Laminate

Abstract

To provide a laminate that has excellent heat insulation property and heat resistance property, as well as is excellent in aesthetic property.SOLUTION: The laminate of the present invention is characterized by being laminated on an urethane foam with a colored coating containing a particular binder and a coloring agent.SELECTED DRAWING: None

Description

Technical Field

[0001] The laminate of the present invention can form a foam excellent in heat insulation, heat resistance, and aesthetics.

Background Art

[0002] Generally, in building structures, in addition to flame-retardant materials, heat insulating materials are installed to enhance heat insulation performance. As such heat insulating materials, mainly organic heat insulating materials such as urethane foam, phenolic foam, and styrene foam are used. For example, urethane foam is widely used because it has characteristics such as excellent heat insulation and can be constructed at a relatively low cost. In recent years, with the improvement of the heat resistance of urethane foam, it has become possible to use urethane foam alone and also as a surface material, and further expansion of applications is expected. (For example, Patent Documents 1, 2, etc.)

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, as such urethane foam is adopted in places that are noticeable with the expansion of applications, the aesthetics of the surface has become a problem, and improving the aesthetics of the surface has become an urgent task for the expansion of applications.

Means for Solving the Problems

[0005] As a result of intensive research to solve the above problems, the present inventors have found that by laminating a colored coating film containing a specific binder and a colorant on a urethane foam, a laminate excellent in adhesion between the urethane foam and the colored coating film and capable of maintaining aesthetic appearance over a long period of time and excellent in heat insulation and heat resistance can be obtained, and thus the present invention has been completed.

[0006] That is, the present invention has the following features. 1. A laminate in which a colored coating film is laminated on a urethane foam, wherein the urethane foam is formed from a polyol compound, a foaming agent, a catalyst, a polyisocyanate compound, and a flame retardant, the colored coating film contains a binder and a colorant It is formed by applying a colorless coating film forming material and drying and curing it , the binder is a synthetic resin emulsion that is an acrylic resin or an acrylic-styrene copolymer resin having a glass transition temperature of 0°C or lower of , and the blending amount of the colorant in the colored coating film is 98 parts by weight or more and 500 parts by weight or less with respect to 100 parts by weight of the solid content of the binder. 2. The laminate according to 1., wherein the flame retardant contains one or more selected from cyclic phosphate esters, phosphinate compounds, phosphoramidates, and cyclic phosphoramidates. 3. The laminate according to 1., wherein the binder is a synthetic resin emulsion that is an acrylic resin or an acrylic-styrene copolymer resin having a glass transition temperature of -30 or higher and -5°C or lower.

Advantages of the Invention

[0007] The laminate of the present invention is excellent in heat insulation and heat resistance and can maintain aesthetic appearance over a long period of time.

Modes for Carrying Out the Invention

[0008] Hereinafter, modes for carrying out the present invention will be described.

[0009] The laminate of the present invention is obtained by laminating a colored coating film on a urethane foam.

[0010] As the urethane foam, for example, those formed from a polyol compound, a foaming agent, a catalyst, and a polyisocyanate compound, and using a flame retardant or the like to impart heat resistance are used.

[0011] Examples of the polyol compound include polyester polyol, polyether polyol, polycarbonate polyol, polylactone polyol, polybutadiene polyol, polypentadiene polyol, castor oil-based polyol, etc., and one or more of these can be used.

[0012] Among these, examples of the polyester polyol include aromatic polyester polyol, aliphatic polyester polyol, aromatic / aliphatic polyester polyol, etc., and one or more of these can be used. Specifically, the aromatic polyester polyol is a polyol having an aromatic hydrocarbon in one molecule. For example, a condensed polyester polyol obtained by reacting an aromatic polybasic acid such as orthophthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, etc. with a polyhydric alcohol, and a phthalic acid-based polyester polyol obtained by decomposing a phthalic acid-based polyester molding such as polyethylene terephthalate, etc. are mentioned. Examples of the polyhydric alcohol include dihydric or higher alcohols and their derivatives, dihydric or higher phenols, polyols, etc. The aliphatic polyester polyol is a polyol having an aliphatic hydrocarbon in one molecule. For example, a condensed polyester polyol obtained by reacting an aliphatic polybasic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, etc. with a polyhydric alcohol is mentioned. The aromatic / aliphatic polyester polyol is a polyol having an aliphatic hydrocarbon and an aromatic hydrocarbon in one molecule. For example, a condensed polyester polyol obtained by reacting an aromatic polybasic acid and an aliphatic polybasic acid with a polyhydric alcohol is mentioned. In the present invention, it is preferable to include a polyester polyol as the polyol compound.

[0013] Examples of the polyether polyol include aromatic polyether polyol, phosphorus-containing polyether polyol, glycerin-based polyether polyol, amino group-containing polyether polyol, and the like. Specifically, examples of the aromatic polyether polyol include bisphenol A-type polyether polyol obtained by adding an alkylene oxide (e.g., ethylene oxide, propylene oxide, etc.) using bisphenol A as an initiator, and aromatic amine-based polyether polyol obtained by adding an alkylene oxide using an aromatic amine (e.g., toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, triethanolamine, Mannich condensate, etc.) as an initiator. Examples of the phosphorus-containing polyether polyol include dialkyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate, which is a diol having a phosphate ester structure. Examples of the glycerin-based polyether polyol include polyether polyol obtained by adding an alkylene oxide using glycerin as an initiator. Examples of the amino group-containing polyether polyol include those obtained by adding an alkylene oxide using a low molecular weight amine (e.g., ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, etc.) as an initiator.

[0014] The hydroxyl value of the polyol compound in the present invention is not particularly limited, but is preferably 50 mgKOH / g or more and 500 mgKOH / g or less. The hydroxyl value is a value represented by the number of milligrams of potassium hydroxide equimolar to the hydroxyl groups contained in 1 g of the sample, and is a value measured based on JIS K 1557-1:2007 Plastics - Polyurethane raw material polyol - Test methods - Part 1: Method for determining hydroxyl value. The hydroxyl value of the polyol compound is a value measured for a mixture of all polyol compounds.

[0015] Examples of the foaming agent include hydrocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, water, liquefied carbon dioxide gas, etc., and one or more of these can be used.

[0016] Among these, examples of the hydrocarbon include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, etc. Examples of the hydrochlorofluorocarbon (HCFC) include 1,1-dichloro-1-fluoroethane (HCFC-141B), 1-chloro-1,1-difluoroethane (HCFC-142B), chlorodifluoromethane (HCFC-22), etc. Examples of the hydrofluorocarbon (HFC) include 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-heptafluoropropane (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), etc.

[0017] Examples of hydrofluoroolefins (HFOs) include pentafluoropropenes such as 1,2,3,3,3-pentafluoropropene (HFO-1225ye), tetrafluoropropenes such as 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2,3,3-tetrafluoropropene (HFO-1234ye), trifluoropropenes such as 3,3,3-trifluoropropene (HFO-1243zf), tetrafluorobutene (HFO-1345), pentafluorobutene (HFO-1354), hexafluorobutene (HFO-1336), heptafluorobutene (HFO-1327), heptafluoropentene (HFO-1447), octafluoropentene (HFO-1438), nonafluoropentene (HFO-1429), or isomers (cis-isomers, trans-isomers) thereof. Examples of hydrochlorofluoroolefins (HCFOs) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), dichlorotrifluoropropene (HCFO-1223), or isomers (cis-isomers, trans-isomers) thereof. As the foaming agent in the present invention, one or more selected from hydrofluoroolefins, hydrochlorofluoroolefins, and water are preferred. For example, hydrofluoroolefins and water, hydrochlorofluoroolefins and water, hydrofluoroolefins and hydrochlorofluoroolefins and water, etc., can be used in combination of each foaming agent.

[0018] 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. Further, when the foaming agent contains hydrofluoroolefin and / or hydrochlorofluoroolefin and water, the mixing ratio (weight ratio) of hydrofluoroolefin and / or hydrochlorofluoroolefin to water is preferably 100:0.5 to 100:5 (more preferably 100:0.8 to 100:4). By being in such a range, a foam having excellent low thermal conductivity, heat resistance, and further excellent strength can be obtained.

[0019] The catalyst is not particularly limited, and examples thereof include a nucleating catalyst, a resinifying catalyst, a foaming catalyst, etc., and one or more of these can be used.

[0020] As the nurate-forming catalyst, there is no particular limitation as long as it is a catalyst effective for isocyanurate formation. For example, hydroxides of tetraalkylammonium such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, trimethylbenzylammonium, or organic acid salts thereof (as the organic acid, for example, acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, lactic acid, etc.), hydroxides of trialkylhydroxyalkylammonium such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, triethylhydroxyethylammonium, or organic acid salts thereof (as the organic acid, for example, acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, lactic acid, etc.), metal salts of alkylcarboxylic acids (for example, acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, lactic acid, etc.), metal chelate compounds of β-diketones such as aluminum acetylacetone, lithium acetylacetone, Friedel-Crafts catalysts such as aluminum chloride, boron trifluoride, organometallic compounds such as titanium tetrabutyrate, tributylantimony oxide, amino group-containing compounds such as hexamethylsilazane, etc. can be mentioned, and one or more of these can be used.

[0021] Examples of the resinification catalyst include tertiary amines such as 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’’-pentamethyldipropylenetriamine, N,N,N’,N’-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine or organic acid salts thereof; organometals such as bismuth tris(2-ethylhexanoate), bismuth tris(neodecanoate), bismuth tris(palmitate), bismuth tetramethylheptanedioate, bismuth octylate, bismuth naphthenate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, dioctyltin diacetate, tin octylate; imidazoles such as 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 1-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). One or more of these can be used.

[0022] Examples of the blowing catalyst include tertiary amines such as 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’’’-hexamethyltriethylenetetramine, N,N,N’,N’’-tetramethyl-N’’-(2-hydroxyethyl)triethylenediamine, N,N,N’,N’’-tetramethyl-(2-hydroxypropyl)triethylenediamine, or organic acid salts thereof, and one or more of these can be used.

[0023] The mixing amount of the catalyst is preferably 0.1 part by weight or more and 50 parts by weight or less, more preferably 0.5 part by weight or more and 48 parts by weight or less, still more preferably 1 part by weight or more and 45 parts by weight or less, and most preferably 3 parts by weight or more and 40 parts by weight or less, based on 100 parts by weight of the polyol compound. When the catalyst contains an active hydrogen-containing component, the isocyanate index is calculated considering the active hydrogen-containing component contained in the catalyst. In the present invention, in particular, it is preferable to contain a resinification catalyst and / or a blowing catalyst together with the nucleating catalyst, which is advantageous for foam formation properties as well as workability. When the catalyst contains an active hydrogen-containing component, the isocyanate index is calculated considering the active hydrogen-containing component contained in the catalyst.

[0024] Examples of the flame retardant include halogen-based flame retardants, organic bromine-based flame retardants, nitrogen-based flame retardants, phosphorus-based flame retardants, metal hydrate-based flame retardants, antimony-based flame retardants, boron-based flame retardants, silicon-based flame retardants, etc. In the present invention, in particular, phosphorus-based flame retardants are preferable, and examples of the phosphorus-based flame retardants include phosphate esters, cyclic phosphate esters, polyphosphate compounds, phosphinate compounds, halogenated phosphazenes, phosphoramidates, cyclic phosphoramidates, red phosphorus, phosphorus trichloride, phosphorus pentachloride, etc., and one or more of these can be used.

[0025] Specifically, examples of the phosphate ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, trisnonylphenyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl 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) monooctyl phosphate, hydroquinonyl diphenyl phosphate, phenyl nonylphenyl hydroquinonyl phosphate, phenyl dinonylphenyl phosphate, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonate, dimethyl-4-hydroxy-3,5-dibromobenzyl phosphonate, diphenyl-4-hydroxy-3,5-dibromobenzyl phosphonate, and the like.

[0026] Examples of the cyclic phosphate ester include 3,9-bis(phenylmethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2-methylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((3-methylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((4-methylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4-dimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,6-dimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((3,5-dimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4,6-trimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2-sec-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((4-sec-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4-di-sec-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,6-di-sec-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4,6-tri-sec-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] Undecane, 3,9-bis((2-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((4-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4-di-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,6-di-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4,6-tri-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((4-biphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((1-naphthyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2-naphthyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((1-anthryl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2-anthryl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((9-anthryl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(1-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2-methyl-2-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] Undecane, 3,9-bis(diphenylmethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(triphenylmethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-phenylmethyl-9-((2,6-dimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-phenylmethyl-9-((2,4-di-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-phenylmethyl-9-(1-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-phenylmethyl-9-diphenylmethyl-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-((2,6-dimethylphenyl)methyl)-9-(1-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-((2,4-di-tert-butylphenyl)methyl)-9-(1-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-diphenylmethyl-9-(1-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-diphenylmethyl-9-((2,6-dimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-diphenylmethyl-9-((2,4-di-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane and the like can be mentioned.

[0027] Examples of the polyphosphate compound include ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melem polyphosphate, melam polyphosphate, melon polyphosphate and the like.

[0028] Examples of the phosphinate compound include sodium phosphinate, calcium phosphinate, aluminum phosphinate, zinc phosphinate, calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, aluminum tris(diethylphosphinate), aluminum tris(methylethylphosphinate), aluminum tris(dibutylphosphinate), aluminum tris(butylethylphosphinate), aluminum tris(diphenylphosphinate), zinc bis(diethylphosphinate), zinc bis(methylethylphosphinate), zinc bis(diphenylphosphinate), titanyl bis(diethylphosphinate), titanyl tetrakis(diethylphosphinate), titanyl bis(methylethylphosphinate), titanyl tetrakis(methylethylphosphinate), titanyl bis(diphenylphosphinate), and titanyl tetrakis(diphenylphosphinate). One or more of these can be used.

[0029] Examples of the halogenated phosphazene include hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene, dodecachlorocyclohexaphosphazene, hexabromocyclotriphosphazene, hexafluorocyclotriphosphazene, octafluorocyclotetraphosphazene, decafluorocyclopentaphosphazene, dodecafluorocyclohexaphosphazene, hexamethoxycyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, hexaphenoxycyclotriphosphazene, diethoxytetrafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, methoxypentafluorocyclotriphosphazene, propoxypentafluorocyclotriphosphazene, and butoxypentafluorocyclotriphosphazene.

[0030] Examples of the phosphoramidate include compounds described in Formula 1 or Formula 2, etc. (Formula 1) O-R1 │ O=P-N(R2)2 │ O-R1 (Formula 2) O-R1 O-R1 │ │ O=P-N(R2)-R3-(R2)N-P=O │ │ O-R1 O-R1 R1 may be the same or different and is an alkyl group having 1 or more and 12 or less carbon atoms, R2 may be the same or different and is a hydrogen atom or an alkyl group having 1 or more and 12 or less carbon atoms, R3 is an alkylene group having 1 or more and 12 or less carbon atoms, and N(R2)2 and N(R2)-R3-(R2)N may be a nitrogen-containing heterocyclic structure.

[0031] Examples of the cyclic phosphoramidate include compounds described in Formula 3 or Formula 4, etc. (Formula 3) R2 R1-O \ / \ C P=O / \ / \ R2 R1-O N(R3)2 (Formula 4) R2 R1-O O-R1 R2 \ / \ / \ / C P=O O=P C / \ / \ / \ / \ R2 R1-O N(R3)-R4-(R3)N O-R1 R2 R1 may be the same or different and is an alkylene group having 1 or more and 3 or less carbon atoms, R2 may be the same or different and is an alkyl group having 1 or more and 12 or less carbon atoms, R3 may be the same or different and is a hydrogen atom or an alkyl group having 1 or more and 12 or less carbon atoms, R4 is an alkylene group having 1 or more and 12 or less carbon atoms, and N(R3)2 and N(R3)-R4-(R3)N may be a nitrogen-containing heterocyclic structure.

[0032] In the present invention, the mixing amount of the flame retardant is preferably 1 part by weight or more and 1000 parts by weight or less, more preferably 5 parts by weight or more and 600 parts by weight or less, still more preferably 10 parts by weight or more and 400 parts by weight or less, based on 100 parts by weight of the polyol compound. In the present invention, as the flame retardant, it preferably contains one or more selected from cyclic phosphate esters, phosphinate compounds, phosphoramidates, and cyclic phosphoramidates, and further preferably contains one or more selected from phosphinate compounds and cyclic phosphoramidates. This can provide excellent workability and further improve heat resistance. Particularly when a phosphinate compound is included, in the present invention, it is preferable to use a phosphate ester and a phosphinate compound in combination. When using a phosphate ester and a phosphinate compound in combination, based on 100 parts by weight of the polyol compound, 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, still more preferably 50 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). Also, the mixing ratio (weight ratio) of the phosphate ester and the phosphinate compound is preferably in the range of phosphate ester:phosphinate compound ratio of 90:10 to 50:50, further preferably 85:15 to 55:45, and still more preferably 80:20 to 60:40. Being within such a range can provide excellent workability and further improve heat resistance. Particularly when a cyclic phosphoramidate is included, based on 100 parts by weight of the polyol compound, the cyclic phosphoramidate is preferably 1 part by weight or more and 100 parts by weight or less (more preferably 5 parts by weight or more and 70 parts by weight or less, still more preferably 10 parts by weight or more and 50 parts by weight or less). Being within such a range can provide excellent workability and further improve heat resistance.

[0033] As the polyisocyanate compound, various polyisocyanate compounds known in the technical field of polyurethanes can be used. Examples of the polyisocyanate compound 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 in terms of ease of handling, reaction speed, physical properties of the resulting foam, and cost advantages. Examples of MDI include monomeric MDI, polymeric MDI (polymethylene polyphenyl isocyanate), and the like.

[0034] Further, it is preferable that the isocyanate index is 130 or more and 500 or less (more preferably 150 or more and 480 or less, and even more preferably 170 or more and 450 or less). By mixing the polyol compound and the polyisocyanate compound within such a range, excellent heat resistance can be obtained. When a phosphinate compound is included as the flame retardant, it is preferable that the isocyanate index is 250 or more and 500 or less (more preferably 280 or more and 480 or less, and even more preferably 300 or more and 450 or less). The isocyanate index is represented by 100 times the value obtained by dividing the equivalent number of isocyanate groups of the polyisocyanate compound by the total equivalent number of active hydrogens of the active hydrogen-containing components (polyol compound, water, etc.).

[0035] In the urethane foam of the present invention, in addition to the above-described components, a foam stabilizer can be included. Examples of the foam stabilizer include silicone-based foam stabilizers such as polyether-modified silicone compounds, and fluorine-containing compound-based foam stabilizers. These can be used alone or in combination of two or more. Examples of the polyether-modified silicone compound include graft copolymers of polydimethylsiloxane and polyoxyethylene glycol or polyoxyethylene-propylene glycol. The mixing amount of the foam stabilizer is preferably 0.1 part by weight or more and 40 parts by weight or less, more preferably 0.5 part by weight or more and 30 parts by weight or less, based on 100 parts by weight of the polyol compound.

[0036] Further, the urethane foam of the present invention can include an ethylenically unsaturated double bond-containing compound in addition to the above-described components. Examples of the ethylenically unsaturated double bond include (meth)acryloyl group, allyl group, propenyl group, and the like. In the present invention, by using such an ethylenically unsaturated double bond-containing compound, heat resistance, storage stability, workability, etc. can be further enhanced. Particularly in the present invention, when a phosphinate compound is included as a flame retardant together with the ethylenically unsaturated double bond-containing compound, the flame retardant effect is enhanced and more excellent heat resistance can be imparted. Also, when a cyclic phosphoramidate is included as a flame retardant, the flame retardant effect is enhanced and more excellent heat resistance can be imparted.

[0037] As the ethylenically unsaturated double bond-containing compound, from the viewpoints of the above-described effects and the like, those having an ethylenically unsaturated double bond concentration of 0.5 mmol / g or more and 20 mmol / g or less in one molecule are preferable, and those having an ethylenically unsaturated double bond concentration of 5 mmol / g or more and 15 mmol / g or less are more preferable. The ethylenically unsaturated double bond concentration in the molecule is represented by the number of moles of the ethylenically unsaturated double bond in the molecule, and is represented by 1000 times (mmol / g) of the value obtained by dividing the number of ethylenically unsaturated double bonds in the molecule by the molecular weight.

[0038] Specific examples of the ethylenically unsaturated double bond-containing compound include, for example, reaction products of polyhydric alcohols (e.g., dihydric or higher alcohols and their derivatives, dihydric or higher phenols, polyols, etc.) and unsaturated carboxylic acids ((meth)acrylic acid, etc.), reaction products of amines (e.g., dihydric or higher amines, alkanolamines, etc.) and unsaturated carboxylic acids, thioesters of thiols with unsaturated carboxylic acids or unsaturated alkyl thioethers, bisphenol A-based (meth)acrylate compounds, reaction products of glycidyl group-containing compounds and unsaturated carboxylic acids, (meth)acrylate compounds having a urethane bond in the molecule, nonylphenoxypolyethyleneoxy acrylate, and the like. These can be used alone or in combination of two or more.

[0039] Among these, examples of the reaction product of a polyhydric alcohol and an unsaturated carboxylic acid include, for example, 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, ditrimethylolpropane 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.

[0040] Examples of the above-mentioned bisphenol A-based (meth)acrylate compounds include, for example, 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane, and the like.

[0041] Examples of the (meth)acrylate compound having a urethane bond in the molecule include addition reaction products of a hydroxyl group-containing (meth)acrylic monomer and a diisocyanate compound, tris((meth)acryloxy tetraethylene glycol isocyanate) hexamethylene isocyanurate, alkylene oxide-modified urethane di(meth)acrylate, and the like.

[0042] The mixing amount of the ethylenically unsaturated double bond-containing compound is preferably 1 part by weight or more and 100 parts by weight or less, more preferably 5 parts by weight or more and 90 parts by weight or less, and still more preferably 10 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the polyol compound. When the ethylenically unsaturated double bond-containing compound contains a plurality of hydroxyl groups, it is regarded as a polyol compound. The isocyanate index is calculated in consideration of the active hydrogen-containing components contained in the ethylenically unsaturated double bond-containing compound.

[0043] In addition to the above components, for example, a colorant, a surfactant, a polymerization inhibitor, fibers, etc. can be mixed in the urethane foam of the present invention. Examples of the colorant include pigments, dyes, and the like. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and the like. Such surfactants can impart storage stability and dispersion stability. Examples of the polymerization inhibitor include hydroquinone-based polymerization inhibitors, benzoquinone-based polymerization inhibitors, catechol-based polymerization inhibitors, piperidine-based polymerization inhibitors, and the like. Such polymerization inhibitors impart long-term storage stability and also contribute to production stability when added during the polyol production process. Examples of the fiber include organic fibers such as cellulose fiber, polyester fiber, polyethylene fiber, polypropylene fiber, wood fiber, and polyamide fiber, and inorganic fibers such as glass fiber and ceramic fiber. Such fibers can impart workability, foam formability, dimensional stability, etc. 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.

[0044] The laminate of the present invention is obtained by laminating a colored coating film on the above urethane foam.

[0045] The colored coating film contains a binder and a colorant.

[0046] The binder contains a synthetic resin emulsion having a glass transition temperature of 0 °C or lower (preferably -40 °C or higher and -5 °C or lower, more preferably -30 °C or higher and -10 °C or lower). Such a synthetic resin emulsion has excellent adhesion to the urethane foam, and the colored coating film containing the synthetic resin emulsion has excellent adhesion to the urethane foam and can maintain aesthetic properties over a long period of time. When the glass transition temperature is higher than 0 °C, the adhesion to the urethane foam may be poor, and the aesthetic properties may not be maintained over a long period of time. The glass transition temperature is a value determined by the FOX calculation formula.

[0047] Examples of such synthetic resin emulsions include acrylic resin, acrylic silicone resin, vinyl acetate resin, acrylic vinyl acetate resin, polyethylene resin, styrene resin, acrylic styrene resin, vinyl propionate resin, vinyl versatic acid resin, ethylene vinyl acetate resin, vinyl chloride resin, epoxy resin, urethane resin, fluororesin, polyester resin, phenol resin, petroleum resin, polybutadiene resin, alkyd resin, and melamine resin. One or more of these can be used.

[0048] In the present invention, in particular, it is preferably a polymer polymerized from a monomer group containing an acrylic monomer (preferably one or more selected from an acrylic resin, an acrylic silicone resin, an acrylic vinyl acetate resin, and an acrylic styrene resin), and has excellent adhesion to a urethane foam.

[0049] Examples of the acrylic monomer include alkyl (meth)acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate. Carboxyl group-containing (meth)acrylic monomers such as (meth)acrylic acid. Amino group-containing (meth)acrylic monomers such as N-methylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, N-(2-dimethylaminoethyl)acrylamide, and N-(2-dimethylaminoethyl)methacrylamide. Hydroxyl group-containing (meth)acrylic monomers such as 2-hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate. Nitrile group-containing (meth)acrylic monomers such as (meth)acrylonitrile. Amide group-containing (meth)acrylic monomers such as (meth)acrylamide, N-methylol (meth)acrylamide, and diacetoneacrylamide. Carbonyl group-containing (meth)acrylic monomers such as acrolein, diacetone (meth)acrylamide, vinyl methyl ketone, vinyl ethyl ketone, and vinyl butyl ketone. And the like, and one or more of these can be used. In addition to the above acrylic monomers, aromatic monomers such as styrene, 2-methylstyrene, vinyltoluene, chlorostyrene, vinyl anisole, vinyl naphthalene, divinylbenzene, etc., and other monomers such as ethylene, propylene, isoprene, butadiene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl ether, vinyl ketone, etc. can also be copolymerized.

[0050] Examples of the colorant include pigments, dyes, etc., and one or more of these can be used. The pigment is not particularly limited. For example, titanium oxide, zinc oxide, carbon black, graphite, black iron oxide, copper chromium black, cobalt black, copper manganese iron black, ferric oxide (vermilion), lead chromate (molybdate orange), permanent red, permanent carmine, lead yellow, yellow iron oxide, titanium yellow, chrome green, cobalt green, ultramarine, navy blue, cobalt blue inorganic pigments, azo-based, naphthol-based, pyrazolone-based, anthraquinone-based, perylene-based, quinacridone-based, disazo-based, isoindolinone-based, benzimidazole-based, phthalocyanine-based, quinophthalone-based, dioxazine-based and other organic coloring pigments, pearl pigments, fluorescent pigments, phosphorescent pigments, metallic pigments, etc. can be mentioned, and these can be used singly or in combination of two or more. The color tone of the colored coating film can be appropriately set by adjusting the types, mixing amounts, etc. of such pigments and dyes. The blending amount of the colorant in the colored coating film is preferably 10 parts by weight or more and 500 parts by weight or less, more preferably 20 parts by weight or more and 300 parts by weight or less, based on 100 parts by weight of the solid content of the binder.

[0051] In addition to the above components, the colored coating film of the present invention may contain, to the extent that the effects of the present invention are not impaired, extender pigments such as heavy calcium carbonate, clay, kaolin, talc, precipitated barium sulfate, barium carbonate, white carbon, diatomaceous earth, inorganic aggregates such as silica sand and gypsum spar, inorganic lightweight aggregates such as perlite and expanded vermiculite, endothermic substances such as aluminum hydroxide, magnesium hydroxide, zeolite, halloysite, allophane, ettringite, foaming agents such as melamine, dicyandiamide, azodicarbonamide, charring agents such as pentaerythritol and dipentaerythritol, flame retardants, fibers, reinforcing materials, plasticizers, preservatives, fungicides, defoaming agents, thickeners, leveling agents, water reducing agents, pigment dispersants, anti-settling agents, anti-dripping agents, ultraviolet absorbers, antioxidants and other additives.

[0052] The laminate of the present invention can be used as a building material, for example, it can be laminated on a substrate and suitably used as a surface material. For example, when used as a surface material, examples of applicable substrates include color steel plates, galvanized steel plates, vinyl chloride steel plates, stainless steel plates, aluminum plates, copper plates, titanium plates, aluminum-plated steel plates, zinc-plated steel plates, clad steel plates, sandwich steel plates, concrete, mortar, porcelain tiles, fiber-reinforced cement boards, calcium silicate cement boards, slag cement perlite boards, ALC boards, siding boards, extruded boards, gypsum boards, plywood, plastic boards, heat insulation boards, etc.

[0053] When laminating the laminate of the present invention on such a substrate, a method of preparing a laminate in which a colored coating film is laminated on urethane foam in advance and attaching the laminate to the substrate, or a method of directly coating the components for forming urethane foam on the substrate, forming urethane foam on the substrate, and then laminating a material for forming a colored coating film on the urethane foam, etc. can be mentioned.

[0054] The method for obtaining a urethane foam is preferably, for example, to keep it in a two-component form during distribution and mix and use it at the time of use (when forming the foam). In such a two-component form, for example, the first liquid can be in a form containing a polyol compound (foaming agent, catalyst, and flame retardant), and the second liquid can be in a form containing a polyisocyanate compound.

[0055] The viscosity of the above-mentioned first 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 even more preferably 50 mPa·s or more and 250 mPa·s or less from the viewpoints of the storage stability of the first liquid, handleability, workability during foam formation, etc. The viscosity is the viscosity (pointer value at the fourth rotation) at 20 rpm measured with a BH-type viscometer at a temperature of 20°C. With such a viscosity, while sufficiently ensuring the storage stability of the curable composition, the curable composition can be set to a relatively low viscosity. Thereby, stirring operations during construction etc. are reduced, and advantageous effects can also be obtained in terms of handleability, workability, miscibility with the polyisocyanate compound, etc. Also, the viscosity of the above-mentioned 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 even more preferably 50 mPa·s or more and 250 mPa·s or less.

[0056] When applying the urethane foam to a substrate, for example, a spray foaming machine for spraying work (for example, a two-component tip-mixing spray coating machine, etc.) can be used to spray and apply the mixture of the first liquid and the second liquid. In this case, it is preferable to set the temperatures of the first liquid and the second liquid to be 20°C or more and 60°C or less, more preferably 30°C or more and 50°C or less, respectively. 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 substrate to form a foam on the substrate. As the spraying environment, it can preferably be constructed at 5°C or more and 45°C or less. The mixing of the first liquid and the second liquid is preferably about 1:1 in terms of volume ratio. The foam formed in such a manner can exhibit excellent performance in terms of low thermal conductivity, heat resistance, etc. The thickness of the foam is not particularly limited and may be appropriately set according to required performance, etc., but is preferably 10 mm or more, more preferably about 15 mm or more and 500 mm or less.

[0057] In the method of laminating a colored coating film on the upper (surface) of the urethane foam, a colored coating film can be formed by applying a material for forming the colored coating film (a colored coating film forming material containing a binder, a colorant, etc.) and drying and curing it. At this time, additives, water, etc. can be mixed with the colored coating film forming material as necessary. The colored coating film forming material is preferably applied directly onto the urethane foam. When applying the colored coating film forming material, coating tools such as a spatula, a spray, a roller, a brush, etc. can be appropriately used. The thickness of the formed colored coating film may be appropriately set according to the application site, use, required performance, etc., but is preferably 0.01 mm or more and 5 mm or less, more preferably 0.03 mm or more and 3 mm or less.

Examples

[0058] Examples are shown below to clarify the features of the present invention.

[0059] (Urethane Foam) As the first liquid, a polyol composition prepared by uniformly mixing the following raw materials at the weight ratios shown in Table 1 was prepared. As the second liquid, one composed 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-based 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: Hydrochlorofluorocarbon · Blowing Agent 2: Water (hydroxyl value: 6233 mgKOH / g) · Catalyst 1: Nureation catalyst (glycol solution of tetraalkylammonium 2-ethylhexanoate) · Catalyst 2: Resinification catalyst (octanoic acid solution of bismuth octanoate) · Flame Retardant 1: Phosphate compound (aluminum tris(diethylphosphate), average particle size 4 μm, density 1.35 g / cm 3 ) · Flame Retardant 2: Phosphate compound (sodium phosphate, 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 ) · Flame Retardant 4: Cyclic phosphoramidate (in Formula 4, R1: all methylene groups, R2: all methyl groups, R3: all hydrogen atoms, R4: butylene group cyclic phosphoramidate, average particle size 3 μm) · Flame Retardant 5: Cyclic phosphoramidate (in Formula 4, R1: all methylene groups, R2: all methyl groups, N(R3)-R4-(R3)N: cyclic phosphoramidate with a nitrogen-containing 6-membered ring structure (piperidine structure), average particle size 3 μm) · Double Bond Compound 1: Ethylenically unsaturated double bond-containing compound (trimethylolpropane triacrylate, ethylenically unsaturated double bond concentration 10 mmol / g, acid value: 0 mgKOH / g) · Foam Stabilizer: Silicone-based foam stabilizer (Colored coating film) As a colored coating film forming material, a mixture prepared by uniformly mixing the following raw materials at the weight ratios shown in Table 2 was prepared. · Organic Binder 1: Acrylic resin (glass transition temperature -15°C, solid content 50 wt%) · Organic binder 2: Acrylic-styrene copolymer resin (glass transition temperature 15 °C, solid content 50% by weight) · Organic binder 3: Acrylic-styrene copolymer resin (glass transition temperature -3 °C, solid content 50% by weight) · Coloring pigment 1: Titanium oxide · Coloring pigment 2: Carbon black · Coloring pigment 3: Ferric oxide · Additive: Thickening agent, defoaming agent

[0060] (Examples 1 to 17, Comparative Example 1) The first liquid and the second liquid were each heated to 40 °C, and these were mixed so as to have the isocyanate index shown in Table 1. The obtained mixed liquid was sprayed onto a substrate (slate board) with a spray gun in a 5 °C atmosphere and foamed to obtain a urethane foam (thickness 50 mm) in which the entire one side of the substrate was covered with foam. After standing at room temperature (temperature 23 °C, relative humidity 50%) for 24 hours, a colored coating film forming material prepared with the formulation shown in Table 2 was applied by spraying at room temperature to form a colored coating film (thickness 0.1 mm), and a test piece was obtained. Each test was carried out on the obtained test piece by the following method. The results are shown in Tables 1 and 3.

[0061] (1) Foam formability The state of the formed foam was visually observed. The evaluation criteria are as follows. ◎: A homogeneous foam was formed. ○: A substantially homogeneous foam was formed. △: Some abnormalities (brittleness, non-uniform foaming, poor adhesion, etc.) were observed in the foam. ×: Abnormalities were observed in the foam.

[0062] (2) Thermal conductivity The foam portion of the test piece was cut out, and the thermal conductivity was measured using a thermal conductivity meter. The evaluation criteria are as follows. ○: Thermal conductivity is 0.03 W / (m·K) or less ×: Thermal conductivity exceeds 0.03 W / (m·K)

[0063] (3) Aesthetic test Immediately after obtaining the test specimen (1), and after leaving it to stand at room temperature (temperature 23°C, relative humidity 50%) for 14 days (2), the surface of the test specimen was visually observed and evaluated. The evaluation was as follows. ◎: No cracks were found, and it had excellent aesthetics. ○: Almost no cracks were found, and it had good aesthetics. ×: Cracks were prominent, and the aesthetics were impaired.

[0064] [Table 1]

[0065] [Table 2]

[0066] [Table 3]

Claims

1. A laminate in which a colored coating film is laminated on a urethane foam, The urethane foam is formed from a polyol compound, a blowing agent, a catalyst, a polyisocyanate compound, and a flame retardant; The colored coating film is formed by applying a colored coating film-forming material containing a binder and a colorant, and drying and curing the material. the binder is a synthetic resin emulsion of an acrylic resin or an acrylic-styrene copolymer resin having a glass transition temperature of 0° C. or lower; A laminate characterized in that the amount of the colorant in the colored coating film is 98 parts by weight or more and 500 parts by weight or less per 100 parts by weight of the solid content of the binder.

2. 2. The laminate according to claim 1, wherein the flame retardant comprises at least one selected from the group consisting of cyclic phosphate esters, phosphinate compounds, phosphoramidates, and cyclic phosphoramidates.

3. 2. The laminate according to claim 1, wherein the binder is a synthetic resin emulsion of an acrylic resin or an acrylic-styrene copolymer resin having a glass transition temperature of -30° C. or higher and -5° C. or lower.

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