JP6894209B2 - Polyol-containing compositions, foamable polyurethane compositions and polyurethane foams - Google Patents

Description

The present invention relates to a polyol-containing composition, a foamable polyurethane composition, and a polyurethane foam for reacting with polyisocyanate to obtain a polyurethane foam.

Polyurethane foam resin is used as a heat insulating material for buildings such as condominiums, detached houses, various school facilities, and commercial buildings. Since urethane resin has low flame retardancy, it may impart flame retardancy to the heat insulating urethane material.

For example, Patent Documents 1 and 2 disclose a rigid polyurethane foam having high flame retardancy and a method for producing the same.

JP 2000-230028 Japanese Patent Application Laid-Open No. 2004-339269

However, it has not been confirmed that any of the rigid polyurethane foams of Patent Documents 1 and 2 satisfies the nonflammability under the Building Standards Act.

Further, when a certain amount of solid content is used to impart flame retardancy to polyurethane foam (polyurethane foam), the solution becomes highly viscous and caking (sedimentation and aggregation) occurs. When caking occurs, there is a problem that the flame retardant performance deteriorates after the polyol solution is allowed to stand. Therefore, a means for improving the storage stability when the polyol solution is stored for a long period of time is required.

Patent Documents 1 and 2 do not describe means for improving storage stability when stored for a long period of time.

An object of the present invention is to provide a foamable polyurethane composition and a polyurethane foam having flame retardancy and excellent storage stability in which flame retardancy is maintained even after long-term storage.

As a result of various studies to achieve the above object, the inventors of the present application have found a foamable polyurethane composition having flame retardancy and excellent storage stability by enhancing the thixophilicity of the polyol-containing composition. We have found that it can be obtained and have completed the present invention.

That is, the present invention includes the following aspects.

Item 1. A polyol-containing composition for reacting with a polyisocyanate to obtain a polyurethane foam, wherein the polyol-containing composition contains a polyol compound, a foam stabilizer, a catalyst, a foaming agent, and a flame retardant.
A polyol-containing composition characterized in that the viscosity of the polyol-containing composition at a rotation speed of 100 rpm at 25 ° C. is 105 mPas or more, and the chixo value calculated by the following formula is 1.9 or more.
(Chixo value) = (Viscosity at 25 ° C. rotation speed 1 rpm) / (Viscosity at 25 ° C. rotation speed 10 rpm)

Item 2. Item 2. The polyol-containing composition according to Item 1, wherein the solid component is 35 parts by weight or more with respect to 100 parts by weight of the polyol compound.

Item 3. A foamable polyurethane composition, which comprises reacting the polyol-containing composition according to Item 1 or 2 with a polyisocyanate.

Item 4. A polyurethane foam obtained by curing the foamable polyurethane composition according to Item 3.

Item 5. Item 2. The polyurethane foam according to Item 4, which is a molded product.

The foamable polyurethane composition of the present invention has both excellent flame retardancy and improved storage stability, and is excellent in flame retardancy.

The graph of the viscosity (25 ° C.) measurement result of the sample of the cured foamable polyurethane composition of Examples 1-3 and Comparative Examples 1-3.

The present invention is a polyol-containing composition for reacting with polyisocyanate to obtain a polyurethane foam, wherein the polyol-containing composition contains a polyol, a foam stabilizer, a catalyst, a foaming agent, and a flame retardant, and the polyol. It includes a polyol-containing composition characterized in that the viscosity of the contained composition at a rotation speed of 100 rpm at 25 ° C. is 105 mPas or more and the chixo calculated by the following formula is 1.9 or more.
(Chixo value) = (Viscosity at 25 ° C. rotation speed 1 rpm) / (Viscosity at 25 ° C. rotation speed 10 rpm)

In the present specification, "cured" refers to a state after the main agent and the curing agent of the foamable polyurethane composition are mixed, foamed and cured to complete the reaction.

The foamable polyurethane composition is formed by reacting the above-mentioned polyol-containing composition with polyisocyanate. The polyisocyanate as the main component of the urethane resin and the polyol as the curing agent of the urethane resin contained in the above-mentioned polyol-containing composition are cured by a chemical reaction to form a urethane resin. Hereinafter, each component will be described.

1. 1. Polyisocyanate Examples of the polyisocyanate that is the main component of the urethane resin include aromatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.

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

Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

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

One type or two or more types of polyisocyanate can be used. As the main agent of the urethane resin, aromatic polyisocyanate is preferable, and diphenylmethane diisocyanate is more preferable, because it is easy to use and easily available.

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

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

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

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

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

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

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

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

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

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

Polyhydric alcohols include, for example, trihydric alcohols such as glycerin and trimethylolpropane; pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol and the like, sucrose, glucose, mannose, fructose, methylglucoside and Tetra-octavalent alcohols such as derivatives thereof; phenol, fluoroglycerin, 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 phenol polybutadiene polyols; castor oil polyol; (co) polymer of hydroxyalkyl (meth) acrylate and polyfunctional (eg, polyvinyl alcohol) such as polyvinyl alcohol. Examples thereof include polyols having a number of functional groups of 2 to 100) and condensates (novolac) of phenol and formaldehyde.

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

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

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

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

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

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

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

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

The blending amount of the foam stabilizer can be appropriately set according to the urethane resin. As an example, the blending amount of the foam stabilizer is preferably in the range of 0.1 part by weight to 10 parts by weight with respect to 100 parts by weight of the polyol compound. With respect to 100 parts by weight of the urethane resin, for example, the range of 0.1 parts by weight to 10 parts by weight is preferable.

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

4. Catalyst Examples of the catalyst include a trimerization catalyst.

The trimerization catalyst reacts the isocyanate group contained in the polyisocyanate, which is the main component of the polyurethane resin, to tritrate it, and promotes the formation of an isocyanurate ring.

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

The amount of the trimerization catalyst is preferably in the range of 0.2 parts by weight to 30 parts by weight, and more preferably in the range of 1.2 parts by weight to 24 parts by weight with respect to 100 parts by weight of the polyol compound. , 1.2 parts by weight to 18 parts by weight, more preferably 1.2 parts by weight to 9.0 parts by weight. When it is 0.2 parts by weight or more, there is no problem that the triglyceride of polyisocyanate is inhibited, and when it is 30 parts by weight or less, an appropriate foaming rate can be maintained and it is easy to handle.

The amount of the trimerization catalyst is preferably in the range of 0.1 parts by weight to 10 parts by weight, and 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 parts by weight to 6 parts by weight, and most preferably in the range of 0.6 parts by weight to 3.0 parts by weight. The range may be in the range of 0.6 parts by weight to 10 parts by weight with respect to 100 parts by weight of the urethane resin. When it is at least the above lower limit, there is no problem that the triglycerate of polyisocyanate is inhibited, and when it is 10 parts by weight or less, an appropriate foaming rate can be maintained and it is easy to handle.

In addition to the trimerization catalyst, the following catalysts can be mentioned as catalysts: alkylated polyalkylene polyamine, triethylamine, N ", N" -pentamethyldiethylenetriamine, N, N, N'-trimethylaminoethyl-ethanolamine, urethane. Amines such as catalysts; N-methylmorpholinbis (2-dimethylaminoethyl) ether, N, N, N', bis (2-dimethylaminoethyl) ether, N-methyl-N'-di-8 methylaminoethyl piperazine, Examples thereof include nitrogen atom-containing catalysts such as imidazole compounds in which the secondary amine functional group in the imidazole ring is replaced with a cyanoethyl group.

The amount of the catalyst other than the trimerization catalyst added is the total amount of the trimerization catalyst and the catalyst other than the trimerization catalyst, and is in the range of 0.6 parts by weight to 30 parts by weight with respect to 100 parts by weight of the polyol compound. It is more preferably in the range of 1.2 parts by weight to 24 parts, further preferably in the range of 1.2 parts by weight to 18 parts by weight, and 1.2 parts by weight to 9.0 parts by weight. Most preferably it is in the range.

When it is 0.6 parts by weight or more, there is no problem that the formation of urethane bond is hindered, and when it is 30 parts by weight or less, an appropriate foaming rate can be maintained and it is easy to handle.

When the foamable polyurethane composition contains a catalyst other than the trimerization catalyst, the amount of the catalyst added is the total amount of the trimerization catalyst and the catalyst other than the trimerization catalyst, which is 0.3 weight by weight based on 100 parts by weight of the urethane resin. The range is preferably in the range of 10 parts by weight, more preferably in the range of 0.6 parts by weight to 8 parts, still more preferably in the range of 0.6 parts by weight to 6 parts by weight, and 0. Most preferably, it is in the range of 6 parts by weight to 3.0 parts by weight. The range may be in the range of 0.6 parts by weight to 10 parts by weight with respect to 100 parts by weight of the urethane resin.

When it is at least the above lower limit value, there is no problem that the formation of urethane bond is hindered, and when it is 10 parts by weight or less, an appropriate foaming rate can be maintained and it is easy to handle.

One type or two or more types of catalysts can be used.

5. Foaming agent The foaming agent promotes the foaming of urethane resin. Examples of the effervescent agent include water; low boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptan; dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, etc. Chlorinated aliphatic hydrocarbon compounds such as isobutyl chloride, pentyl chloride, and isopentyl chloride; _{fluorine compounds such as CHF 3} , CH ₂ F ₂ , and CH ₃ F; trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane, Hydrochlorofluorocarbon compounds such as (eg, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)); HFC-245fa (1, Hydrofluorocarbons such as 1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane); ether compounds such as diisopropyl ether, or mixtures of these compounds, etc. Examples thereof include organic physical foaming agents, nitrogen gas, oxygen gas, argon gas, carbon dioxide gas and other inorganic physical foaming agents.

The blending amount of the foaming agent is not particularly limited, but is preferably in the range of 0.2 parts by weight to 90 parts by weight with respect to 100 parts by weight of the polyol compound. The foaming agent is more preferably in the range of 0.2 parts by weight to 54 parts by weight, further preferably in the range of 1 part by weight to 54 parts by weight, with respect to 100 parts by weight of the polyol compound. Most preferably, it is in the range of ~ 30 parts by weight.

When the range of the foaming agent is 0.2 parts by weight or more, foaming is promoted and the density of the obtained molded product can be reduced, and when it is 90 parts by weight or less, the foam does not foam and the foam is formed. It can be prevented that it is not done.

The blending amount of the foaming agent is preferably in the range of 0.1 parts by weight 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 parts by weight to 18 parts by weight, further preferably in the range of 0.5 parts by weight to 18 parts by weight, with respect to 100 parts by weight of the urethane resin. Most preferably, it is in the range of 10 parts by weight to 10 parts by weight.

When the range of the foaming agent is 0.1 parts by weight or more, foaming is promoted and the density of the obtained molded product can be reduced, and when it is 30 parts by weight or less, the foam does not foam and the foam is formed. It can be prevented that it is not done.

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

6. Flame Retardants The flame retardant comprises at least one selected from red phosphorus, phosphate esters, phosphate-containing flame retardants, bromine-containing flame retardants, boric acid-containing flame retardants, antimony-containing flame retardants, and metal hydroxides. Preferably, the flame retardant is red phosphorus and at least one selected from a phosphate ester, a phosphate-containing flame retardant, a bromine-containing flame retardant, a boric acid-containing flame retardant, an antimony-containing flame retardant, and a metal hydroxide. Including.

As the flame retardant, a commercially available product can be appropriately selected and used.

The phosphoric acid ester used in the present invention is not particularly limited, but it is preferable to use a monophosphoric acid ester, a condensed phosphoric acid ester, or the like.

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

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

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

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

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

The amount of the phosphoric acid ester added is preferably in the range of 3 parts by weight to 156 parts by weight, more preferably in the range of 3 parts by weight to 60 parts by weight, based on 100 parts by weight of the polyol compound. It is more preferably in the range of 0 parts by weight to 45 parts by weight, and most preferably in the range of 4.0 parts by weight to 30 parts by weight.

When the range of the phosphoric acid ester is 3 parts by weight or more, the molded product made of the foamable polyurethane composition can prevent the dense residue formed by the ripening of the fire from cracking, and when it is 156 parts by weight or less, it is foamable. Foaming of the polyurethane composition is not inhibited.

The amount of the phosphoric acid ester added is preferably in the range of 1.5 parts by weight to 52 parts by weight, and 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 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.

When the range of the phosphoric acid ester is 1.5 parts by weight or more, the molded product made of the foamable polyurethane composition can prevent the dense residue formed by the ripening of the fire from cracking, and when it is 52 parts by weight or less, it can be prevented from cracking. Foaming of the foamable polyurethane composition is not inhibited.

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, and examples thereof include monophosphoric acid, pyrophosphoric acid, polyphosphoric acid, and various phosphoric acids such as combinations thereof.

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

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

Further, examples of the aromatic amine include pyridine, triazine, melamine, ammonium and the like.

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

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

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

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

Among these, monophosphate is preferably used, and ammonium dihydrogen phosphate is more preferable, because the self-extinguishing property of the phosphate-containing flame retardant is improved.

One or more types of 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 3 parts by weight to 156 parts by weight, preferably in the range of 3 parts by weight to 60 parts by weight, based on 100 parts by weight of the polyol compound. It is more preferably in the range of 4.0 parts by weight to 45 parts by weight, and most preferably in the range of 4.0 parts by weight to 30 parts by weight.

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, preferably 1.5 parts by weight to 20 parts by weight, based on 100 parts by weight of the urethane resin. The range is more preferably in the range of parts by weight, further 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 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 the aromatic brominated compound include hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, and bis (pentabromo). Fenoxy) Ethane, ethylene-bis (tetrabromophthalimide), tetrabromobisphenol A and other monomeric organobromine compounds; polycarbonate oligomers produced from brominated bisphenol A as raw materials, copolymers of polycarbonate oligomers and bisphenol A, etc. Bromineed polycarbonate; diepoxy compounds produced by the reaction of brominated bisphenol A with epichlorohydrin, brominated epoxy compounds such as monoepoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin; poly (bromineed benzyl acrylate) Brominated polyphenylene ether; Condensate of brominated bisphenol A, cyanur chloride and brominated phenol; brominated polystyrene such as brominated (polystyrene), poly (brominated styrene), crosslinked brominated polystyrene; crosslinked or non-crosslinked brominated Examples thereof include halogenated bromine compound polymers such as poly (-methylstyrene).

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

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

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, preferably 1.5 parts by weight to 20 parts by weight, based on 100 parts by weight of the urethane resin. The range 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 amount of the bromine-containing flame retardant used in the present invention is preferably in the range of 3 parts by weight to 156 parts by weight, preferably in the range of 3 parts by weight to 60 parts by weight, based on 100 parts by weight of the polyol compound. Is more preferable, and it is more preferably in the range of 4.0 parts by weight to 45 parts by weight, and most preferably in the range of 4.0 parts by weight to 30 parts by weight.

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

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

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

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, borate. Examples thereof include zirconium acid, zinc borate, aluminum borate, and ammonium borate.

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

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

The 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, preferably 1.5 parts by weight to 20 parts by weight, based on 100 parts by weight of the urethane resin. The enclosure is more preferably in the range of 2.0 parts by weight to 15 parts by weight, most preferably in the range of 2.0 parts by weight to 10 parts by weight.
The amount of the boron-containing flame retardant used in the present invention is preferably in the range of 3 parts by weight to 156 parts by weight with respect to 100 parts by weight of the polyol compound, and is surrounded by 3 parts by weight to 60 parts by weight. Is more preferable, and it is more preferably in the range of 4.0 parts by weight to 45 parts by weight, and most preferably in the range of 4.0 parts by weight to 30 parts by weight.

Examples of the antimony-containing flame retardant used in the present invention include antimony oxide, antimonate, and pyroantimonate.

Examples of antimony oxide include antimony trioxide and antimony pentoxide.

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

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

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

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

The amount of the antimony-containing flame retardant added is preferably in the range of 1.5 parts by weight to 52 parts by weight, and 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 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 amount of the antimony-containing flame retardant added is preferably in the range of 3 parts by weight to 156 parts by weight, more preferably in the range of 3 parts by weight to 60 parts by weight, based on 100 parts by weight of the polyol compound. It is more preferably in the range of 0.0 parts by weight to 45 parts by weight, and most preferably in the range of 4.0 parts by weight to 30 parts by weight.

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

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

The amount of the metal hydroxide added is preferably in the range of 1.5 parts by weight to 52 parts by weight, and 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 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 amount of the metal hydroxide added is preferably in the range of 3 parts by weight to 156 parts by weight, more preferably in the range of 3 parts by weight to 60 parts by weight, based on 100 parts by weight of the polyol compound. It is more preferably in the range of 0.0 parts by weight to 45 parts by weight, and most preferably in the range of 4.0 parts by weight to 30 parts by weight.

The total amount of the flame retardant used in the present invention is preferably in the range of 4.5 parts by weight to 70 parts by weight, preferably in the range of 4.5 parts by weight to 40 parts by weight with respect to 100 parts by weight of the urethane resin. Is more preferable, and the range is further preferably in the range of 4.5 parts by weight to 30 parts by weight.
The total amount of the flame retardant used in the present invention is preferably in the range of 9 parts by weight to 210 parts by weight, more preferably in the range of 9 parts by weight to 120 parts by weight, based on 100 parts by weight of the polyol compound. It is more preferably in the range of 9 parts by weight to 90 parts by weight.

When the total amount of the flame retardant is 4.5 parts by weight or more, the molded product made of the foamable polyurethane composition can prevent the dense residue formed by the heat of the fire from cracking, and when it is 70 parts by weight or less. Does not inhibit the foaming of the foamable polyurethane composition.

In a preferred embodiment, the foamable polyurethane composition is based on 100 parts by weight of a urethane resin composed of a polyisocyanate and a polyol, of which 50 to 85 parts by weight is polyisocyanate and 0.1 parts by weight is a foam stabilizer. Contains 10 parts by weight, 3.5 to 10 parts by weight of catalyst, 0.1 to 30 parts by weight of foaming agent, 4.5 parts by weight to 70 parts by weight of flame retardant, and 3 parts by weight of red phosphorus among the flame retardants. In the range of parts to 18 parts by weight, at least one selected from phosphate ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, and metal hydroxide is 1.5. It is a part by weight to 52 parts by weight. In this case, the flame retardant is preferably 4.5 parts by weight to 52 parts by weight, more preferably 4.5 parts by weight to 30 parts by weight. At least one selected from phosphoric acid ester, phosphate-containing flame retardant, bromine-containing flame retardant, boron-containing flame retardant, antimony-containing flame retardant, and metal hydroxide is a boron-containing flame retardant, and the preferred range is 1. The range is from 5 parts by weight to 9 parts by weight.

7. Other components The inorganic filler is not particularly limited, but for example, silica, diatomaceous earth, alumina, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, basic magnesium carbonate, calcium carbonate. , Magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salts such as calcium silicate, talc, clay, mica, wollastonite, montmorillonite, bentonite, active white clay, Sepiolite, Imogolite, Cerisite, Glass Fiber, Glass Beads, Silica Parun, Aluminum Nitride, Boron Nitride, Silicon Nitide, Carbon Black, Graphite, Carbon Fiber, Carbon Parun, Charcoal Powder, Various Metal Powders, Potassium Titanium, Magnesium Sulfate, Titanium Examples thereof include lead acid zirconate, aluminum porate, molybdenum sulfide, silicon carbide, stainless fibers, various magnetic powders, slag fibers, fly ash, silica-alumina fibers, alumina fibers, silica fibers, and zirconia fibers.

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

In a preferred embodiment of the present invention, fine silica powder is preferably used in the polyol-containing composition of the present invention in order to improve storage stability. Fine silica is called fumed silica, colloidal silica, or the like. The fine silica powder forms a network structure in the polyol-containing composition and exerts an effect of suppressing caking (precipitation and aggregation) of solid components.

The amount of fine silica added is preferably in the range of 0.01 parts by weight to 10 parts by weight, more preferably in the range of 0.1 parts by weight to 5 parts by weight, based on 100 parts by weight of the polyol compound. , 0.50 parts by weight to 2 parts by weight is more preferable.

When the range of fine silica is 0.01 parts by weight or more, the effect of storage stability of the polyol-containing composition can be exhibited, and when it is 10 parts by weight or less, the flow is not too high and suitable for forming polyurethane foam. Sex can be achieved.

The amount of fine silica added is preferably in the range of 0.005 parts by weight to 4 parts by weight with respect to 100 parts by weight of the urethane resin. It is more preferably in the range of 0.05 parts by weight to 2 parts by weight, and further preferably in the range of 0.1 parts by weight to 1 part by weight.

When the range of fine silica is 0.005 parts by weight or more, the storage stability of the polyol-containing composition can be exhibited, and when it is 10 parts by weight or less, the fluidity is not too high and suitable for forming polyurethane foam. Can be achieved.

The foamable polyurethane composition contains, as necessary, phenol-based, amine-based, sulfur-based antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents, etc., as long as the object of the present invention is not impaired. It can contain auxiliary components such as stabilizers, cross-linking agents, lubricants, softeners, pigments, antistatic resins, and antistatic agents such as polybutene and petroleum resins.

Above 1. ~ 7. The components of are mixed and the effervescent polyurethane composition reacts and cures, so its viscosity changes over time. Therefore, before using the effervescent polyurethane composition, the effervescent polyurethane composition is divided into two or more to prevent the effervescent polyurethane composition from reacting and curing. Then, when the foamable polyurethane composition is used, the foamable polyurethane composition can be obtained by combining the foamable polyurethane compositions divided into two or more into one.

When the effervescent polyurethane composition is divided into two or more, each component of the effervescent polyurethane composition divided into two or more does not start curing, and after mixing each component of the effervescent polyurethane composition. Each component may be divided so that the curing reaction starts.

The effervescent polyurethane composition may be cured by mixing and at room temperature, but each component may be preheated.

The polyol-containing composition of the present invention is a polyol premix for reacting with polyisocyanate to obtain a polyurethane foam.

The foamable polyurethane composition produced by mixing a polyisocyanate with a polyol premix containing a polyol, a foam stabilizer, a catalyst, a foaming agent, and a flame retardant is foamed and cured to form a polyurethane foam. The present invention also includes a polyurethane foam molded from an effervescent polyurethane composition containing the above components.

The polyol-containing composition of the present invention has a viscosity of 105 mPas or more, preferably 105 or more and 800 mPas or less at a rotation speed of 100 rpm at 25 ° C., and a thixotropy value (also referred to as thixotropy index) calculated by the following formula is 1.9 or more. It is characterized by being.
(Chixo value) = (Viscosity at 25 ° C. rotation speed 1 rpm) / (Viscosity at 25 ° C. rotation speed 10 rpm)

By setting the viscosity at a rotation speed of 100 rpm at 25 ° C. to 105 mPas or more, the occurrence of liquid dripping is suppressed, and the decrease in flame retardancy when the solid content is small is suppressed. Further, it is preferable that the viscosity at a rotation speed of 100 rpm at 25 ° C. is 800 mPas or less because the foamable polyurethane composition is prevented from being lowered in fluidity and the polyurethane foam forming ability is excellent.

As used herein, the term "viscosity" refers to a measured value using an E-type viscometer.

Further, the polyol-containing composition of the present invention preferably has a solid component of 35 parts by weight or more with respect to 100 parts by weight of the polyol compound. By setting the solid component to 35 parts by weight or more, a polyurethane foam having improved flame retardancy can be obtained.

The "solid component" means an insoluble component contained in the polyol-containing composition. "Solid component" is red phosphorus; flame retardant of phosphoric acid compound such as phosphoric acid ester and phosphate-containing flame retardant; flame retardant of organic halogen compound such as bromine-containing flame retardant; boric acid-containing flame retardant; antimony-containing flame retardant Flame retardants of metal compounds such as fuel agents and metal hydroxides; include flame retardants such as inorganic fillers such as silica compounds or inorganic fillers that are insoluble components. As a preferable example, the above 6. The flame retardant described in the flame retardant or 7. Examples of the inorganic filler described in the other components include those which are insoluble components.

In one aspect of the present invention, the polyol-containing composition of the present invention is one or more (preferably all) selected from the group consisting of red phosphorus, boric acid-containing flame retardants and fillers based on 100 parts by weight of the polyol compound. ) Is included in 35 parts by weight with respect to 100 parts by weight of the polyol compound.

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

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

The use of the foamable polyurethane composition and the polyurethane foam of the present invention is not particularly limited, but is usually used for filling openings or gaps in buildings. Here, "building" includes arbitrary structures that make up the building, and not only structural materials of the building such as walls, ceilings, roofs, and floors, but also windows (sliding windows, hinged windows, raising and lowering windows). , Etc.), obstacles, doors (that is, doors), doors, bran, windows, and other fittings are also included. The "opening" refers to any opening that occurs in the building, including joints that occur between the structural materials of the building and holes that occur in one structural material, but the "gap" refers to the opening. Among the two facing members or parts, such as between structural materials and structural materials, between structural materials and fittings, between fittings and fittings, and between structural materials or fittings and furniture (kitchen sinks, etc.). Refers to the resulting opening.

In addition, the foamable polyurethane composition is not only directly filled in the opening or gap of the building, but also poured into a mold or the like to fit the opening or gap of the building (length, width, and thickness). The polyurethane foam is placed in the opening or gap of the building after being molded into a container or discharged from the mixing container to another location and cut to the specified dimensions (length, width, and thickness) as the polyurethane foam. It may be attached.

Polyisocyanurate foams made by foaming and curing a foamable polyurethane composition are excellent in waterproofness, airtightness, and fire resistance, and are therefore generated by water, smoke, flames, and combustion through openings or gaps in buildings. It is possible to effectively block the intrusion of gas and the like.

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

Production Example 1 Production of Foamable Polyurethane Resin Composition and Flame Retardant Rigid Polyurethane Foam The foamable polyurethane resin compositions according to Examples 1 to 3 and Comparative Examples 1 to 3 were prepared according to the formulations shown in Table 1 (1). ) Polyol premix and (2) Polyisocyanate were prepared separately. The details of each component in the table are as follows.

(1) Polyol premix polyol p-phthalate polyester polyol (manufactured by Kawasaki Kasei Chemicals, product name: Maximol RLK-087, hydroxyl value = 200 mgKOH / g)
・ Defoaming agent Polyalkylene glycol-based defoaming agent (manufactured by Toray Dow Corning, product name: SH-193)
-Catalyst triad catalyst (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark) -TRX)
Quantifier catalyst (manufactured by Sun Appro Co., Ltd., product name: U-CAT 18X)
Alkylated polyalkylene polyamine (tertiary amine) (manufactured by Tosoh Corporation, product name: TOYOCAT®-TT)
Urethane catalyst of tertiary amine (imidazole compound, manufactured by San-Apro Co., Ltd., product name: U-CAT 202)
Tertiary amine (mixture of 1,2-dimethylimidazole and ethylene glycol, manufactured by Tosoh Corporation, product name: TOYOCAT®-DM70)
・ Foaming 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, called "TMCPP")
Red phosphorus (manufactured by Phosphorus Chemical Industry Co., Ltd., product name: Nova Excel 140)
Zinc borate (manufactured by Hayakawa Shoji Co., Ltd., product name: FIRebreak ZB)
-Inorganic filler Wollastonite (SiO ₂ · CaO) (manufactured by Kinsei Matek, product name: SH-1250)
Fine silica (manufactured by Nippon Aerosil Co., Ltd., product name: Aerosil R976S).

(2) Polyisocyanate 4,4'-diphenylmethane diisocyanate (4,4'-MDI) (manufactured by Manka Kagaku Japan Co., Ltd., product name: PM200).

According to the formulation in Table 1 below, 600 L of polyol premix (polyol-containing composition) was prepared using a suitable container and a suitable homomixer. For Examples 1 to 3 and Comparative Examples 1 and 3, each time the solid component 1 raw material was added, stirring and dispersion were performed at a rotation speed of 3600 rpm for 40 minutes (“sufficient stirring”). In Comparative Example 2, after all the raw materials were added, stirring and dispersion were performed at a rotation speed of 3600 rpm for 20 minutes (“insufficient stirring”).

The (1) polyol premix immediately after stirring or after standing for 2 weeks (2w) was stirred for 30 minutes using a homomixer, and then the required amount of the kneaded mixture of the components of the (1) polyol premix was taken out. (2) Polyisocyanate was added to this polyol premix, and the mixture was stirred with a hand mixer for about 10 seconds to prepare a foamable polyurethane resin composition. The obtained foamable polyurethane resin composition lost its fluidity with the passage of time, and a flame-retardant rigid polyurethane foam was obtained. The polyol premix and the foam were evaluated according to the following criteria, and the results are shown in Table 1 (the ratio of each component is shown in parts by weight with respect to 100 parts by weight of urethane resin).

Test Example 1 Viscosity measurement The viscosity of the polyol premix (polypoly-containing composition) immediately after stirring was measured at 25 ° C. using a Viscometer / TV-22 (manufactured by Toki Sangyo Co., Ltd.). The rotation speed was set in the order of 0.5 rpm, 1 rpm, 5 rpm, 10 rpm, 20 rpm, 50 rpm, and 100 rpm, and the numerical value was read when it became stable.

The chixo value was determined by the ratio of the viscosity at a rotation speed of 1 rpm to the viscosity at a rotation speed of 10 rpm.

The measurement results of the viscosity and the thixo value are shown in Table 1 and the graph of FIG.

As shown in Table 1, the viscosities of Examples 1 to 3 at a rotation speed of 100 rpm at 25 ° C. are 136, 109, and 154, respectively, and the viscosities of Comparative Examples 1 to 3 at a rotation speed of 100 rpm at 25 ° C. are They were 218, 102, and 143, respectively.

As shown in Table 1, the chixo values of Examples 1 to 3 were 2.9, 2.7 and 2.1, respectively, and the chixo values of Comparative Examples 1 to 3 were 1.5, 2.3 and 1.8, respectively.

Test Example 2 Flame Retardant Test A sample for corn calorimeter test was cut out from the cured foam of the foamable polyurethane resin composition so as to have a size of 10 cm × 10 cm × 5 cm, and a radiant heat intensity of 50 kW / m ^{2 was obtained in accordance with ISO-5660.} The maximum heat generation rate and the total heat generation amount when heated for 20 minutes were measured.

This measurement method is a test method specified by the Building Comprehensive Laboratory, which is a public institution stipulated in Article 108-2 of the Building Standards Law Enforcement Ordinance, as corresponding to the standard by the corn calorimeter method. It conforms to the ISO-5660 test method.

It passed when the total calorific value of the corn calorimeter was 8 MJ / m ² or less after heating for 20 minutes, but in this test, ^{those exceeding 8 MJ / m 2} after heating for 20 minutes were x, and those exceeding 8 MJ / m 2 after heating for 20 minutes. Was marked as ○.

As shown in Table 1, Examples 1 to 3 passed the test regardless of whether (1) the polyol premix immediately after production or after standing for 2 weeks was used. Comparative Examples 1 and 3 were (1) passed when the polyol premix immediately after production was used, but failed when the one after standing for 2 weeks was used. Example 2 was unacceptable when either (1) the polyol premix immediately after production or the one after standing for 2 weeks was used.

Claims (5)

A polyol-containing composition for reacting with polyisocyanate to obtain a polyurethane foam.
The polyol-containing composition contains a polyol compound, a foam stabilizer, a catalyst, a foaming agent, fine silica powder and a flame retardant.
The flame retardant was contained in the range of 9 to 210 parts by weight with respect to 100 parts by weight of the polyol compound.
The content of the solid component is 35 parts by weight or more with respect to 100 parts by weight of the polyol compound.
A polyol-containing composition characterized in that the viscosity of the polyol-containing composition at a rotation speed of 100 rpm at 25 ° C. is 105 mPas or more, and the chixo value calculated by the following formula is 1.9 or more.
(Chixo value) = (Viscosity at 25 ° C. rotation speed 1 rpm) / (Viscosity at 25 ° C. rotation speed 10 rpm) The polyol-containing composition according to claim 1, wherein the fine silica powder is contained in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyol compound. A foamable polyurethane composition, which comprises reacting the polyol-containing composition according to claim 1 or 2 with a polyisocyanate. A polyurethane foam obtained by curing the foamable polyurethane composition according to claim 3. The polyurethane foam according to claim 4, which is a molded product.

Images