JP7144246B2 - Metal-clad structure - Google Patents

Description

The present invention relates to novel metallization structures.

2. Description of the Related Art When structures such as buildings and civil engineering structures are exposed to high temperatures due to fire or the like, there is a problem that the physical strength of metal members such as steel frames constituting these structures is abruptly reduced. On the other hand, a coating structure is known in which a metal member is coated with a coating material to delay the temperature rise of the metal member in the event of a fire, thereby suppressing the deterioration of the physical strength of the metal member.
Examples of such a coating material include foamable fire-resistant paints, etc., and the coating film foams and carbonizes as the temperature rises in a fire or the like to form a porous carbonized heat insulating layer, which can be used as a metal member in the event of a fire. By delaying the temperature rise of the metal member, it is possible to suppress the decrease in the physical strength of the metal member.

JP 2008-019394 A

The present invention approaches the coating of metal members from a viewpoint different from that of the prior art, and provides a novel metal coating structure.

As a result of intensive research, the present inventors have found that a urethane heat insulating material using a phosphinate compound as a flame retardant is excellent in heat-resistant protection of metal members, and have completed the present invention.

That is, the present invention has the following features.
1. A metal coating structure in which a coating material layer formed from a coating material is laminated on a metal member,
The covering material is a urethane heat insulating material containing a polyol compound, a blowing agent, a catalyst, a flame retardant, and a polyisocyanate compound,
the flame retardant comprises a phosphate ester and a phosphinate compound;
The mixing ratio (weight ratio) of the phosphate ester and the phosphinate compound is 85:15 to 60:40.
A metal clad structure characterized by:
2. The phosphate ester is 30 parts by weight or more and 900 parts by weight or less with respect to 100 parts by weight of the polyol compound,
The phosphinate compound is 10 parts by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the polyol compound,
The metallized structure according to claim 1, characterized in that:
3. 1. The phosphinate compound includes an alkylphosphinate metal salt compound. A metal clad structure as described in .
4. 1. The coating material further contains an ethylenically unsaturated double bond-containing compound. A metal clad structure as described in .

The metal-coated structure of the present invention is lightweight and excellent in heat-resistant protection, and since the heat-insulating layer is already formed, the temperature rise during the daytime and in the summer and the temperature decrease during the night and in the winter are mitigated, and the metal member can be used for a long period of time. can be protected.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated.

The covering structure of the present invention is obtained by laminating a covering material layer formed of a covering material on a metal member.

Applicable metal members are not particularly limited as long as they are known, and examples thereof include square steel pipes, round steel pipes, square steels, round steels, H-shaped steels, I-shaped steels, flat steel plates, corrugated steel plates, and the like. . In addition, the metal member can also use the thing which performed antirust treatment.

A urethane heat insulating material containing a polyol compound, a foaming agent, a catalyst, a flame retardant and a polyisocyanate compound is used as the covering material.

Examples of polyol compounds include polyester polyols, polyether polyols, polycarbonate polyols, polylactone polyols, polybutadiene polyols, polypentadiene polyols, and castor oil-based polyols, and one or more of these can be used.

Among these, polyester polyols include, for example, aromatic polyester polyols, aliphatic polyester polyols, aromatic/aliphatic polyester polyols, and the like, and one or more of these can be used.
Specifically, an aromatic polyester polyol is a polyol having an aromatic hydrocarbon in one molecule. Condensed polyester polyols obtained by reacting with , and phthalic acid-based polyester polyols obtained by decomposing phthalic acid-based polyester moldings such as polyethylene terephthalate. Examples of polyhydric alcohols include dihydric or higher alcohols and derivatives thereof, dihydric or higher phenols, and polyols.
Aliphatic polyester polyol is a polyol having an aliphatic hydrocarbon in one molecule, for example, aliphatic polybasic acids and polyvalent Examples thereof include condensed polyester polyols obtained by reacting with alcohol.
Aromatic/aliphatic polyester polyols are polyols containing aliphatic hydrocarbons and aromatic hydrocarbons in one molecule, and are obtained by reacting aromatic polybasic acids and aliphatic polybasic acids with polyhydric alcohols. and condensed polyester polyols.
In the present invention, it is preferred that polyester polyol is included as the polyol compound.

Examples of polyether polyols include aromatic polyether polyols, phosphorus-containing polyether polyols, glycerin-based polyether polyols, and amino group-containing polyether polyols. Specifically, aromatic polyether polyols include, for example, bisphenol A-type polyether polyols obtained by adding alkylene oxide (e.g., ethylene oxide, propylene oxide, etc.) using bisphenol A as an initiator, aromatic amines ( For example, toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, triethanolamine, Mannich condensate, etc.) by adding an alkylene oxide as an initiator. The resulting aromatic amine-based polyether polyol and the like can be mentioned. Phosphorus-containing polyether polyols include, for example, dialkyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonates, which are diols having a phosphate ester structure. Examples of glycerin-based polyether polyols include polyether polyols obtained by adding alkylene oxide using glycerin as an initiator. Examples of amino group-containing polyether polyols include those obtained by adding an alkylene oxide to a low-molecular-weight amine (eg, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, etc.) as an initiator.

Although the hydroxyl value of the polyol compound in the present invention is not particularly limited, it is preferably 50 mgKOH/g or more and 500 mgKOH/g or less.
The hydroxyl value is a value represented by the number of mg of potassium hydroxide that is equimolar to the hydroxyl groups contained in 1 g of the sample, and is defined in JIS K 1557-1:2007 Plastics-Polyurethane raw material polyol test method-Part 1: Hydroxyl value. It is a value measured based on the method of obtaining. The hydroxyl value of a polyol compound is a value measured with a mixture of all polyol compounds.

Examples of foaming agents include hydrocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, water, liquefied carbon dioxide, and the like, and one or more of these can be used.

Among these, examples of hydrocarbons include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane. Hydrochlorofluorocarbons (HCFC) include, for example, 1,1-dichloro-1-fluoroethane (HCFC-141B), 1-chloro-1,1-difluoroethane (HCFC-142B), chlorodifluoromethane (HCFC-22) etc. Hydrofluorocarbons (HFC) include, for example, difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,1-trifluoroethane (HFC143a), 1,1, 2,2-tetrafluoroethane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), 1,1,1,2,3,3,3-hepta fluoropropane (HFC227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluorobutane (HFC365mfc), 1,1,1,2,2, 3,4,5,5,5-decafluoropentane (HFC4310mee) and the like.

Hydrofluoroolefins (HFO) include, for example, pentafluoropropenes such as 1,2,3,3,3-pentafluoropropene (HFO1225ye), 1,3,3,3-tetrafluoropropene (HFO1234ze), 2, Tetrafluoropropenes such as 3,3,3-tetrafluoropropene (HFO1234yf), 1,2,3,3-tetrafluoropropene (HFO1234ye), trifluoropropenes such as 3,3,3-trifluoropropene (HFO1243zf) , tetrafluorobutene (HFO1345), pentafluorobutene (HFO1354), hexafluorobutene (HFO1336), heptafluorobutene (HFO1327), heptafluoropentene (HFO1447), octafluoropentene (HFO1438), nonafluoropentene (HFO1429), etc. , or isomers thereof (cis isomers, trans isomers), and the like. Examples of hydrochlorofluoroolefins (HCFO) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), Dichlorotrifluoropropene (HCFO1223) and the like, or isomers thereof (cis isomer, trans isomer) and the like can be mentioned.
As the foaming agent in the present invention, one or more selected from hydrofluoroolefins, hydrochlorofluoroolefins and water are suitable. Each blowing agent, such as hydrochlorofluoroolefin and water, can be used in combination.

The mixing amount of the foaming agent is preferably 10 parts by weight or more and 200 parts by weight or less, more preferably 20 parts by weight or more and 180 parts by weight or less, and still more preferably 30 parts by weight or more and 150 parts by weight or less with respect to 100 parts by weight of the polyol compound. is.

The catalyst is not particularly limited, but includes, for example, nurate-forming catalysts, resin-forming catalysts, foaming catalysts, and the like, and one or more of these can be used.

Nurate-forming catalysts are not particularly limited as long as they are effective catalysts for isocyanurate-forming. Salts (organic acids such as acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, lactic acid, etc.), trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium , trialkylhydroxyalkylammonium hydroxides such as triethylhydroxyethylammonium or organic acid salts thereof (organic acids such as acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid , lactic acid, etc.), metal salts of alkylcarboxylic acids (e.g., acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, lactic acid, etc.), β of aluminum acetylacetone, lithium acetylacetone, etc. - Metal chelate compounds of diketones, Friedel-Crafts catalysts such as aluminum chloride and boron trifluoride, organometallic compounds such as titanium tetrabutylate and tributylantimony oxide, and aminosilyl group-containing compounds such as hexamethylsilazane. , one or more of these can be used.

Examples of the resinification catalyst include triethylenediamine (TEDA), triethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N ,N′,N′-tetramethylpropylenediamine, N,N,N′,N″,N″-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N′,N″,N′ tertiary amines such as '-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine or Organic acid salts, bismuth tris (2-ethylhexanoate), bismuth tris (neodecanoate), bismuth tris (palmitate), bismuth tris (palmitate), bismuth tetramethylheptanedioate, bismuth octylate, bismuth naphthenate, dibutyltin dilaurate, dibutyltin dimaleate, Organic metals such as dibutyltin diacetate, dioctyltin diacetate, tin octylate, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 1- Imidazoles such as isobutyl-2-methylimidazole, or N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, N-methylpiperazine, N-methylmorpholine, N-ethylmorpholine , 1,8-diazabicyclo[5.4.0]undecene-7, 1,1′-(3-(dimethylamino)propyl)imino)bis(2-propanol) and the like, one or two of these More than one species can be used.

Examples of foaming catalysts include N,N,N',N',N''-pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl) ether, N,N,N',N',N''- pentamethyldipropylenetriamine, N,N-dimethylaminoethoxyethanol, N,N,N'-trimethylaminoethoxyethanol, N,N,N',N'',N''',N'''-hexamethyl Triethylenetetramine, N,N,N',N''-tetramethyl-N''-(2-hydroxylethyl)triethylenediamine, N,N,N',N''-tetramethyl-(2-hydroxylpropyl ) tertiary amines such as triethylenediamine and organic acid salts thereof, and the like, and one or more of these can be used.

The amount of the catalyst to be mixed is preferably 0.1 to 50 parts by weight, more preferably 5 to 48 parts by weight, and still more preferably 10 to 45 parts by weight with respect to 100 parts by weight of the polyol compound. , most preferably 20 parts by weight or more and 40 parts by weight or less. When the catalyst contains an active hydrogen-containing component, the isocyanate index is calculated in consideration of the active hydrogen-containing component contained in the catalyst.
In the present invention, it is particularly preferable to include a resinification catalyst and/or a foaming catalyst together with the nurate catalyst, which is advantageous in workability and urethane heat insulation formability. When the catalyst contains an active hydrogen-containing component, the isocyanate index is calculated in consideration of the active hydrogen-containing component contained in the catalyst.

The flame retardant is characterized by containing a phosphinate compound. By containing the phosphinate compound, it is possible to impart heat-resistant protection to the metal member.

Examples of phosphinate compounds include sodium phosphinate, calcium phosphinate, aluminum phosphinate, zinc phosphinate, calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, and ethylmethylphosphinate. Aluminum, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, aluminum tris(diethylphosphinate), aluminum tris(methylethylphosphinate), aluminum tris(dibutylphosphinate), tris( butylethylphosphinate)aluminum, tris(diphenylphosphinate)aluminum, bis(diethylphosphinate)zinc, bis(methylethylphosphinate)zinc, bis(diphenylphosphinate)zinc, bis(diethylphosphinate)titanyl, tetrakis ( diethylphosphinate) titanyl, bis(methylethylphosphinate) titanyl, tetrakis(methylethylphosphinate) titanyl, bis(diphenylphosphinate) titanyl, tetrakis(diphenylphosphinate) titanyl, etc., one or two of these More than one species can be used.
In the present invention, in particular, aluminum tris(diethylphosphinate), aluminum tris(methylethylphosphinate), aluminum tris(dibutylphosphinate), aluminum tris(butylethylphosphinate), aluminum tris(diphenylphosphinate), bis( diethylphosphinate)zinc, bis(methylethylphosphinate)zinc, bis(diphenylphosphinate)zinc, bis(diethylphosphinate)titanyl, tetrakis(diethylphosphinate)titanyl, bis(methylethylphosphinate)titanyl, tetrakis( methylethylphosphinate) titanyl, bis(diphenylphosphinate) titanyl, tetrakis(diphenylphosphinate) titanyl, and other alkylphosphinate metal salt compounds are preferably used. Aluminum tris(alkylphosphinate) selected from aluminum methylethylphosphinate, aluminum tris(butylethylphosphinate), aluminum tris(diphenylphosphinate) is preferred.

Flame retardants other than the above phosphinate compounds may also be included as flame retardants. For example, halogen-based flame retardants, organic bromine-based flame retardants, nitrogen-based flame retardants, metal hydrate-based flame retardants, antimony-based flame retardants, boron-based flame retardants, silicon-based flame retardants, etc., phosphate esters, polyphosphoric acid Phosphorus-based flame retardants such as salt compounds, halogenated phosphazenes, red phosphorus, phosphorus trichloride and phosphorus pentachloride can be used, and one or more of these can be used.

Specific examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, trisnonylphenyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresylphenyl Phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, trixylenyl phosphate, diisopropylphenyl phosphate, tris(2-ethylhexyl) phosphate, resorcinol bisdiphenyl phosphate, bisphenol A bis(diphenyl phosphate), resorcinol bisdixylenyl phosphate, tris (chloroethyl) phosphate, tris(chloropropyl) phosphate, tris(dichloropropyl) phosphate, bis(2,3-dibromopropyl)-2,3-dichloropropyl phosphate, tris(2,3-dibromopropyl) phosphate, bis( chloropropyl)monooctylphosphate, hydroquinonyldiphenylphosphate, phenylnonylphenylhydroquinonylphosphate, phenyldinonylphenylphosphate, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzylphosphonate, dimethyl- 4-hydroxy-3,5-dibromobenzylphosphonate, diphenyl-4-hydroxy-3,5-dibromobenzylphosphonate and the like.

Examples of polyphosphate compounds include ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melem polyphosphate, melam polyphosphate, and melon polyphosphate.

Halogenated phosphazenes include, for example, hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene, dodecachlorocyclohexaphosphazene, hexabromocyclotriphosphazene, hexafluorocyclotriphosphazene, octafluorocyclotetraphosphazene, deca fluorocyclopentaphosphazene, dodecafluorocyclohexaphosphazene, hexamethoxycyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, hexaphenoxycyclotriphosphazene, diethoxytetrafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, methoxypentafluorocyclotri phosphazene, propoxypentafluorocyclotriphosphazene, butoxypentafluorocyclotriphosphazene and the like.

In the present invention, the amount of the flame retardant mixed is 10 parts by weight or more and 1000 parts by weight or less (preferably 30 parts by weight or more and 600 parts by weight or less, more preferably 50 parts by weight or more and 400 parts by weight or less) with respect to 100 parts by weight of the polyol compound. below).
In the present invention, it is particularly preferable to use a phosphinate compound as the flame retardant, which exhibits better heat protection and workability.
Furthermore, in the present invention, it is preferable to use a phosphate ester and a phosphinate compound in combination. When a phosphate ester and a phosphinate compound are used in combination, the phosphate ester is 30 parts by weight or more and 900 parts by weight or less (preferably 40 parts by weight or more and 600 parts by weight or less, more preferably 50 parts by weight or less) relative to 100 parts by weight of the polyol compound. parts by weight or more and 400 parts by weight or less), and the phosphinate compound is 10 parts by weight or more and 200 parts by weight or less (more preferably 20 parts by weight or more and 120 parts by weight or less, still more preferably 25 parts by weight or more and 100 parts by weight or less, most preferably 30 parts by weight or more and 70 parts by weight or less). Further, the mixing ratio (weight ratio) of the phosphate ester and the phosphinate compound is 90:10 to 50:50, further 85:15 to 55:45, and further It is preferably 80:20 to 60:40. Within such a range, heat protection and workability can be further improved.

As the polyisocyanate compound, various polyisocyanate compounds known in the technical field of polyurethane can be used. Examples of polyisocyanate compounds include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI) and the like. In the present invention, MDI is preferred from the viewpoints of ease of handling, speed of reaction, physical properties of the resulting urethane heat insulating material, superiority in terms of cost, and the like. Examples of MDI include monomeric MDI and polymeric MDI (polymethylene polyphenyl isocyanate).

Also, the isocyanate index is preferably 250 or more and 500 or less (more preferably 280 or more and 480 or less, further 300 or more and 450 or less).
Excellent fire resistance can be obtained by mixing the polyol compound and the polyisocyanate compound in such a range. The isocyanate index is expressed as 100 times the numerical value obtained by dividing the equivalent number of isocyanate groups of the polyisocyanate compound by the total number of active hydrogen equivalents of the active hydrogen-containing component (polyol compound, water, etc.). be.

The urethane heat insulating material of the present invention can contain a foam stabilizer in addition to the components described above. Examples of foam stabilizers include silicone-based foam stabilizers such as polyether-modified silicone compounds, fluorine-containing compound-based foam stabilizers, and the like. These can be used singly or in combination of two or more. Examples of polyether-modified silicone compounds include graft copolymers of polydimethylsiloxane and polyoxyethylene glycol or polyoxyethylene-propylene glycol. The amount of the foam stabilizer mixed is preferably 0.1 parts by weight or more and 40 parts by weight or less, more preferably 0.5 parts by weight or more and 30 parts by weight or less, relative to 100 parts by weight of the polyol compound.

Moreover, the urethane heat insulating material of the present invention can contain an ethylenically unsaturated double bond-containing compound in addition to the above components. Examples of ethylenically unsaturated double bonds include (meth)acryloyl groups, allyl groups, propenyl groups and the like. In the present invention, the use of such an ethylenically unsaturated double bond-containing compound can further improve fire resistance, storage stability, workability, and the like.

The ethylenically unsaturated double bond-containing compound preferably has an ethylenically unsaturated double bond concentration of 0.5 mmol/g or more and 20 mmol/g in one molecule from the viewpoint of the above effects. More preferably, it is 15 mmol/g or more. The concentration of ethylenically unsaturated double bonds in a molecule is expressed by the number of moles of ethylenically unsaturated double bonds in the molecule, and the number of ethylenically unsaturated double bonds in the molecule is the molecular weight. It is expressed by 1000 times (mmol/g) of the numerical value divided by .

Specific examples of ethylenically unsaturated double bond-containing compounds include, for example, polyhydric alcohols (e.g., dihydric or higher alcohols and derivatives thereof, dihydric or higher phenols, polyols, etc.) and unsaturated carboxylic acids (( meth)acrylic acid, etc.), reaction products of amines (e.g., divalent or higher amines, alkanolamines, etc.) and unsaturated carboxylic acids, unsaturated carboxylic acid thioesters or unsaturated alkylthioethers of thiols, Examples include bisphenol A-based (meth)acrylate compounds, reaction products of glycidyl group-containing compounds and unsaturated carboxylic acids, (meth)acrylate compounds having urethane bonds in the molecule, nonylphenoxypolyethyleneoxyacrylate, and the like. These can be used singly or in combination of two or more.

Among them, examples of reaction products of polyhydric alcohols and unsaturated carboxylic acids include pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta( meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, ditri Examples include methylolpropane tetra(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene/polypropylene glycol di(meth)acrylate, alkylene oxide-modified trimethylolpropane tri(meth)acrylate, and the like.

Examples of the bisphenol A-based (meth)acrylate compounds include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypoly propoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane, etc. is mentioned.

Examples of the (meth)acrylate compound having a urethane bond in the molecule include an addition reaction product of a hydroxyl group-containing (meth)acrylic monomer and a diisocyanate compound, tris ((meth)acryloxytetraethyleneglycol isocyanate) hexamethylene isocyanurate, alkylene Examples thereof include oxide-modified urethane di(meth)acrylate.

The amount of the ethylenically unsaturated double bond-containing compound mixed is preferably 1 part by weight or more and 100 parts by weight or less, more preferably 5 parts by weight or more and 80 parts by weight or less, still more preferably 10 parts by weight, per 100 parts by weight of the polyol compound. It is from 50 parts by weight to 50 parts by weight. If the ethylenically unsaturated double bond-containing compound contains a plurality of hydroxyl groups, it is regarded as a polyol compound. Also, the isocyanate index is calculated in consideration of the active hydrogen-containing component contained in the ethylenically unsaturated double bond-containing compound.

In the urethane heat insulating material of the present invention, in addition to the components described above, for example, a coloring agent, a surfactant, a polymerization inhibitor, fibers, and the like can be mixed.
Examples of coloring agents include pigments and dyes.
Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and the like. Such surfactants can impart storage stability and dispersion stability.
Examples of polymerization inhibitors include hydroquinone-based polymerization inhibitors, benzoquinone-based polymerization inhibitors, catechol-based polymerization inhibitors, and piperidine-based polymerization inhibitors. Such a polymerization inhibitor imparts long-term storage stability and also contributes to production stability when added during the polyol production process.
Examples of fibers include organic fibers such as cellulose fibers, polyester fibers, polyethylene fibers, polypropylene fibers, wood fibers and polyamide fibers, and inorganic fibers such as glass fibers and ceramic fibers. Such fibers can impart workability, urethane heat insulation formability, dimensional stability, and the like. In the present invention, fibers may not be used, but when fibers are mixed, the effect can be exhibited with a small amount of fibers.

In the covering structure of the present invention, the covering material layer can be laminated by applying the urethane heat insulating material to the metal member.

It is preferable that the urethane heat insulating material is, for example, in the form of a two-liquid type at the time of distribution, and mixed at the time of use. In such a two-component form, for example, the first liquid may contain a polyol compound (a foaming agent, a catalyst, and a flame retardant), and the second liquid may contain a polyisocyanate compound.

The viscosity of the first liquid is preferably 20 mPa·s or more and 500 mPa·s or less, more preferably 30 mPa·s or more, from the viewpoint of the storage stability of the first liquid, handleability, workability when forming a urethane heat insulating material, and the like. It is 350 mPa·s or less, more preferably 50 mPa·s or more and 250 mPa·s or less. The viscosity is the viscosity measured at 20 rpm with a BH type viscometer at a temperature of 20° C. (guideline value for the fourth rotation). With such a viscosity, a relatively low viscosity can be set while sufficiently ensuring storage stability. As a result, stirring work and the like during construction can be reduced, and advantageous effects can be obtained in terms of handleability, workability, miscibility with the polyisocyanate compound, and the like.
The viscosity of the second liquid is preferably 20 mPa·s or more and 500 mPa·s or less, more preferably 30 mPa·s or more and 350 mPa·s or less, and still more preferably 50 mPa·s or more and 250 mPa·s or less.

When applying the urethane heat insulating material to the metal member, for example, using a spray foaming machine for spraying work (for example, a two-liquid tip mixing type spray coating machine, etc.), A mixture with the second liquid may be applied by spraying. In this case, the temperatures of the first liquid and the second liquid are preferably set to 20° C. or higher and 60° C. or lower, more preferably 30° C. or higher and 50° C. or lower. The first liquid and the second liquid set to the predetermined temperature are mixed at the tip of the spray gun and sprayed toward the metal member to form a coating material layer on the metal member. As for the spraying environment, it is possible to carry out construction preferably at 5°C or higher and 45°C or lower.
It is preferable to mix the first liquid and the second liquid at a volume ratio of about 1:1. Such a urethane heat insulating material can exhibit excellent performance in terms of heat protection and can also be used as a fireproof covering material. The thickness of the coating material layer made of the urethane heat insulating material is not particularly limited, and may be appropriately set according to the required performance and the like.

To the extent that the effects of the present invention are not impaired, the metal member may be pretreated with an antirust treatment or a primer treatment, and the surface of the urethane heat insulating material may be subjected to a coloring treatment. A fire-resistant foam coating, a fire-resistant foam sheet, or the like may be laminated on one or both sides of the urethane heat insulating material.

Examples are shown below to further clarify the features of the present invention.

As a first liquid, a polyol composition was prepared by uniformly mixing the following raw materials in the weight ratios shown in Table 1. As the second liquid, one made of polymeric MDI was prepared.
- Polyol compound 1: aromatic polyester polyol (terephthalic acid-based polyester polyol, viscosity 1900 mPa s, acid value: 0 mgKOH/g, hydroxyl value: 250 mgKOH/g)
· Polyol compound 2: aromatic / aliphatic polyester polyol (phthalic acid / adipic acid polyester polyol, viscosity 900 mPa s, acid value: 0 mgKOH / g, hydroxyl value: 350 mgKOH / g)
Polyol compound 3: Aliphatic polyester polyol (fumaric acid-based polyester polyol, viscosity 6000 mPa s, acid value: 0 mgKOH/g, hydroxyl value: 150 mgKOH/g)
・Blowing agent 1: hydrochlorofluoroolefin ・Blowing agent 2: water (hydroxyl value: 6233 mgKOH/g)
Catalyst 1: nurate catalyst (glycol solution of tetraalkylammonium 2-ethylhexanoate)
- Catalyst 2: Resin catalyst (octylic acid solution of bismuth octylate)
・Flame retardant 1: phosphinate compound (tris(diethylphosphinate) aluminum, average particle size 4 μm, density 1.35 g/cm ³ )
- Flame retardant 2: phosphinate compound (sodium phosphinate, average particle size 8 µm, density 1.39 g/cm ³ )
・Flame retardant 3: organic phosphate ester compound (tris(chloropropyl) phosphate, density 1.29 g/cm ³ )
· Double bond compound 1: ethylenically unsaturated double bond-containing compound (trimethylolpropane triacrylate, ethylenically unsaturated double bond concentration 10 mmol / g, hydroxyl value: 0 mg KOH / g)
・Foam stabilizer: Silicone foam stabilizer

(Examples 1 to 9, Comparative Example 1)
The first liquid and the second liquid were each heated to 40°C and mixed so that the isocyanate indices shown in Table 1 were obtained. , thickness 6 mm) with a spray gun and foamed to obtain a test piece (thickness 50 mm) in which the entire one side of the substrate was coated with foam. Each test was carried out on the obtained specimens by the following methods. Results are shown in Table 1.

(1) Formability The state of the formed foam was visually observed. Evaluation criteria are as follows.
A: A homogeneous foam was formed.
◯: Almost homogeneous foam was formed.
Δ: Some abnormalities (brittleness, uneven foaming, poor adhesion, etc.) were observed in the foam.
x: Abnormalities were observed in the foam.

(2) Thermal conductivity A foam portion of the specimen was cut out and thermal conductivity was measured using a thermal conductivity meter. Evaluation criteria are as follows.
○: Thermal conductivity is 0.03 W / (m K) or less ×: Thermal conductivity is greater than 0.03 W / (m K)

(3) Heat protection property The 1st liquid and the 2nd liquid were each heated to 40°C and mixed so that the isocyanate index shown in Table 1 was obtained. 300 mm, thickness 6 mm) to form a covering layer of urethane heat insulating material to obtain a test specimen. The thickness of the coating material layer was 60 mm. A heat resistance test was carried out on the obtained specimens by the following method. Results are shown in Table 1.
This specimen was subjected to a heating test for 60 minutes according to the standard heating curve of ISO834, and the temperature of the back surface of the specimen after 60 minutes was measured with a thermocouple and evaluated. The evaluation results are as follows. Results are shown in Table 1.
◎: less than 500 ° C. ○: 500 ° C. or higher and less than 550 ° C. △: 550 ° C. or higher and less than 600 ° C. ×: 600 ° C. or higher

Claims (4)

A metal coating structure in which a coating material layer formed from a coating material is laminated on a metal member,
The covering material is a urethane heat insulating material containing a polyol compound, a blowing agent, a catalyst, a flame retardant, and a polyisocyanate compound,
the flame retardant comprises a phosphate ester and a phosphinate compound;
The mixing ratio (weight ratio) of the phosphate ester and the phosphinate compound is 85:15 to 60:40.
A metal clad structure characterized by: The phosphate ester is 30 parts by weight or more and 900 parts by weight or less with respect to 100 parts by weight of the polyol compound,
The phosphinate compound is 10 parts by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the polyol compound,
The metallized structure according to claim 1, characterized in that: 2. The metal clad structure of claim 1, wherein the phosphinate compound comprises an alkylphosphinate metal salt compound. 2. The metal clad structure of claim 1, wherein said coating material further comprises an ethylenically unsaturated double bond containing compound.