JP5166209B2 - Fireproof and heat insulating structure and method for forming the same - Google Patents

Description

  The present invention relates to a fireproof and heat insulating structure excellent in heat insulating properties and fireproofing properties, and a method for forming the same.

In a building material such as an outer wall or a roof that constitutes a building, a heat insulating material or the like is installed on the indoor side in order to improve the heat insulating performance. As such a heat insulating material, for example, an organic heat insulating material such as urethane foam, phenol foam, cellulose fiber or the like is used, and among them, urethane foam is excellent in heat insulating properties and is constructed at a relatively low cost. It is frequently used because it has features such as being able to do so.
However, organic heat insulating materials such as urethane foam are weaker than heat compared to inorganic heat insulating materials. Therefore, for parts that require fire resistance in addition to heat insulating properties such as building materials such as outer walls and roofs, organic heat insulating materials are used. Fireproof materials are laminated to give fireproof performance. (For example, Patent Documents 1 to 3 etc.)

Japanese Patent Application Laid-Open No. 2004-137691 JP 2003-261814 A JP 2007-320057 A

However, when a fire or the like occurs, even if a fireproof material or the like is laminated on the organic heat insulating material, heat is eventually transmitted to the organic heat insulating material, and the organic heat insulating material may shrink due to the heat.
For such a problem, it is usually possible to obtain a sufficient fireproof performance by increasing the thickness of the organic heat insulating material or by increasing the thickness of the fireproof material. However, it is not always the best method for compressing the living space, and a thin fireproof and heat insulating material that does not press the living space is required.

  In the present invention, as a result of intensive studies in view of such problems, a urethane foam layer having an NCO / OH ratio of 0.5 or more and less than 1.5, and an NCO / OH ratio of 1.5 or more and 5.0 or less. It was found that the fireproof and heat insulating structure in which the urethane foam layer and the fireproof layer were laminated in this order was excellent in heat insulation and fire resistance even when the total thickness of the urethane foam layer was thin, and the present invention was completed.

  The present invention for solving the above problems is as follows.

  The fireproof and heat insulating structure of the present invention is excellent in heat insulating properties and fireproofing properties even when the urethane foam is thin.

The fireproof and heat insulating structure of the present invention comprises a polyol compound (1) containing water as a polyol compound, a catalyst, a flame retardant, and a foaming agent, and a polyisocyanate component having an NCO / OH ratio of 0.5 or more and 1.5. Urethane foam layer (1) obtained by mixing to be less than
Obtained by mixing a polyol compound (2) containing water as a polyol compound, catalyst, flame retardant, and foaming agent and a polyisocyanate component so that the NCO / OH ratio is 1.5 or more and 5.0 or less. Urethane foam layer (2),
Fire protection layer (3),
Are sequentially stacked.

The urethane foam layer (1) comprises a polyol compound (1) containing water as a polyol compound, a catalyst, a flame retardant, and a foaming agent, and a polyisocyanate component having an NCO / OH ratio of 0.5 or more and less than 1.5. (Preferably 0.8 to 1.4, more preferably 1.01 to 1.3).
When the NCO / OH ratio is 0.5 or more and less than 1.5, it is possible to impart excellent heat insulating properties and excellent adhesion to the substrate described later.

The urethane foam layer (2) comprises a polyol compound (2) containing water as a polyol compound, a catalyst, a flame retardant, and a foaming agent, and a polyisocyanate component having an NCO / OH ratio of 1.5 or more and 5.0 or less. (Preferably 1.8 to 4.0, more preferably 2.0 to 3.0).
When the NCO / OH ratio is 1.5 or more and 5.0 or less, excellent fire resistance can be imparted. Moreover, it is excellent in adhesiveness with a urethane foam layer (1).

In the present invention, by using such a urethane foam layer (1) and urethane foam layer (2), it is possible to achieve both excellent heat insulation and excellent fire resistance, and the thickness of the entire urethane foam is thin. Even in this case, it is possible to obtain a fireproof and heat insulating structure excellent in heat insulating properties and fireproofing properties.
When a urethane foam layer is only a urethane foam layer (1), it is excellent in heat insulation, but tends to be inferior in fire resistance.
Moreover, when a urethane foam layer is only a urethane foam layer (2), it is excellent in fireproof property, but there exists a tendency to be inferior to adhesiveness with a base material, and heat insulation.

  Although it does not specifically limit as a polyol compound in polyol composition (1), (2), What contains polyether polyol and / or aromatic ester polyol is preferable.

  Examples of polyether polyols include aromatic polyether polyols, glycerin polyether polyols, tertiary amino group-containing polyether polyols, and the like.

As the aromatic polyether polyol, bisphenol A type polyether polyol obtained by adding alkylene oxide such as ethylene oxide and propylene oxide with bisphenol A as an initiator, and aromatic amines, that is, toluenediamine, diethyltoluenediamine 4,4′-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, triethanolamine, Mannich condensation product, etc. as an initiator to obtain an alkylene oxide such as ethylene oxide or propylene oxide. Aromatic amine polyether polyols can be mentioned.
As the aromatic polyether polyol, an aromatic amine-based polyether polyol, particularly a Mannich-modified polyether polyol obtained by adding an alkylene oxide to a formalin condensate of a phenol and an amine compound is particularly preferable. As such an aromatic polyether polyol, a hydroxyl value of 200 to 400 mgKOH / g is preferable in terms of foam flame retardancy and dimensional stability. When deviating from this range, the flame retardancy and dimensional stability of the resulting foam may be reduced.

The glycerin-based polyether polyol is preferably a polyether polyol obtained by ring-opening addition of at least one alkylene oxide such as ethylene oxide and propylene oxide using glycerin as an initiator.
The hydroxyl value of the glycerin-based polyether polyol is preferably 350 to 600 mgKOH / g in terms of storage stability of the polyol composition, adhesion to the base material and the urethane foam layer, and the fireproof layer. When deviating from this range, there is a risk that the storage stability and the adhesion of the polyol composition may be lowered.

  Examples of the tertiary amino group-containing polyether polyol include low molecular weight amines such as alkylene diamine and alkanol amine, that is, ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, neopentyl diamine and the like having 2 to 8 carbon atoms And those obtained by ring-opening addition of at least one alkylene oxide such as ethylene oxide and propylene oxide.

  Examples of polyether polyols include glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexylene glycol, and cyclohexanedimethanol. Or a polyether polyol obtained by ring-opening addition of at least one of alkylene oxides such as ethylene oxide and propylene oxide using trimethylolpropane, sorbitol, sucrose, etc. as an initiator.

As the polyether polyol, it is particularly preferable to include an aromatic polyether polyol. By using the aromatic polyether polyol, it is possible to obtain a rigid polyurethane foam excellent in storage stability of the polyol composition, foamability, curability, foam flame retardancy, dimensional stability, and heat insulation, in particular. it can.
The aromatic polyether polyol is used in the polyether polyol in an amount of 50 to 100% by weight, more preferably 70 to 100% by weight. The storage stability of the polyol composition, the foamability, the flame retardancy of the foam, and the dimensional stability It is suitable in terms of the above. When the amount is less than 50% by weight, foamability, flame retardancy of the obtained foam, and the like may be lowered.

  Such a polyether polyol is used in a total amount of polyol compound of 20 to 100% by weight, more preferably 25 to 95% by weight, foam foaming property, adhesion to a base material, a urethane foam layer, and a fireproof layer, etc. This is preferable. If it is less than 20% by weight, foam foaming and adhesion may be lowered.

  The aromatic ester polyol includes at least one glycol selected from ethylene glycol, diethylene glycol, 1,6-hexanediol, and the like, and at least one aromatic dicarboxylic acid selected from phthalic acid, isophthalic acid, terephthalic acid, and the like. Examples of the ester polyol include those having as a main component an ester skeleton obtained by dehydration condensation of a dicarboxylic acid having a phthalic acid skeleton and a glycol compound.

  Such an aromatic ester polyol is preferably used in an amount of 0 to 80% by weight, more preferably 5 to 75% by weight in the total amount of the polyol compound, in terms of flame retardancy and dimensional stability. If it is more than 80% by weight, the foaming property of the foam may be lowered. The hydroxyl value of such an aromatic ester polyol is preferably 100 to 400 mgKOH / g.

  In the present invention, in particular, in the polyol composition (1), the aromatic ester polyol is 50 to 80% by weight, the polyether polyol is 20 to 50% by weight, and the polyol composition (2) is aromatic. It is preferable to contain 0 to 60% by weight of the group ester polyol and 40 to 100% by weight of the polyether polyol.

  As the catalyst, known catalysts such as tertiary amine catalysts, imidazole catalysts, and fatty acid alkali metal salt catalysts can be used without limitation.

  As the tertiary amine catalyst, specifically, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N N-alkylpolyalkylenepolyamines such as', N ″ -pentamethyldiethylenetriamine, diazabicycloundecene (DBU), bis (β-dimethylaminoethyl) ether, N, N, N-dimethylaminopropylhexahydrotriazine, etc. The tertiary amine catalyst can be exemplified.

Examples of the imidazole catalyst include 1-isobutyl-2-methylimidazole, 1-methylimidazole, 1,2-dimethylimidazole, and examples of the fatty acid alkali metal salt catalyst include potassium octylate and potassium acetate. it can.
In addition to these catalysts, an amine catalyst or an organometallic catalyst may be used in combination.

  The addition amount of the catalyst is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polyol compound.

Flame retardants include tricresyl phosphate, diphenyl cresyl phosphate, tris (β-chloroethyl) phosphate, tris (β-chloropropyl) phosphate, tributoxyethyl phosphate, tributyl phosphate, triethyl phosphate, cresyl phenyl phosphate, dimethyl Organophosphorus compounds such as methylphosphonate; Chlorinated compounds such as chlorinated polyphenyl, chlorinated polyethylene, diphenyl chloride, triphenyl chloride, pentachloride fatty acid ester, perchloropentacyclodecane, chlorinated naphthalene, tetrachlorophthalic anhydride; Antimony compounds such as antimony oxide and antimony pentachloride; phosphorus compounds such as phosphorus trichloride, phosphorus pentachloride, ammonium phosphate and ammonium polyphosphate; other zinc borates and sodium borate A known flame retardant such as an inorganic compound can be used without limitation.
In the present invention, since an effect as a flame retardant and a viscosity reducing agent is exhibited, an organic phosphorus compound is preferable, and tris (β-chloropropyl) phosphate is preferably used, but is not limited thereto. is not.

  In particular, in the case of the polyol composition (1), the amount of the flame retardant added is preferably 5 to 20% by weight based on the polyol composition. Moreover, in the case of a polyol composition (2), it is preferable to contain 20 to 60 weight% with respect to a polyol composition.

Water as a foaming agent is 1 to 6 parts by weight, more preferably 1.5 to 4 parts by weight, based on 100 parts by weight of the polyol composition. If the amount is less than 1 part by weight, the resulting foam may be densified. If the amount is more than 6 parts by weight, the foam is brittle and the adhesion to the housing surface may be reduced.
In particular, in the case of the polyol composition (1), it is preferable to contain 2.5 to 4 parts by weight with respect to 100 parts by weight of the polyol composition.
Moreover, in the case of a polyol composition (2), it is preferable to contain 1.5-3 weight part with respect to 100 weight part of polyol composition.

  Furthermore, the polyol compositions (1) and (2) of the present invention include polyoxyethylene sorbitan fatty acid esters, alkoxysilane condensates having a three-dimensional crosslinked structure, and other foam stabilizers and compatibilizers well known to those skilled in the art. Agents, surfactants, colorants, antioxidants and the like. In particular, it is preferable that at least one of polyoxyethylene sorbitan fatty acid ester and an alkoxysilane condensate having a three-dimensional crosslinked structure is contained.

  Polyoxyethylene sorbitan fatty acid ester is a compound having a chemical structure represented by Chemical Formula 1 (Chemical Formula 1).

(Chemical formula 1)
O (CH ₂ CH ₂ O) mH
│
CH
/ \
_{H (CH 2 CH 2 O)} pO─CH CHO (CH 2 CH 2 O) nH
│ │
CH ₂ CHCH ₂ OCOR
\ /
O

R is an alkyl group having 8 to 18 carbon atoms, an alkenyl group, or an alkadienyl group. Specifically, R is an alkyl having 8 or more carbon atoms such as an octyl group, a stearyl group, a lauryl group, an oleyl group, and a palmityl group. Group, alkenyl group and alkadienyl group are exemplified. m + n + p is 15 or more, more preferably 20 or more (provided that m + n is 1 or more), and HLB is preferably 10 or more, more preferably 13 or more, and even more preferably 15 or more.
In addition, HLB is hydrophilic-lipophilic balance, and is a value calculated by the Griffin method in the present invention.

Among such polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan monoalkylate can be preferably used particularly in the present invention.
Since polyoxyethylene sorbitan monoalkylate has a predetermined hydroxyl value, it has excellent compatibility with polyol and water, and it contributes to improving the dimensional stability of foam by being incorporated into the polyol skeleton during foaming There is. Among polyoxyethylene sorbitan monoalkylates, the total number of repeating units of ethylene oxide units (m + n + p) is 15 or more, further 20 or more, and HLB is 10 or more, further 13 or more, and more than 15 In particular, polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monooleate are preferable.

  The amount of polyoxyethylene sorbitan fatty acid ester added is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of the polyol composition. In such a range, sufficient storage stability of the polyol composition can be secured, and a urethane foam excellent in foaming stability, foam dimensional stability and heat insulation can be obtained. When deviating from this range, sufficient storage stability of the polyol composition may not be obtained, and the dimensional stability and heat insulating property of the foam may be deteriorated.

  As an alkoxysilane condensate having a three-dimensional crosslinked structure, for example, an alkoxysilane compound represented by Chemical Formula 2 (Chemical Formula 2) can be obtained by mixing and condensing by a known method.

(Chemical formula 2)
(R) _m (RO) _3-m- (Si-O) n-X
R represents a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, an amino group, an epoxy group, or halogen, and R may be the same or different.
X represents a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, hydrogen, or —Si (R) ₃ .
Some of carbon atoms and hydrogen atoms may be replaced with nitrogen atoms, halogen atoms, or the like.
n is an integer of 1 or more (preferably n is 1).
m is an integer of 0-3. In addition, 5 weight% or more of the alkoxysilane compound used by this invention is a compound whose m is 0-1.

Examples of the alkoxysilane compound include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, and tetra-t-butoxysilane. , Dihydroxydimethoxysilane, dihydroxydiethoxysilane, dihydroxydi-n-propyloxysilane, trihydroxymethoxysilane, trihydroxyethoxysilane, trihydroxy-n-propyloxysilane, diphenoxydiethoxysilane, methyltrimethoxysilane, methyltri Ethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxy Lan, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltributoxysilane, isobutyltrimethoxysilane, phenyltrimethoxy Silane, phenyltriethoxysilane, phenyltributoxysilane, hexyltrimethoxysilane, cyclohexyltriethoxysilane, decyltrimethoxysilane, naphthyltriethoxysilane, 4-chlorophenyltriethoxysilane, 4-cyanophenyltriethoxysilane, 4-amino Phenyltriethoxysilane, 4-nitrophenyltriethoxysilane, 4-methylphenyltriethoxysilane, 4-hydroxyphenyl Liethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltri-n-propyloxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxyepoxypropyltrimethoxysilane, 3-glycidoxyepoxypropyltriethoxysilane, hydroxytrimethoxysilane, hydroxytriethoxysilane, hydride Xytri-n-propyloxysilane, methylhydroxydimethoxysilane, phenylhydroxydimethoxysilane, methyl (phenoxy) diethoxysilane, phenyl (phenoxy) diethoxysilane, triphenoxyethoxysilane, methyl (diphenoxy) ethoxysilane, phenyl (diphenoxy) Ethoxysilane Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane , Dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane Diphenyldibutoxysilane, methylethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylcyclohexyldiethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-glycidoxyepoxypropyl Methyldiethoxysilane, dimethyl (phenoxy) ethoxysilane, diphenyl (phenoxy) ethoxysilane, methyl (phenyl) (phenoxy) ethoxysilane trimethylmethoxysilane, trimethylethoxysilane, trimethyl-n-propyloxysilane, dimethyl (ethyl) ethoxysilane , Dimethyl (cyclohexyl) ethoxysilane, dimethyl (phenyl) ethoxysilane, methyl (diphenyl) ethoxysilane, etc., or their condensation Etc. The.

  The details of such an alkoxysilane condensate are unknown, but it is incompatible with the polyol compound, but is efficiently dispersed in the polyol composition by the action of the polyoxyethylene sorbitan fatty acid ester. It seems to be excellent in improving the performance. Furthermore, it is considered that the alkoxysilane condensate is efficiently incorporated into the polyurethane skeleton, and a rigid polyurethane foam excellent in long-term dimensional stability can be obtained by the action of the incorporated alkoxysilane condensate.

  Moreover, when obtaining an alkoxysilane condensate, a known catalyst can be used.

  The addition amount of the alkoxysilane condensate is suitably 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.3 to 3% by weight, based on the total amount of the polyol composition. When the amount is less than 0.01% by weight, long-term foam dimensional stability may not be obtained. When the amount is more than 10% by weight, foam stability may be inferior.

As the foam stabilizer, a known silicone foam stabilizer for rigid polyurethane foam, that is, a graft copolymer (polyether-modified silicone compound) of polydimethylsiloxane and polyoxyethylene glycol or polyoxyethylene-propylene glycol is used without limitation. be able to. Such foam stabilizers include SH-193, L-5420, L-5340, SZ-1698, SZ-1704, SZ-1923, SZ-1932 (Toray Dow Corning), F-502, F-506 (Shin-Etsu Chemical). Industrial) and the like.
In the present invention, by using the alkoxysilane condensate and polyoxyethylene sorbitan fatty acid ester in combination with the silicone foam stabilizer, a rigid polyurethane foam having particularly excellent storage stability of the polyol composition can be obtained.

  The polyisocyanate component that forms a rigid polyurethane foam by mixing and reacting with the polyol compositions (1) and (2) is not particularly limited, and polyisocyanate components known in the technical field of polyurethane can be used without limitation. . For example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI (c-MDI)), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), etc. In the present invention, liquid MDI such as crude MDI (c) is usually used because of ease of handling, reaction speed, physical properties of the resulting rigid polyurethane foam, and low cost. -MDI) is preferably used.

Moreover, the temperature at the time of formation of rigid polyurethane foam (1), (2) is adjusted so that the temperature of the said polyol composition (1), (2) and the said polyisocyanate component may be about 30-80 degreeC, respectively. It is preferable to keep it.
The viscosity of the polyol compositions (1) and (2) is preferably 1000 mPa · s (20 ° C.) or less, and 500 mPa · s (20 ° C.) from the viewpoint of easy production of a rigid polyurethane foam by a spray method. The following is more preferable.
In the formation of such a rigid polyurethane foam, there is no particular limitation as long as the polyol compositions (1) and (2) and the polyisocyanate component can be uniformly mixed, and a known apparatus can be used. For example, low pressure and high pressure foaming machines for injection foaming, low pressure and high pressure foaming machines for slab foaming, low pressure and high pressure foaming machines for continuous lines, and spraying work used when manufacturing small mixers and ordinary urethane foam. For example, a spray foaming machine can be used.
Further, the foam density of the rigid polyurethane foam (1) and the rigid polyurethane foam (2) is not particularly limited, and may be about 25 kg / m ³ or more and 70 kg / m ³ or less. Specifically, the foam density of the rigid polyurethane foam (1) is preferably 25 kg / ^{m 3} or more 60 kg / ^{m 3} or less (more 30kg / ^{m 3} or more 40 kg / ^m less than ³⁾ is about. Further, the foam density of the rigid polyurethane foam (2) is preferably larger than the foam density of the rigid polyurethane foam (1), and specifically, 30 kg / m ³ or more and 70 kg / m ³ or less (more 40 kg / m ³ or more and 60 kg / m ³ or less) is preferable.

  The fireproof layer (3) is not particularly limited, such as a dry material or a wet material, and can be used.

  As dry materials, color steel plate, galvanium steel plate, PVC steel plate, stainless steel plate, aluminum plate, copper plate, titanium plate, aluminized steel plate, galvanized steel plate, clad steel plate, sandwich steel plate, calcium silicate plate, gypsum board, lightweight concrete plate Non-combustible boards such as fiber mats such as rock wool mats and ceramic wool mats, fireproof sheets, foam fireproof sheets and the like.

  Examples of the wet material include a fireproof material composition such as a fireproof coating material and a foam fireproof material.

Examples of the fireproof covering material include those containing a binder, inorganic aggregate, and the like.
Binders include inorganic binders such as cement, gypsum and silicone resin, acrylic resin, vinyl resin, vinyl acetate resin, vinyl propionate resin, vinyl versatate resin, vinyl acrylate resin, ethylene vinyl acetate resin, vinyl chloride resin, epoxy Examples thereof include organic binders such as resins, and one or more of these can be used in combination. In particular, it is preferable to use a binder containing an inorganic binder from the viewpoint of fire resistance.
Examples of inorganic aggregates include oxalate, carbonate, aluminum oxide, aluminum hydroxide, metal hydrate, clay, clay, shirasu, mica, titanium dioxide, and perlite, expanded shale, expanded vermiculite, pumice, Examples include inorganic lightweight aggregates such as shirasu balloons, hollow glass balloons, ALC pulverized products, and aluminosilicate foams. In the present invention, by including the inorganic lightweight aggregate, it is possible to form a fireproof layer that is excellent in fire resistance and also in light weight.
In addition to the above components, the fireproof coating material includes organic resin powder, heat absorbing material, reinforcing material, flame retardant, filler, fiber, plasticizer, preservative, antifungal agent, antifoaming agent, leveling agent. In addition, components such as a pigment dispersant, an anti-settling agent, an anti-sagging agent, an ultraviolet absorber, and an antioxidant may be included.

Examples of the foam fireproof material include those containing a binder, a foaming agent and the like.
Binders include inorganic binders such as cement, gypsum and silicone resin, acrylic resin, vinyl resin, vinyl acetate resin, vinyl propionate resin, vinyl versatate resin, vinyl acrylate resin, ethylene vinyl acetate resin, vinyl chloride resin, epoxy Examples include resins, biogum, galactomannan derivatives, alginic acid and derivatives thereof, gelatin, casein and albumin, and organic derivatives such as these derivatives, cellulose and cellulose derivatives. Among these, one or more of these may be used in combination. Can be used. In particular, it is preferable to use an organic binder, particularly a binder containing a thermoplastic organic binder from the viewpoint of foamability.
Examples of the foaming agent include phosphorus compounds such as ammonium polyphosphate, nitrogen-containing compounds such as melamine, and thermally expandable graphite.
In addition to the above components, foam fireproofing materials include flame retardants, carbonizing agents, fillers, reinforcing materials, fibers, plasticizers, preservatives, antifungal agents, antifoaming agents, leveling agents, pigment dispersants, and anti-settling agents. Components such as an agent, a sagging inhibitor, a UV absorber, and an antioxidant may be included.

The method of laminating such a urethane foam layer (1), urethane foam layer (2), and fireproof layer (3) to form a fireproof heat insulating structure is not particularly limited, such as a wet method, a dry method, etc. A polyol compound (1) containing a polyol compound, a catalyst and water as a foaming agent and a polyisocyanate component are mixed on the material so that the NCO / OH ratio is 0.5 or more and less than 1.5. Forming a urethane foam layer (1) obtained by
On the urethane foam layer (1), a polyol composition (2) containing water as a polyol compound, a catalyst and a blowing agent, and a polyisocyanate component have an NCO / OH ratio of 1.5 to 5.0. Forming a urethane foam layer (2) obtained by mixing so that
Forming a fireproof layer (3) on the urethane foam layer (2);
Formed by a process including:

  The substrate used in the present invention is not particularly limited. For example, concrete, mortar, lightweight mortar, lightweight concrete, calcium silicate plate, ALC plate, gypsum board, slate plate, extruded plate, ceramic siding material, metal Siding materials, plastic siding materials, various plywoods and the like. Moreover, clay tiles, slate tiles, press cement tiles, concrete tiles, metal roofing materials, and the like are also included. It can also be used as a composite type substrate formed by combining two or more of these materials.

The step of forming the urethane foam layer (1) on the substrate is not particularly limited, and a method of sticking the urethane foam layer (1) prepared in advance using an adhesive or the like, , Low pressure for injection foaming, high pressure foaming machine, low pressure for slab foaming, high pressure foaming machine, low pressure for continuous line, high pressure foaming machine, spray foaming machine for spraying construction, etc. The method of forming by coating the mixture of (1) and a polyisocyanate component, etc. are mentioned.
In this invention, the method of forming by coating a base material using various foaming machines etc. is preferable. In such a method, the temperature at the time of molding the urethane foam layer (1) is preferably adjusted so that the temperatures of the polyol composition (1) and the polyisocyanate compound are about 30 to 80 ° C., respectively. .

Furthermore, the urethane foam layer (2) may be formed by the same method as that for the urethane foam layer (1).
In the present invention, a urethane foam is formed by applying a mixture of the polyol composition (1) and the polyisocyanate component once or twice or more and then applying a mixture of the polyol composition (2) and the polyisocyanate component. A layer can be formed.

  As the viscosity of the polyol composition (1) or the mixture of the polyol composition (1) and the polyisocyanate component, the viscosity of the polyol composition (2) or the mixture of the polyol composition (2) and the polyisocyanate component, rigid polyurethane foam is used. Although it is not particularly limited as long as it can be formed, it is preferably 1500 mPa · s (20 ° C.) or less, and preferably 1000 mPa · s (20 ° C.) or less from the viewpoint of easily producing a rigid polyurethane foam by a spray method. Is more preferable. Moreover, it does not specifically limit as a lower limit, However, It is preferable that it is 80 mPa * s (20 degreeC) or more, Furthermore, it is 150 mPa * s (20 degreeC) or more.

  Although it does not specifically limit as a method of forming a fire prevention layer (3) on a urethane foam layer (2), What is necessary is just to stick using a well-known adhesive material etc. in the case of a dry material. In the case of a wet material, it can be applied directly onto the urethane foam layer (2), or it may be laminated after applying a primer such as some sealer or primer. Alternatively, the fireproof material composition can be preliminarily formed into a sheet shape or a board shape and adhered with an adhesive or the like.

  The wet material coating method is not particularly limited. For example, the wet material may be applied once or several times by using a coating tool such as a roller, a brush, a trowel, a spray, a pressure feeder, or a spraying machine.

The thickness of the urethane foam layer (1), the urethane foam layer (2), and the fireproof layer (3) is not particularly limited, but of course, when the thickness is thick, excellent heat insulation even when the thickness is thin, Fireproofness can be obtained, and can be appropriately set for a wide range of applications.
Specifically, the thickness of the urethane foam layer (1) is usually about 1 mm to 40 mm (preferably about 1 mm to 30 mm), and the thickness of the urethane foam layer (2) is usually about 1 mm to 40 mm (preferably 1 mm to About 30 mm). The total thickness of the urethane foam layer (1) and the urethane foam layer (2) may be 2 mm to 60 mm (preferably about 3 mm to 50 mm). The urethane foam layer (1) has particularly excellent heat insulation properties, and the urethane foam layer (2) has excellent heat insulation properties and excellent fireproofing properties. Even if the total thickness of the foam layer is thin, excellent heat insulation and fire resistance can be obtained.
Further, the thickness of the fireproof layer (3) may be appropriately set depending on the use, but in the case of the non-foaming type fireproof layer, it is usually about 1 mm to 20 mm (preferably about 1 mm to 15 mm), and the foaming type fireproof layer (3). Is usually about 0.5 mm to 10 mm.

(Manufacture of polyol composition)
Using the raw materials shown in Table 1, a polyol composition was prepared with the formulation shown in Table 2.

The following test was done about the obtained polyol composition.
(Foam density)
Using a commercially available two-component mixing type spray foaming machine, a urethane composition prepared by mixing various polyol compositions and isocyanate components at a liquid temperature of 40 ° C. at the same volume ratio is placed on a slate plate (900 mm × 900 mm × 6 mm). Each urethane foam layer was formed with an average thickness of 25 mm.
The evaluation sample prepared by cutting the obtained urethane foam layer into 100 mm × 100 mm × 25 mm was left at 25 ° C. for 3 days, and then weighed to calculate the density (kg / m ³ ). The results are shown in Table 2.

(Test Example 1)
Using a commercially available two-component mixing type spray foaming machine, a slate plate (900 mm × 900 mm × 6 mm) was prepared by mixing a polyol composition (1) and an isocyanate component at a liquid temperature of 40 ° C. at the same volume ratio. A urethane foam layer (1) was formed thereon with an average thickness of 25 mm.
Next, the urethane foam layer (2) having an average thickness of 15 mm is formed on the urethane foam layer (1) by mixing the urethane composition obtained by mixing the polyol composition (6) and the isocyanate component in the same volume ratio at a liquid temperature of 40 ° C. Formed.
Next, on the urethane foam layer (2), a calcium silicate plate (900 mm × 900 mm × 6 mm) was attached using a urethane adhesive to obtain a test body.
The test described below was performed on the obtained specimen.

(Fireproof test)
The total calorific value was measured with a cone calorimeter defined by ISO 5660. The brand name “CONE2A” (manufactured by Atlas) was used as the corn calorimeter. The heating intensity was 50 kW / m ² and the heating time was 20 minutes. The evaluation criteria are as follows.
◎: gross calorific value of less than 7MJ / ^{m 2} ○: total calorific value 7 mJ / ^{m 2} or more 8 MJ / ^{m 2} less ×: total calorific value 8 MJ / ^{m 2} or more (Evaluation of Appearance)
The presence or absence of the non-burning part (normal part) of the urethane foam layer was visually observed with respect to the test piece after the fire resistance test.
○: Normal part exists ×: Normal part does not exist

(Test Example 2)
A specimen was obtained in the same manner as in Test Example 1 except that the polyol composition (1) was replaced with the polyol composition (2) and the polyol composition (6) was replaced with the polyol composition (7).
About the obtained test body, the test similar to Test Example 1 was done.

(Test Example 3)
A specimen was obtained in the same manner as in Test Example 1, except that the polyol composition (1) was replaced with the polyol composition (3) and the polyol composition (6) was replaced with the polyol composition (8).
About the obtained test body, the test similar to Test Example 1 was done.

(Test Example 4)
A specimen was obtained in the same manner as in Test Example 1, except that the polyol composition (1) was replaced with the polyol composition (4) and the polyol composition (6) was replaced with the polyol composition (8).
About the obtained test body, the test similar to Test Example 1 was done.

(Test Example 5)
A specimen was obtained in the same manner as in Test Example 1, except that the polyol composition (1) was replaced with the polyol composition (5) and the polyol composition (6) was replaced with the polyol composition (9).
About the obtained test body, the test similar to Test Example 1 was done.

(Test Example 6)
Using a commercially available two-component mixing type spray foaming machine, a slate plate (900 mm × 900 mm × 6 mm) was prepared by mixing a polyol composition (1) and an isocyanate component at a liquid temperature of 40 ° C. at the same volume ratio. A urethane foam layer (1) was formed thereon with an average thickness of 25 mm.
Next, the urethane foam layer (2) having an average thickness of 15 mm is formed on the urethane foam layer (1) by mixing the urethane composition obtained by mixing the polyol composition (6) and the isocyanate component in the same volume ratio at a liquid temperature of 40 ° C. Formed.
Next, on the urethane foam layer (2), a fireproof coating material consisting of 100 parts by weight of Portland cement, 100 parts by weight of vermiculite, and 200 parts by weight of aluminum hydroxide is applied and dried so that the dry film thickness becomes 10 mm. A specimen was obtained.
About the obtained test body, the test similar to Test Example 1 was done.

(Test Example 7)
A specimen was obtained in the same manner as in Test Example 6 except that the polyol composition (1) was replaced with the polyol composition (2) and the polyol composition (6) was replaced with the polyol composition (7).
About the obtained test body, the test similar to Test Example 1 was done.

(Test Example 8)
A test specimen was obtained in the same manner as in Test Example 6 except that the polyol composition (1) was replaced with the polyol composition (3) and the polyol composition (6) was replaced with the polyol composition (8).
About the obtained test body, the test similar to Test Example 1 was done.

(Test Example 9)
A test specimen was obtained in the same manner as in Test Example 6 except that the polyol composition (1) was replaced with the polyol composition (4) and the polyol composition (6) was replaced with the polyol composition (8).
About the obtained test body, the test similar to Test Example 1 was done.

(Test Example 10)
A specimen was obtained in the same manner as in Test Example 6 except that the polyol composition (1) was replaced with the polyol composition (5) and the polyol composition (6) was replaced with the polyol composition (9).
About the obtained test body, the test similar to Test Example 1 was done.

(Test Example 11)
Using a commercially available two-component mixing type spray foaming machine, a slate plate (900 mm × 900 mm × 6 mm) was prepared by mixing a polyol composition (1) and an isocyanate component at a liquid temperature of 40 ° C. at the same volume ratio. A urethane foam layer having an average thickness of 40 mm was formed thereon.
Next, a calcium silicate plate (900 mm × 900 mm × 6 mm) was pasted on the urethane foam layer using a urethane adhesive to obtain a test body.
About the obtained test body, the test similar to Test Example 1 was done.

Claims (2)

Obtained by mixing a polyol compound (1) containing water as a polyol compound, catalyst, flame retardant, and foaming agent and a polyisocyanate component so that the NCO / OH ratio is 0.5 or more and less than 1.5. Urethane foam layer (1),
Obtained by mixing a polyol compound (2) containing water as a polyol compound, catalyst, flame retardant, and foaming agent and a polyisocyanate component so that the NCO / OH ratio is 1.5 or more and 5.0 or less. Urethane foam layer (2),
Fire protection layer (3),
A fire-proof and heat-insulating structure characterized in that are sequentially laminated. A polyol composition (1) containing water as a polyol compound, a catalyst, a flame retardant, and a foaming agent on a substrate, and a polyisocyanate component have an NCO / OH ratio of 0.5 or more and less than 1.5. Forming a urethane foam layer (1) obtained by mixing so that
On the urethane foam layer (1), a polyol composition (2) containing water as a polyol compound, a catalyst, a flame retardant, and a foaming agent and a polyisocyanate component have an NCO / OH ratio of 1.5 or more and 5 A step of forming a urethane foam layer (2) obtained by mixing so as to be 0.0 or less,
Forming a fireproof layer (3) on the urethane foam layer (2);
A method for forming a fireproof and heat insulating structure, comprising: