component. May continue.
Even if the expansion residue of the polyurethane foam does not burn, the fire spreads from the place where the polyurethane foam is installed such as a vehicle, a household appliance, or an electronic device while the combustible component contained in the polyurethane foam is burning. There's a problem.

Further, regarding the flame retardancy of polyurethane foam, a second urethane resin composition is proposed in which 1 to 70 parts by mass of ammonium polyphosphate having a polymerization degree of 10 to 40 is blended with respect to 100 parts by mass of polyol (Patent Document 2). ).
Furthermore, a third urethane resin composition using diphenylmethane diisocyanate having an NCO index in the range of 1.8 to 3.0 and containing a melamine resin and an organic phosphorus system has also been proposed (Patent Document 3).

JP 2011-148903 A JP 2007-191554 A Japanese Patent Laid-Open No. 2001-20028

However, each of the above prior arts has a problem that the polyurethane foam obtained easily ignites.
The objective of this invention is providing the urethane resin composition which is excellent in a softness | flexibility and excellent in a flame retardance.

  As a result of intensive studies by the present inventors in order to solve the above problems, the weight average molecular weight of the polyol compound is in the range of 1000 to 20000, red phosphorus is an essential component, and in addition to red phosphorus, phosphate esters The urethane resin composition comprising a combination of at least one selected from the group consisting of a phosphate-containing flame retardant, a bromine-containing flame retardant and a metal hydroxide meets the object of the present invention, and completes the present invention. It came to do.

That is, the present invention
[1] including a polyisocyanate compound, a polyol compound, a foaming agent, a foam stabilizer and an additive,
The polyol compound has a weight average molecular weight in the range of 1000 to 20000,
The additive comprises red phosphorus as an essential component, in addition to the red phosphorus, in combination with at least one selected from the group consisting of phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants and metal hydroxides. A urethane resin composition is provided.

One of the present invention is
[2] The additive is in the range of 4.5 to 70 parts by weight based on 100 parts by weight of the urethane resin composed of the polyisocyanate compound and the polyol compound.
The additive excluding the red phosphorus provides the urethane resin composition according to the above [1], which is in the range of 1.5 to 52 parts by weight based on 100 parts by weight of the urethane resin.

One of the present invention is
[3] The urethane resin composition includes a trimerization catalyst that promotes a trimerization reaction of isocyanate groups contained in the polyisocyanate compound,
The urethane resin composition according to [1] or [2], wherein the trimerization catalyst is in a range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the urethane resin composed of the polyisocyanate compound and the polyol compound. It provides things.

The present invention also provides
[4] A molded article obtained by molding the urethane resin composition according to any one of [1] to [3] is provided.

  The polyurethane foam obtained by using the urethane resin composition according to the present invention is excellent in flexibility and difficult to ignite, so that it can exhibit excellent flame retardancy.

The urethane resin composition according to the present invention will be described.
First, the urethane resin used for the urethane resin composition will be described.
As said urethane resin, what contains the polyisocyanate compound as a main ingredient, the polyol compound as a hardening | curing agent, etc. are mentioned, for example.
Examples of the polyisocyanate compound that is the main component of the urethane resin include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.

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

  The said polyisocyanate compound can use 1 type, or 2 or more types.

The polyol compound which is the curing agent for the urethane resin used in the present invention has a weight average molecular weight of 1000 to 20000.
This range is preferably in the range of 1500-15000, more preferably in the range of 2000-10000.
When the weight average molecular weight of the polyol compound is in the range of 1000 to 20000, the polyurethane foam obtained by curing the urethane resin composition according to the present invention is excellent in flexibility and easy to handle.
Even when the polyol compound used in the present invention contains a compound having a molecular weight of less than 1000, the weight average molecular weight of the polyol compound as a whole is in the range of 1000 to 20000 by combining with a compound having a large molecular weight. It is possible to fit in.

  The weight average molecular weight of the polyol compound can be determined by comparing a compound having a known weight average molecular weight with the polyol compound using a high performance liquid chromatography apparatus, for example, a measurement value by a parallax refractometer. .

  Examples of the polyol compound include polylactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polymer polyol, polyether polyol, and the like.

Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.
The polycarbonate polyol can be obtained, for example, by dealcoholization reaction of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with diethylene carbonate, dipropylene carbonate, and the like. Polyol etc.

Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolak, and cresol novolak.
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, and a polymer obtained by ring-opening polymerization of a lactone such as ε-caprolactone and α-methyl-ε-caprolactone. And a condensate of hydroxycarboxylic acid and the above polyhydric alcohol.

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-hexane glycol, and neopentyl glycol. It is done.
Specific examples of the hydroxycarboxylic acid include castor oil, a reaction product of castor oil and ethylene glycol, and the like.

  Examples of the polymer polyol include graft polymerization of ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl acrylate, and methacrylate on the aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, polyether polyol, and the like. Examples thereof include polymers, polybutadiene polyols, modified polyols of polyhydric alcohols, and hydrogenated products thereof.

Examples of the modified polyol of the polyhydric alcohol include those modified by reacting a raw material polyhydric alcohol with an alkylene oxide.
Examples of the polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane,
Pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc., tetra- to octavalent alcohols such as sucrose, glucose, mannose, fructose, methyl glucoside and 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 -Phenols such as tetrahydroxyanthracene and 1-hydroxypyrene,
Polybutadiene polyol,
Castor oil-based polyol,
Examples include (co) polymers of hydroxyalkyl (meth) acrylates and polyfunctional (eg, 2 to 100 functional group) polyols such as polyvinyl alcohol, and condensates (novolaks) of phenol and formaldehyde.

The method for modifying the polyhydric alcohol is not particularly limited, but a method of adding alkylene oxide (hereinafter abbreviated as AO) is preferably used.
Examples of the AO include 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-propyloxide, 1,2 -Butylene oxide, 1, 4- butylene oxide, etc. are mentioned.
Among these, PO, EO, and 1,2-butylene oxide are preferable from the viewpoint of properties and reactivity, and PO and EO are more preferable.
When two or more types of AO are used (for example, PO and EO), block addition or random addition may be used, or a combination thereof may be used.

Examples of the polyether polyol include ring-opening polymerization of at least one alkylene oxide such as ethylene oxide, propylene oxide, and tetrahydrofuran in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogens. And the resulting polymer.
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,
Triols such as glycerin and trimethylolpropane,
Examples include amines such as ethylenediamine and butylenediamine.

  The polyol used in the present invention is preferably a polyester polyol or a polyether polyol because a polyurethane foam obtained by curing the urethane resin composition is difficult to ignite.

In the present invention, the index is defined by [number of equivalents of isocyanate] × 100 ÷ [number of equivalents of polyol + number of equivalents of water].
Here, the equivalent number of the polyol compound is represented by [hydroxyl value of polyol compound (mgKOH / g)] × [weight of polyol compound (g)] ÷ [molecular weight of potassium hydroxide].
The equivalent number of the isocyanate compound is represented by [molecular weight of isocyanate group] × 100 ÷ [weight% of isocyanate group].
The equivalent number of water is represented by [weight of water (g)] × 2 ÷ [molecular weight of water].
The index range is preferably in the range of 100 to 300.
When the equivalent ratio is 300 or less, foaming failure can be prevented, and when the equivalent ratio is 100 or more, good heat resistance can be obtained.

In the present invention, a urethane resin curing catalyst can be used in addition to the urethane resin.
Examples of the urethane curing catalyst include amino compounds, tin compounds, and acetylacetone metal salts.

Examples of the amino compound include pentamethyldiethylenetriamine, triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″. -Pentamethyldiethylenetriamine, N, N, N'-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl, N'-dimethylaminoethylpiperazine, secondary amine function in imidazole ring Imidazole compound substituted with cyanoethyl group, N, N-dimethylcyclohexylamine, diazabicycloundecene, triethylenediamine, tetramethylhexamethylenediamine, N-methylimidazole, trimethylaminoethylpiperazine, tripropi Ruamine,
Examples thereof include tetramethylammonium salt, tetraethylammonium salt, and triphenylammonium salt.

  Examples of the tin compound include stannous octylate, dibutyltin diacetate, dibutyltin dilaurate, and the like.

  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, and acetylacetone zirconium. It is done.

  One or two or more of the urethane resin curing catalysts can be used.

The addition amount of the urethane resin curing catalyst used in the urethane resin composition according to the present invention is not particularly limited, but is preferably in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. The range is more preferably 0.01 to 8.0 parts by weight, still more preferably 0.01 to 6.0 parts by weight, and more preferably 0.01 to 1.5 parts by weight. Most preferred.
In the case of 0.01 parts by weight or more and 10 parts by weight or less, it is easy to handle and the reaction is easily controlled.

  As the polyurethane resin used in the present invention, those obtained by reacting an isocyanate group contained in a polyisocyanate compound, which is a main component of the polyurethane resin, to trimerize, and promoting the formation of an isocyanurate ring can be used.

  In order to promote the formation of an isocyanurate ring, for example, as a catalyst, tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) hexahydro Aromatic compounds such as -S-triazine, potassium acetate, sodium acetate, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, quaternary ammonium compounds such as tertiary amine carboxylates, 2-ethylaziridine, etc. Amine compounds such as aziridines, lead compounds such as diazabicycloundecene, lead naphthenate and lead octylate, alcoholate compounds such as sodium methoxide, phenolate compounds such as potassium phenoxide, quaternary ammonium salts of carboxylic acids, etc. Can be used.

The addition amount of the trimerization catalyst used in the flame-retardant urethane resin composition according to the present invention is not particularly limited, but is preferably in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. The range is more preferably 0.01 to 8.0 parts by weight, still more preferably 0.01 to 6.0 parts by weight, and 0.5 to 1.5 parts by weight. Is most preferred.
When the amount is 0.01 parts by weight or more, the problem that the trimerization of isocyanate is inhibited does not occur, and when the amount is 10 parts by weight or less, the problem that the urethane bond is inhibited can be reduced.

  One or two or more trimerization catalysts can be used.

In the present invention, a foaming agent is used in addition to the urethane resin.
In order to promote foaming of the urethane resin contained in the urethane resin composition according to the present invention, a foaming agent can be added to the urethane resin composition according to the present invention.
Examples of the foaming agent include water,
Low boiling point hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane,
Chlorinated aliphatic hydrocarbon compounds such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride,
Fluorine compounds such as trichloromonofluoromethane, trichlorotrifluoroethane, CHF ₃ , CH ₂ F ₂ , CH ₃ F,
Hydrochlorofluorocarbon compounds such as dichloromonofluoroethane (for example, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane),
Hydrofluorocarbon compounds such as HFC-245fa (1, 1, 1, 3, 3-pentafluoropropane), HFC-365mfc (1, 1, 1, 3, 3-pentafluorobutane),
Organic physical foaming agents such as ether compounds such as diisopropyl ether, or mixtures of these compounds,
Examples include inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas.

  The foaming agent used in the present invention is preferably pentane, hydrofluorocarbon, or water, and more preferably water.

  Moreover, the foaming agent used for this invention can use 1 type, or 2 or more types.

The amount of the foaming agent added to the urethane resin composition according to the present invention is not particularly limited, but is preferably in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. The range is more preferably 15 parts by weight, still more preferably 1.0 to 15 parts by weight, and most preferably 1.5 to 10 parts by weight.
When the amount of the foaming agent added is 0.1 parts by weight or more, foaming is promoted, and the density of the obtained molded body can be reduced. It is possible to introduce bubbles that are continuous with each other.

A foam stabilizer can also be used in the urethane resin composition according to the present invention.
Examples of the foam stabilizer include surfactants such as polyoxyalkylene foam stabilizers such as polyoxyalkylene alkyl ether, silicone foam stabilizers such as organopolysiloxane, and the like.
The amount of the foam stabilizer used for the urethane resin cured by the chemical reaction is appropriately set according to the urethane resin cured by the chemical reaction to be used. For example, for example, 100 parts by weight of the urethane resin On the other hand, it is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 4.0 parts by weight, and still more preferably 1.0 to 3.0 parts by weight.

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

Next, although the urethane resin composition according to the present invention contains an additive, red phosphorus which is one of the additives used in the present invention will be described.
There is no limitation in red phosphorus used for this invention, A commercial item can be selected suitably and can be used.

Moreover, the addition amount of red phosphorus used for the urethane resin composition according to the present invention is in the range of 3.0 to 20 parts by weight with respect to 100 parts by weight of the urethane resin. The amount of red phosphorus added is preferably in the range of 3.0 to 18 parts by weight.
When the range of the red phosphorus is 3.0 parts by weight or more, the self-extinguishing property of the urethane resin composition according to the present invention is maintained, and when it is 20 parts by weight or less, the urethane resin composition according to the present invention Foaming is not hindered.

  The urethane resin composition according to the present invention is selected from the group consisting of phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant and metal hydroxide in addition to the red phosphorus described above as an additive. At least one of which can be used.

Examples of the phosphate-containing flame retardant include salts of the various phosphoric acids and at least one metal or compound selected from metals of Group IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. Can be mentioned.
Examples of the metals in groups 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 ammonium.
The phosphate-containing flame retardant may be subjected to a known water resistance improving treatment such as silane coupling agent treatment or coating with a melamine resin, and 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.

Although not particularly limited as the monophosphate, for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate,
Sodium salts such as monosodium phosphate, disodium phosphate, trisodium phosphate, monosodium phosphite, disodium phosphite, sodium hypophosphite,
Potassium salts such as monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, monopotassium phosphite, dipotassium phosphite, potassium hypophosphite,
Lithium salts such as monolithium phosphate, dilithium phosphate, trilithium phosphate, monolithium phosphite, dilithium phosphite, lithium hypophosphite,
Barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, tribarium phosphate, barium hypophosphite,
Magnesium salts such as magnesium monohydrogen phosphate, magnesium hydrogen phosphate, trimagnesium phosphate, magnesium hypophosphite,
Calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite,
Zinc salts such as zinc phosphate, zinc phosphite, zinc hypophosphite,
Examples thereof include aluminum salts such as primary aluminum phosphate, secondary aluminum phosphate, tertiary aluminum phosphate, aluminum phosphite, and aluminum hypophosphite.

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

  Among these, since the self-extinguishing property of the monophosphate-containing flame retardant is improved, it is preferable to use a monophosphate, such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, primary aluminum phosphate, phosphoric acid It is more preferable to use at least one selected from the group consisting of monosodium and tertiary aluminum phosphate, and it is more preferable to use ammonium dihydrogen phosphate.

  The said phosphate containing flame retardant can use 1 type, or 2 or more types.

The amount of the phosphate-containing flame retardant used in the present invention is preferably in the range of 1.0 to 18 parts by weight with respect to 100 parts by weight of the urethane resin, and 1.5 to 9.0 parts by weight. If it is a range, it is more preferable.
When the range of the phosphate-containing flame retardant is 1.0 part by weight or more, the self-extinguishing property of the urethane resin composition according to the present invention is maintained, and when it is 18 parts by weight or less, the urethane according to the present invention is maintained. Foaming of the resin composition is not inhibited.

  Although there is no limitation in particular as said phosphate ester, It is preferable to use monophosphate ester, condensed phosphate ester, etc.

  The monophosphate ester is not particularly limited, and examples thereof include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, and 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, phenylphosphonic acid Examples include diethyl, resilsinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, tris (β-chloropropyl) phosphate, and the like.

The condensed phosphate ester is not particularly limited, and examples thereof include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate (trade name PX- manufactured by Daihachi Chemical Industry Co., Ltd.). 200), hydroquinone poly (2,6-xylyl) phosphate and condensed phosphates 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 ADK STAB PFR), bisphenol A polycresyl phosphate (trade names FP-600, FP-700), and the like.

  Among these, it is preferable to use a monophosphate ester because it is highly effective in reducing the viscosity in the composition before curing and reducing the initial calorific value, and using tris (β-chloropropyl) phosphate. Is more preferable.

  The said phosphate ester can use 1 type, or 2 or more types.

Moreover, the addition amount of the phosphate ester used for this invention is the range of 0.1-200 weight part with respect to 100 weight part of said urethane resins. The addition amount of the phosphate ester is preferably in the range of 0.1 to 100 parts by weight, more preferably in the range of 0.1 to 50 parts by weight, and in the range of 5.0 to 15 parts by weight. More preferred.
When the range of the phosphoric acid ester is 0.1 parts by weight or more, the molded article made of the urethane resin composition according to the present invention is difficult to ignite, and when it is 200 parts by weight or less, the urethane resin composition according to the present invention. The foaming of objects is not hindered.

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.
Specific examples of the aromatic brominated compound include, for example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (penta Monomeric organic bromine compounds such as bromophenoxy) ethane, ethylene-bis (tetrabromophthalimide), tetrabromobisphenol A,
A polycarbonate oligomer produced from brominated bisphenol A as a raw material, a brominated polycarbonate such as a copolymer of the polycarbonate oligomer and bisphenol A,
Brominated epoxy compounds such as diepoxy compounds produced by reaction of brominated bisphenol A with epichlorohydrin, monoepoxy compounds obtained by reaction of brominated phenols with epichlorohydrin,
Poly (brominated benzyl acrylate),
Brominated polyphenylene ether,
A condensate of brominated bisphenol A, cyanuric chloride and brominated phenol,
Brominated polystyrene such as brominated (polystyrene), poly (brominated styrene), cross-linked brominated polystyrene,
Halogenated bromine compound polymers such as crosslinked or non-crosslinked brominated poly (-methylstyrene).
From the viewpoint of enhancing the self-extinguishing property of the urethane resin composition according to the present invention, brominated polystyrene, hexabromobenzene and the like are preferable, and hexabromobenzene is more preferable.

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

Although there is no limitation in particular in the addition amount of the bromine containing flame retardant used for this invention, it is preferable that it is the range of 0.1-60 weight part with respect to 100 weight part of urethane resins, 0.1-50 weight part Is more preferable, the range of 0.1 to 40 parts by weight is further preferable, and the range of 2.0 to 5.0 parts by weight is most preferable.
When the range of the bromine-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the urethane resin composition according to the present invention is maintained, and when it is 60 parts by weight or less, the urethane resin composition according to the present invention. The foaming of objects is not hindered.

  Examples of the metal hydroxide used in the present invention include aluminum hydroxide, magnesium hydroxide, dawsonite, calcium aluminate, dihydrate gypsum, calcium hydroxide and the like.

  The said metal hydroxide can use 1 type, or 2 or more types.

In the present invention, a boron-containing flame retardant can also be used. Examples of the boron-containing flame retardant include borax, boron oxide, boric acid, and borate.
Examples of the boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.
Examples of the borate include alkali metals, alkaline earth metals, elements of Group 4, Group 12, and Group 13 of the periodic table, and ammonium borate.
Specifically, alkali metal borate such as lithium borate, sodium borate, potassium borate, cesium borate, alkaline earth metal borate such as magnesium borate, calcium borate, barium borate, boron Examples thereof include zirconium acid, zinc borate, aluminum borate, and ammonium borate.

  The boron-containing flame retardant used in the present invention is preferably a borate, and 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 in the range of 0.1 to 60 parts by weight with respect to 100 parts by weight of the urethane resin. The amount of boron-containing flame retardant added is preferably in the range of 0.1 to 50 parts by weight, more preferably in the range of 0.1 to 40 parts by weight, and in the range of 1.0 to 10 parts by weight. More preferably it is.
When the range of the boron-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the urethane resin composition according to the present invention is maintained, and when it is 60 parts by weight or less, the urethane resin composition according to the present invention. The foaming of objects is not hindered.

In the present invention, an antimony-containing flame retardant can also be used. Examples of the antimony-containing flame retardant include antimony oxide, antimonate, and pyroantimonate.
Examples of the antimony oxide include antimony trioxide and antimony pentoxide.
Examples of the antimonate include sodium antimonate and potassium antimonate.
Examples of the pyroantimonate include sodium pyroantimonate and potassium pyroantimonate.

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

  The said antimony containing flame retardant can use 1 type, or 2 or more types.

The amount of the antimony-containing flame retardant added is not particularly limited, but is preferably in the range of 0.1 to 60 parts by weight, and in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the urethane resin. More preferably, the range is from 0.1 to 40 parts by weight, and most preferably from 1.0 to 10 parts by weight.
When the range of the antimony-containing flame retardant is 0.1 parts by weight or more, the self-extinguishing property of the urethane resin composition according to the present invention is maintained, and when it is 60 parts by weight or less, the urethane resin composition according to the present invention. The foaming of objects is not hindered.

Further, the urethane resin composition according to the present invention can use an inorganic filler.
The inorganic filler is not particularly limited. For example, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate, Magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salt of calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, ceviolite, imogolite, seri Site, glass fiber, glass beads, silica balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, dititanate Lead oxide, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, inorganic phosphorus compound, silica alumina fiber, alumina fiber, silica fiber, zirconia fiber, etc. .

  The said inorganic filler can use 1 type, or 2 or more types.

  Furthermore, the urethane resin composition according to the present invention is within a range that does not impair the purpose of the present invention, as necessary, phenol-based, amine-based, sulfur-based antioxidants, heat stabilizers, metal damage inhibitors, An antistatic agent, a stabilizer, a crosslinking agent, a lubricant, a softener, a pigment, an additive such as a tackifier resin, and a tackifier such as polybutene and a petroleum resin can be included.

Since the urethane resin composition according to the present invention reacts and cures, the viscosity changes with time.
Therefore, before using the urethane resin composition according to the present invention, the urethane resin composition is divided into two or more to prevent the urethane resin composition from reacting and curing. And when using the urethane resin composition which concerns on this invention, the urethane resin composition which concerns on this invention is obtained by putting together the said urethane resin composition divided | segmented into two or more.
In addition, when dividing the urethane resin composition into two or more, each component of the urethane resin composition divided into two or more does not start to cure, and is cured after mixing each component of the urethane resin composition. What is necessary is just to divide each component so that reaction may start.

Next, the manufacturing method of the said urethane resin composition is demonstrated.
The method for producing the urethane resin composition is not particularly limited. For example, a method for mixing the components of the urethane resin composition, a method for suspending the urethane resin composition in an organic solvent, a slurry dispersed in a solvent And when the reaction curable resin component contained in the urethane resin composition contains a component that is solid at a temperature of 25 ° C., the urethane resin composition is melted under heating, etc. The urethane resin composition can be obtained by this method.

Alternatively, the main component of urethane resin and the curing agent may be separately kneaded together with a filler or the like and kneaded with a static mixer, a dynamic mixer or the like immediately before injection.
Further, the components of the urethane resin composition excluding the catalyst and the catalyst can be kneaded in the same manner immediately before injection.

  The urethane resin composition according to the present invention can be obtained by the method described above.

Next, a method for curing the urethane resin composition according to the present invention will be described.
When the respective components of the urethane resin composition are mixed, the reaction starts, the viscosity increases with the passage of time, and the fluidity is lost.
For example, a molded body made of the urethane resin composition can be obtained by injecting the urethane resin composition into a container such as a mold or a frame material and curing it.
When obtaining a molded body made of the urethane resin composition, heat can be applied or pressure can be applied.
The specific gravity of the molded article made of the urethane resin composition is not particularly limited, but is preferably in the range of 0.02 to 0.20, more preferably in the range of 0.03 to 0.15. A range of 0.03 to 0.10 is more preferable, and a range of 0.04 to 0.08 is most preferable.
Such a compact is easy to handle because of its low specific gravity.

The polyurethane foam obtained by curing the urethane resin composition according to the present invention has air bubbles inside, but the air bubbles are not independent air bubbles in the polyurethane foam, but open air cells in which the air bubbles are connected to each other. It is preferable that
The polyurethane foam has a characteristic that it is flexible but difficult to ignite.

  Hereinafter, the present invention will be described in detail by way of examples. In addition, this invention is not limited at all by the following examples.

  According to the formulation shown in Table 1, the urethane resin composition according to Example 1 was prepared by being divided into three components (A) to (C). The details of each component shown in Table 1 are as follows.

Component (A): polyol compound (hereinafter referred to as “polyol compound”)
(A) Polyol compound Polyether polyol A-1: Polyether polyol (manufactured by Sanyo Chemical Co., Ltd., product name: Sannix GP-3000, hydroxyl value: 56 mgKOH / g, functional group number: 3 [per molecule])
A-2: Polyether polyol (manufactured by Sanyo Kasei Co., Ltd., product name: Sannix PP-3000, hydroxyl value: 35 mgKOH / g, number of functional groups: 2 [per molecule])
A-3: Polyether polyol (manufactured by Sanyo Chemical Co., Ltd., product name: Sannix GP-1000, hydroxyl value: 168 mgKOH / g, functional group number: 2 [per molecule])
A-4: Polyether polyol (manufactured by Sanyo Chemical Co., Ltd., product name: Sannix GP-4000, hydroxyl value: 42 mgKOH / g, number of functional groups: 2 [per molecule])
(B) Catalyst B-1: Triethylenediamine (manufactured by Tosoh Corporation, product name: TEDA-L33)
B-2: stannous octylate (manufactured by Nitto Kasei Co., Ltd., product name: Neostan U-28)
B-3: Trimerization catalyst (manufactured by Tosoh Corporation, product name: TOYOCAT-TR20)
(C) Foaming agent water (pure water)
(D) Foam stabilizer C-1: Silicone foam stabilizer (manufactured by Toray Dow Corning, product name: SH192)

Component (B): polyisocyanate (hereinafter referred to as “polyisocyanate”)
D-1: TDI (manufactured by Nippon Polyurethane Industry Co., Ltd., product name: Coronate T-80)
D-2: MDI (manufactured by Nippon Polyurethane Industry Co., Ltd., product name: Millionate MR-200, viscosity: 167 mPa · s, isocyanate content 30.5-32.0%)

(C) Component: Additive E-1: Tris (β-chloropropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd., product name: TMCPP)
E-2: Red phosphorus (manufactured by Rin Chemical Industry Co., Ltd., product name: Nova Excel 140)
E-3: Ammonium dihydrogen phosphate (manufactured by Kanto Chemical Co., Ltd., product code: 01309-01)
E-4: Hexabromobenzene (manufactured by Manac, product name HBB-B)
E-5: Aluminum hydroxide (Almorix, product name: B-325)

Next, according to the composition shown in Table 1 below, the components (A) and (C) are weighed in a 1000 ml polypropylene beaker, and a high-speed disperser (manufactured by PRIMIX, product name: homodisper 2.5 type) is used at 25 ° C. The mixture was stirred for 2 minutes at 400 rpm.
A foam stabilizer and a foaming agent were added to the components (A) and (C) after stirring, and the mixture was stirred for about 10 seconds at 25 ° C. and 6000 rpm using a high-speed disperser to prepare a foam.
The obtained urethane resin composition lost fluidity with the passage of time, and a cured product of the urethane resin composition was obtained. The cured product was evaluated according to the following criteria, and the results are shown in Table 1.
Table 1 shows the index of the polyisocyanate used in Example 1. The same applies to the following embodiments.

[Measurement of flame retardancy]
A test body was cut out from the cured urethane resin composition so as to have a size of 125 mm × 13 mm × 10 mm, and a combustion test was conducted in accordance with UL94 of UL standard. Five test specimens were burned, and the combustion performance was judged from the average burning time.
The case corresponding to V-0 is indicated by ◎, the case corresponding to V-1 is indicated by ◯, the case corresponding to V-2 is indicated by △, and the case where performance is inferior to V-2 is indicated by ×. It was shown to.
Also, the change in weight before and after this combustion test is shown in Table 1 as a residual rate in percentage (%).

The experiment was performed in exactly the same manner as in Example 1 except that additive E-5 was not used as compared with Example 1.
The results are shown in Table 1.

Compared with the case of Example 2, it replaced with polyol compound A-1 and used 32.9 weight part of polyol compound A-2, and the usage-amount of polyisocyanate D-2 was 61.6 weight part to 67. The experiment was performed in the same manner as in Example 2 except that the amount was changed to 1 part by weight.
The results are shown in Table 1.

Compared with the case of Example 2, it replaced with polyol compound A-1 and used 23.1 weight part of polyol compound A-3, and the usage-amount of polyisocyanate D-2 was 61.6 weight part to 76. The experiment was performed in the same manner as in Example 2 except that the amount was changed to 9 parts by weight.
The results are shown in Table 1.

Compared to the case of Example 2, in place of polyol compound A-1, 32.2 parts by weight of polyol compound A-4 was used, and the amount of polyisocyanate D-2 was changed from 61.6 parts by weight to 67 parts. The experiment was performed in the same manner as in Example 2 except that the amount was changed to 8 parts by weight.
The results are shown in Table 1.

The experiment was performed in exactly the same manner as in Example 1, except that the additives E-1, E-4, and E-5 were not used as compared with Example 1.
The results are shown in Table 1.

The experiment was performed in exactly the same manner as in Example 1, except that the additives E-3, E-4, and E-5 were not used as compared with Example 1.
The results are shown in Table 1.

The experiment was performed in exactly the same manner as in Example 1, except that the additives E-1, E-3, and E-5 were not used as compared with Example 1.
The results are shown in Table 1.

The experiment was performed in exactly the same manner as in Example 1, except that the additives E-1, E-3, and E-4 were not used as compared with Example 1.
The results are shown in Table 1.

Compared to the case of Example 2, the additive E-5 was not used and the amount of each of the additives E-1 to E-4 was halved, exactly as in the case of Example 2. The experiment was conducted.
The results are shown in Table 1.

Compared to the case of Example 2, the additive E-5 was not used and the amount of each of the additives E-1 to E-4 was tripled. The experiment was conducted.
The results are shown in Table 2.

Compared to the case of Example 2, the amount of the polyol compound used was changed from 38.4 parts by weight to 62.5 parts by weight, instead of polyisocyanate D-2, D-1 was 37.5 parts by weight. The experiment was performed in exactly the same manner as in Example 2 except that catalyst B-3 was not used.
The results are shown in Table 2.

[Comparative Example 1]
Compared with the case of Example 1, the usage-amount of polyol compound A-1 was 54.2 weight part, the catalyst B-3 was not used, and the usage-amount of polyisocyanate D-2 was 45. The experiment was performed in the same manner as in Example 1 except that the amount was 8 parts by weight and no additive was used.
The results are shown in Table 2.

[Comparative Example 2]
Compared to the case of Example 2, the experiment was performed in exactly the same manner as in Example 1 except that no additive was used.
The results are shown in Table 2.

[Comparative Example 3]
Compared to the case of Comparative Example 1, the amount of polyol compound A-1 used was changed to 62.5 parts by weight, and in place of polyisocyanate D-2, 37.5 parts by weight of D-1 was used. The experiment was performed in the same manner as in Comparative Example 1.
The results are shown in Table 2.

  The molded body obtained from the urethane resin composition according to the present invention is very difficult to ignite and can exhibit excellent fire resistance.

  Since the molded product of the urethane resin composition according to the present invention is excellent in fire resistance, the support material such as a cushion for supporting a human body in addition to a cushioning material, a heat insulating material, a sound insulating material, etc. for vehicles, home appliances, electronic devices, etc. The urethane resin composition of the present invention can be widely applied.

Claims (6)

Including polyisocyanate compounds, polyol compounds, foaming agents, foam stabilizers and additives,
The polyol compound has a weight average molecular weight in the range of 1000 to 20000,
The additive comprises red phosphorus as an essential component, in addition to the red phosphorus, in combination with at least one selected from the group consisting of phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants and metal hydroxides. Do Ri,
A trimerization catalyst that promotes a trimerization reaction of isocyanate groups contained in the polyisocyanate compound is included, and the trimerization catalyst is 0.01 to 10 parts by weight based on 100 parts by weight of the urethane resin composed of the polyisocyanate compound and the polyol compound. wherein the range der Rukoto parts by weight, the urethane resin composition. Including polyisocyanate compounds, polyol compounds, foaming agents, foam stabilizers and additives,
  The polyol compound has a weight average molecular weight in the range of 1000 to 20000,
  The urethane resin composition, wherein the additive contains red phosphorus and phosphate as essential components. The urethane resin composition according to claim 2, wherein the additive contains at least one selected from the group consisting of a phosphate-containing flame retardant, a bromine-containing flame retardant, and a metal hydroxide. The urethane resin composition includes a trimerization catalyst that promotes a trimerization reaction of isocyanate groups contained in the polyisocyanate compound,
The urethane resin composition of Claim 2 or 3 whose said trimerization catalyst is the range of 0.01-10 weight part with respect to 100 weight part of urethane resins which consist of the said polyisocyanate compound and the said polyol compound. The additive is in the range of 4.5 to 70 parts by weight based on 100 parts by weight of a urethane resin composed of the polyisocyanate compound and the polyol compound,
The urethane resin composition according to any one of claims 1 to 4 , wherein the additive excluding the red phosphorus is in the range of 1.5 to 52 parts by weight based on 100 parts by weight of the urethane resin. The molded object formed by shape | molding the urethane resin composition in any one of the urethane resin compositions in any one of Claims 1-5 .