JP7367153B2 - insulation laminate - Google Patents

Description

The present invention relates to a heat insulating laminate.

In general, in building structures, in addition to flame retardant materials, heat insulating materials are installed to improve heat insulation performance.
As such heat insulating materials, organic heat insulating materials such as urethane foam, phenol foam, and styrene foam are mainly used. For example, urethane foam is widely used because it has excellent heat insulation properties and can be constructed at relatively low cost.
In recent years, as the heat resistance of urethane foam has improved, it has become possible to use it alone and as a surface material, so it is expected that its applications will further expand. (For example, Patent Documents 1, 2, etc.)

WO2014/112394 JP2015-151524

However, as the use of such urethane foam expanded and it began to be used in highly visible areas, the aesthetic appearance of the surface became a problem. In addition, it may discolor due to exposure to ultraviolet rays, etc., so improving the aesthetic appearance of the surface is an urgent need to expand its use.

As a result of extensive research to solve the above problems, the present inventors have discovered that a colored coating film containing a binder, a colored pigment, and a phosphorus compound having a specific refractive index is laminated on an organic heat insulating layer containing a phosphorus compound. The inventors have discovered that the heat insulating laminate has excellent heat insulation and heat resistance as well as excellent aesthetics, leading to the completion of the present invention.

That is, the present invention has the following features.
1. A heat insulating laminate in which a colored coating film is laminated on an organic heat insulating layer,
The organic heat insulating layer contains a phosphorus compound,
The phosphorus compound includes a phosphate ester and a phosphinate compound,
A heat insulating laminate, wherein the colored coating film contains a binder, a colored pigment, and a phosphorus compound having a refractive index of 1.4 or more and 1.7 or less.
2. 1. A mixing ratio (weight ratio) of the phosphoric acid ester and the phosphinate compound is 99:1 to 40:60. The insulation laminate described in .
3. 1. The binder is an organic binder. The insulation laminate described in .
4. 1. The organic heat insulating layer is a urethane foam formed from a polyol composition containing a polyol compound, a phosphorus compound, and a blowing agent, and a polyisocyanate compound. The insulation laminate described in .
5. 4. The blending ratio of the polyol composition and the polyisocyanate compound is 200 or more and 800 or less in terms of isocyanate index. The insulation laminate described in .

The heat insulating laminate of the present invention has excellent heat insulation properties, heat resistance, and aesthetic appearance.

The present invention is a heat insulating laminate in which a colored coating film is laminated on an organic heat insulating layer,
The organic heat insulating layer contains a phosphorus compound, and the colored coating film contains a binder, a colored pigment, and a phosphorus compound having a refractive index of 1.4 or more and 1.7 or less. be.

The organic heat insulating layer of the present invention contains a phosphorus compound, and independently has both heat insulating performance and heat resistance performance.

Examples of the organic heat insulating layer include foamed organic resin bodies such as urethane foam, phenol foam, polystyrene foam, polyethylene foam, polypropylene foam, polyvinyl chloride foam, and cellulose fiber. By blending a phosphorus compound, an organic heat-insulating layer that has both heat-insulating performance and heat-resistant performance can be obtained.

Examples of the phosphorus compound include phosphoric acid ester, polyphosphate compound, phosphinate compound, halogenated phosphazene, red phosphorus, phosphorus trichloride, phosphorus pentachloride, and the like. Such a phosphorus compound easily forms a good carbonized layer with the organic heat insulation layer component, and provides excellent heat resistance as well as excellent heat insulation properties.

Specifically, examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, trisnonylphenyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, and cresyl phenyl. Phosphate, cresyl diphenyl phosphate, octyldiphenyl phosphate, trixylenyl phosphate, diisopropylphenyl phosphate, tris (2-ethylhexyl) phosphate, resorcinol bis diphenyl phosphate, bisphenol A bis (diphenyl phosphate), resorcinol bis dixylenyl 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, phenylnonylphenyl hydroquinonyl phosphate, phenyl dinonylphenyl phosphate, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonate, dimethyl- Examples include 4-hydroxy-3,5-dibromobenzylphosphonate and diphenyl-4-hydroxy-3,5-dibromobenzylphosphonate.
Examples of the polyphosphate compound include ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melem polyphosphate, melam polyphosphate, and melon polyphosphate.
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, tris(diethylphosphinate)aluminum, tris(methylethylphosphinate)aluminum, tris(dibutylphosphinate)aluminum, tris( butylethylphosphinic acid) aluminum, tris(diphenylphosphinic acid) aluminum, bis(diethylphosphinic acid) zinc, bis(methylethylphosphinic acid) zinc, bis(diphenylphosphinic acid) zinc, bis(diethylphosphinic acid) titanyl, tetrakis( titanyl (diethylphosphinic acid), titanyl bis(methylethylphosphinic acid), titanyl tetrakis(methylethylphosphinic acid), titanyl bis(diphenylphosphinic acid), titanyl tetrakis(diphenylphosphinic acid), etc., and one or two of these titanyl More than one species can be used.
Examples of halogenated phosphazenes include hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene, dodecachlorocyclohexaphosphazene, hexabromocyclotriphosphazene, hexafluorocyclotriphosphazene, octafluorocyclotetraphosphazene, and decachlorocyclotriphosphazene. Fluorocyclopentaphosphazene, dodecafluorocyclohexaphosphazene, hexamethoxycyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, hexaphenoxycyclotriphosphazene, diethoxytetrafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, methoxypentafluorocyclotriphosphazene Examples include phosphazene, propoxypentafluorocyclotriphosphazene, butoxypentafluorocyclotriphosphazene, and the like.

In the present invention, a phosphoric acid ester and a phosphinate compound are used together as the phosphorus compound . When using a phosphoric acid ester and a phosphinate compound together, the mixing ratio (weight ratio) of the phosphoric acid ester:phosphinate compound is 99:1 to 40:60, more preferably 98:2 to 50:50. , more preferably 97:3 to 60:40. With such a mixing ratio, sufficient effects can be obtained in terms of foam formability, strength, heat resistance, etc.

The organic heat insulating layer of the present invention is particularly preferably urethane foam.
As the urethane foam, one formed from a polyol composition containing a polyol compound, a phosphorus compound, and a blowing agent, and a polyisocyanate compound can be used.

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

Among these, examples of polyester polyols include aromatic polyester polyols, aliphatic polyester polyols, aromatic/aliphatic polyester polyols, etc., and one or more of these can be used.
Specifically, aromatic polyester polyol refers to a polyol having an aromatic hydrocarbon in one molecule, for example, an aromatic polybasic acid such as orthophthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, etc. Examples include condensed polyester polyols obtained by reacting with alcohol, phthalic acid polyester polyols obtained by decomposing phthalic acid polyester molded products such as polyethylene terephthalate, and the like. Further, examples of the polyhydric alcohol include alcohols having a valence of 2 or more and derivatives thereof, phenols having a valence of 2 or more, polyols, and the like.
Aliphatic polyester polyols are polyols containing aliphatic hydrocarbons in one molecule, such as aliphatic polybasic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, and fumaric acid. Examples include condensed polyester polyols obtained by reacting with alcohols.
Aromatic/aliphatic polyester polyol is a polyol containing an aliphatic hydrocarbon and an aromatic hydrocarbon in one molecule, and is obtained by reacting an aromatic polybasic acid or an aliphatic polybasic acid with a polyhydric alcohol. Examples include condensed polyester polyols.
In the present invention, it is preferable that a polyester polyol is included as the polyol compound.

Examples of the 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, by adding alkylene oxide using an initiator such as toluene diamine, diethyltoluene diamine, 4,4'-diaminodiphenylmethane, p-phenylene diamine, o-phenylene diamine, naphthalene diamine, triethanolamine, Mannich condensate, etc. Examples include the aromatic amine polyether polyols obtained. 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 glycerin-based polyether polyols include polyether polyols obtained by adding alkylene oxide to glycerin as an initiator. Examples of amino group-containing polyether polyols include those obtained by adding alkylene oxide using a low molecular weight amine (eg, ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, neopentyl diamine, etc.) as an initiator.

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 expressed by the number of mg of potassium hydroxide equivalent to the hydroxyl group contained in 1 g of the sample, and is based on JIS K 1557-1:2007 Plastics - Polyurethane raw material polyol test method - Part 1: Hydroxyl value This is the value measured based on the calculation method. The hydroxyl value of a polyol compound is a value measured for a mixture of all polyol compounds.

As the phosphorus compound, the above-mentioned phosphorus compound can be used, and the mixing amount of the polyol compound of the present invention and the above-mentioned phosphorus compound is preferably 10 parts by weight or more and 1000 parts by weight or less, based on 100 parts by weight of the polyol compound. More preferably, it is 30 parts by weight or more and 600 parts by weight or less, and still more preferably 50 parts by weight or more and 400 parts by weight or less. If it is within such a range, it is suitable in terms of heat resistance and the like.
Further, in the present invention, a phosphoric acid ester and a phosphinate compound are used as the phosphorus compound , and the amount of the phosphoric acid ester mixed is 20 parts by weight or more and 900 parts by weight or less (preferably 40 parts by weight) with respect to 100 parts by weight of the polyol compound. 600 parts by weight or less, more preferably 60 parts by weight or more and 400 parts by weight), and the mixing amount of 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 150 parts by weight or less, even more preferably 20 parts by weight or more and 150 parts by weight or less). is preferably 40 parts by weight or more and 120 parts by weight or less).
Further, in the present invention, a phosphoric acid ester and a phosphinate compound are used together as the phosphorus compound . When using a phosphoric acid ester and a phosphinate compound together, the mixing ratio (weight ratio) of the phosphoric acid ester:phosphinate compound is 99:1 to 40:60, more preferably 98:2 to 50:50. , more preferably 97:3 to 60:40. With such a mixing ratio, sufficient effects can be obtained in terms of foam formability, strength, heat resistance, etc.

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

Among these, examples of hydrocarbons include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and the like. Examples of hydrochlorofluorocarbons (HCFCs) include 1,1-dichloro-1-fluoroethane (HCFC-141B), 1-chloro-1,1-difluoroethane (HCFC-142B), and chlorodifluoromethane (HCFC-22). etc. Examples of hydrofluorocarbons (HFCs) 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-hepta Fluoropropane (HFC227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluorobutane (HFC365mfc), 1,1,1,2,2, Examples include 3,4,5,5,5-decafluoropentane (HFC4310mee).

Examples of hydrofluoroolefins (HFO) include 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) and 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 their isomers (cis form, trans form), etc. Examples of hydrochlorofluoroolefins (HCFO) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), Examples include dichlorotrifluoropropene (HCFO1223) and their isomers (cis form, trans form).
The blowing agent in the present invention is preferably one or more selected from hydrofluoroolefins, hydrochlorofluoroolefins, and water, such as hydrofluoroolefins and water, hydrochlorofluoroolefins and water, and hydrofluoroolefins and water. A combination of blowing agents such as hydrochlorofluoroolefin and water can be used.

The mixing amount of the blowing 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, even more preferably 30 parts by weight or more and 150 parts by weight or less, based on 100 parts by weight of the polyol compound. It is.

Examples of the polyisocyanate compound include, but are not limited to, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenylisocyanate (crude MDI (c-MDI)), xylylene diisocyanate (XDI), and 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 foam, superiority in cost, and the like. Examples of MDI include monomeric MDI and polymeric MDI (polymethylene polyphenylisocyanate).

The blending ratio of the polyol composition and the polyisocyanate compound is not particularly limited, but the isocyanate index is preferably 150 or more, more preferably 200 or more and 800 or less, still more preferably 250 or more and 500 or less, and most preferably 300 or more and 450 or less. It is desirable to mix the above-mentioned polyol composition and the above-mentioned polyisocyanate compound etc. so that If the isocyanate index is within such a range, it is suitable in terms of heat resistance and the like. The isocyanate index is expressed as 100 times the number of equivalents of isocyanate groups in the polyisocyanate compound divided by the total number of equivalents of active hydrogen in the active hydrogen-containing components (polyol compound, water, etc.). be.

In addition to the above-mentioned components, the polyol composition can also contain an ethylenically unsaturated double bond-containing compound. By using the ethylenically unsaturated double bond-containing compound, the effects of the phosphorus compound such as heat resistance can be obtained even more efficiently. Examples of the ethylenically unsaturated double bond include a (meth)acryloyl group, an allyl group, and a propenyl group.

The ethylenically unsaturated double bond-containing compound is preferably one in which the concentration of ethylenically unsaturated double bonds in one molecule is 0.5 mmol/g or more and 20 mmol/g, from the viewpoint of the above-mentioned effects, etc., and 5 mmol/g. More preferably, the amount is 15 mmol/g or more and 15 mmol/g or less. 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 expressed as the molecular weight. It is expressed as 1000 times the value divided by (mmol/g).

Specific examples of ethylenically unsaturated double bond-containing compounds include polyhydric alcohols (e.g., divalent or higher alcohols and their derivatives, divalent 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 alkyl thioethers 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 a urethane bond in the molecule, nonylphenoxy polyethylene oxyacrylate, and the like. These can be used alone or in combination of two or more.

Among these, examples of reactants of polyhydric alcohols and unsaturated carboxylic acids include pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta( meth)acrylate, tetramethylolmethanetri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, trimethylolethanetri(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)acryloxypolyethoxy)phenyl), propoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane, etc. can be mentioned.

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)acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, alkylene Examples include oxide-modified urethane di(meth)acrylate.

The amount of the ethylenically unsaturated double bond-containing compound to be 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 90 parts by weight or less, even more preferably 10 parts by weight or less, based on 100 parts by weight of the polyol compound. It is not less than 80 parts by weight and not more than 80 parts by weight. In addition, when a plurality of hydroxyl groups are contained in the ethylenically unsaturated double bond-containing compound, it is regarded as a polyol compound. The isocyanate index is also calculated by taking into consideration the active hydrogen-containing component contained in the ethylenically unsaturated double bond-containing compound.

In addition to the above components, additives such as flame retardants, catalysts, foam stabilizers, polymerization inhibitors, fibers, surfactants, compatibilizers, colorants, and antioxidants other than those listed above may also be used. .

Examples of flame retardants other than those listed above include halogen flame retardants, organic bromine flame retardants, nitrogen flame retardants, metal hydrate flame retardants, antimony flame retardants, boron flame retardants, silicone flame retardants, etc. Can be mentioned.

Examples of the catalyst include, but are not limited to, a nurate catalyst, a resin catalyst, a foaming catalyst, and the like, and one or more of these can be used.
The nurating catalyst is not particularly limited as long as it is an effective catalyst for isocyanurating, and examples thereof include tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, and trimethylbenzyl ammonium, or their organic acids. 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 , hydroxides of trialkylhydroxyalkylammonium 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 alkyl carboxylic acids (e.g., acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, lactic acid, etc.), β-based compounds such as 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 tetrabutyrate and tributylantimony oxide, and aminosilyl group-containing compounds such as hexamethylsilazane. , one or more of these can be used.

Examples of the resinization 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 their Organic acid salts, bismuth tris (2-ethylhexanoate), bismuth tris (neodecanoate), 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- Imidazole 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), etc., and 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 or organic acid salts thereof, and the like, and one or more of these can be used.

The mixing amount of the catalyst is preferably 0.1 parts by weight or more and 50 parts by weight or less, more preferably 0.5 parts by weight or more and 45 parts by weight or less, and even more preferably 1 part by weight or more and 40 parts by weight, based on 100 parts by weight of the polyol compound. below. Note that 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 resin forming catalyst and/or a foaming catalyst together with a nurating catalyst, which is advantageous for workability and foam forming properties. Note that 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.

Examples of the foam stabilizer include silicone foam stabilizers such as polyether-modified silicone compounds, fluorine-containing compound foam stabilizers, and the like. 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 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, based on 100 parts by weight of the polyol compound.

Examples of the polymerization inhibitor include hydroquinone polymerization inhibitors, benzoquinone polymerization inhibitors, catechol polymerization inhibitors, piperidine polymerization inhibitors, and the like. Such a polymerization inhibitor provides long-term storage stability in the two-part type described below, and also contributes to production stability when added during the polyol production process.

Examples of the 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 provide workability, foam forming properties, dimensional stability, and the like. In the present invention, it is not necessary to use fibers, but if fibers are mixed, the effect can be achieved with a small amount of fibers.

Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. Such surfactants can impart storage stability and dispersion stability.

The colored coating film of the present invention contains a binder, a colored pigment, and a phosphorus compound with a refractive index of 1.4 to 1.7, and maintains the heat insulation properties and heat resistance of the heat insulating laminate while maintaining adhesion. , the aesthetic appearance of the surface can be improved.

Examples of the binder include organic binders and inorganic binders.
Examples of the organic binder include acrylic resin, vinyl acetate resin, acrylic vinyl acetate resin, polyethylene resin, styrene resin, acrylic styrene resin, vinyl propionate resin, vinyl versatate resin, ethylene vinyl acetate resin, vinyl chloride resin, and epoxy. Inorganic binders include resins, urethane resins, polyester resins, phenolic resins, petroleum resins, vinyl chloride resins, epoxy resins, urethane resins, polybutadiene resins, alkyd resins, melamine resins, propylene rubber, chloroprene rubber, butyl rubber, isobutylene rubber, etc. , silicone resin, glass, water glass, etc., and among these, one type or two or more types can be used in combination. Further, it is preferable to use a binder having a refractive index of 1.4 or more and 1.7 or less.
Further, the form is not particularly limited, such as water-soluble resin, water-dispersible resin (resin emulsion), powder resin (re-emulsified emulsion), etc., but water-dispersible resin (resin emulsion) is particularly preferred in the present invention.
In the present invention, it is particularly preferable to use an organic binder, and it is particularly preferable to use a vinyl chloride resin and/or an acrylic styrene resin, and more preferably a vinyl chloride resin and an acrylic styrene resin.

Coloring pigments include, but are not limited to, titanium oxide, zinc oxide, carbon black, graphite, black iron oxide, copper chromium black, cobalt black, copper manganese iron black, ferric oxide, and lead chromate. (molybdate orange), permanent red, permanent carmine, yellow lead, yellow iron oxide, titanium yellow, chrome green, cobalt green, ultramarine, navy blue, cobalt blue inorganic pigments, azo, naphthol, pyrazolone, anthraquinone, Examples include organic coloring pigments such as perylene, quinacridone, disazo, isoindolinone, benzimidazole, phthalocyanine, quinophthalone, and dioxazine, pearl pigments, fluorescent pigments, luminous pigments, and metallic pigments. can be used alone or in combination of two or more. The color tone of the colored coating film can be appropriately set by adjusting the type of coloring pigment, the amount mixed, etc.
The content of the colored pigment 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.

The phosphorus compound used in the colored coating film has a refractive index of 1.4 or more and 1.7 or less (preferably 1.45 or more and 1.68 or less). Such a phosphorus compound has a small difference in refractive index from the binder, and has the effect of not inhibiting the color tone produced by the coloring pigment. Furthermore, the heat resistance can be improved together with the phosphorus compound contained in the organic heat insulating layer, and the heat resistance can be improved as well as the aesthetic appearance.
The phosphorus compound used in the colored coating film is not particularly limited as long as it has a refractive index of 1.4 or more and 1.7 or less, and includes the above-mentioned phosphoric acid esters, polyphosphate compounds, phosphinate compounds, halogenated phosphazenes, and red phosphorus. One or more of phosphorus compounds such as phosphorus trichloride, phosphorus pentachloride, etc. can be used. In particular, in the present invention, it is preferable to use polyphosphate compounds such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melem polyphosphate, melam polyphosphate, and melon polyphosphate.
Note that the refractive index is a value measured using an Abbe refractometer in accordance with JIS K 0062.

The blending amount of the phosphorus compound in the colored coating film is preferably 10 parts by weight or more and 1000 parts by weight or less, more preferably 70 parts by weight or more and 800 parts by weight or less, and even more preferably It is 150 parts by weight or more and 600 parts by weight or less.

In addition to the above components, the colored coating film of the present invention contains extender pigments such as heavy calcium carbonate, clay, kaolin, talc, precipitated barium sulfate, barium carbonate, white carbon, diatomaceous earth, etc., to the extent that the effects of the present invention are not impaired. , inorganic aggregates such as silica sand and anhydrite, inorganic lightweight aggregates such as perlite and expanded vermiculite, endothermic substances such as aluminum hydroxide, magnesium hydroxide, zeolite, halloysite, allophane, and ettringite, melamine, dicyandiamide, and azodicarbonamide. Foaming agents such as pentaerythritol and dipentaerythritol, carbonizing agents such as pentaerythritol and dipentaerythritol, flame retardants, fibers, reinforcing materials, plasticizers, preservatives, antifungal agents, antifoaming agents, thickeners, leveling agents, water reducing agents, pigment dispersions It may also contain agents, anti-settling agents, anti-sag agents, ultraviolet absorbers, antioxidants, etc.

The heat insulating laminate of the present invention can be used as a building material, for example, laminated on a base material and suitably used as a surface material.
For example, when used as a surface material, applicable base materials include color steel plates, galvanium steel plates, PVC steel plates, stainless steel plates, aluminum plates, copper plates, titanium plates, aluminum plated steel plates, galvanized steel plates, clad steel plates, and sandwich plates. Examples include steel plates, concrete, mortar, porcelain tiles, fiber-containing cement plates, cement calcium silicate plates, slag-cement perlite plates, ALC plates, siding plates, extrusion molded plates, gypsum boards, plywood, plastic plates, and heat insulation plates.

When laminating a heat insulating laminate on such a base material, there is a method of preparing a heat insulating laminate in which a colored coating film is laminated on an organic heat insulating layer in advance, and pasting the heat insulating laminate onto the base material. Alternatively, there is a method in which a component that forms an organic heat insulating layer is directly applied to a base material, an organic heat insulating layer is formed on the base material, and then a material that forms a colored coating is laminated on the organic heat insulating layer. It will be done.

For example, in the case of urethane foam, it is preferable to prepare the organic heat insulating layer in a two-component form during distribution, and mix the foam at the time of use (forming the foam layer). In such a two-part type, for example, the first part may contain a polyol composition containing a polyol compound, a phosphorus compound, and a blowing agent, and the second part 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 and 350 mPa·s from the viewpoint of storage stability, handling properties, workability during foam formation, etc. of the first liquid. s or less, more preferably 50 mPa·s or more and 250 mPa·s or less. Note that the viscosity is the viscosity at 20 rpm (the guideline value at the 4th rotation) measured with a BH type viscometer at a temperature of 20°C. With such a viscosity, the first liquid can be set to a relatively low viscosity while ensuring sufficient storage stability of the first liquid. This reduces stirring work and the like during construction, and provides advantageous effects in terms of handling properties, construction properties, miscibility with polyisocyanate compounds, 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 even more preferably 50 mPa·s or more and 250 mPa·s or less.

When applying the urethane foam to the base material, use a spray foaming machine for spraying work (for example, a two-component tip mixing type spray coating machine, etc.) to mix the first liquid and the second liquid together. It can be applied by spraying a mixture of two liquids. In this case, it is preferable that the temperature of the first liquid and the second liquid be set to 20°C or more and 60°C or less, more preferably 30°C or more and 50°C or less. The first liquid and the second liquid, which are set at a predetermined temperature in this way, are mixed at the spray tip and sprayed toward the base material to form a foam on the base material. The spraying environment is preferably 5°C or higher and 45°C or lower.
It is desirable that the first liquid and the second liquid be mixed at a volume ratio of about 1:1. A foam layer formed by such a method can exhibit excellent performance in terms of low thermal conductivity, heat resistance, and the like. The thickness of the foam layer is not particularly limited and may be set appropriately depending on the required performance, etc., but is preferably 10 mm or more, more preferably about 15 to 500 mm. Moreover, such construction can be carried out without particular limitation, such as new construction or renovation.

In the method of laminating a colored coating film on the organic heat insulating layer (surface), materials forming the colored coating film (including a binder, a colored pigment, a phosphorus compound with a refractive index of 1.4 or more and 1.7 or less, etc.) are used. A colored coating film can be formed by applying a colored coating film forming material), drying and curing it. At this time, water or the like may be mixed with the colored coating film-forming material, if necessary.
It is desirable that the colored film-forming material be applied directly onto the organic heat insulating layer. When applying the colored coating film-forming material, a coating tool such as a trowel, spray, roller, or brush can be used as appropriate, and the coating can be applied once or in multiple times.
The thickness of the colored coating film to be formed may be appropriately set depending on the application site, purpose, 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. It is also possible to form two or more types of colored coating films.

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

As the first liquid, a polyol composition was prepared by uniformly mixing the following raw materials in the weight proportions shown in Table 1. In addition, in Table 1, the amount of the active ingredient is described for the catalyst.
In addition, a uniform mixture of the following raw materials in the weight proportions shown in Table 2 was prepared as a colored coating film forming material.
・Polyol compound 1: Aromatic polyester polyol (terephthalic acid polyester polyol, hydroxyl value: 250 mgKOH/g)
・Polyol compound 2: Aliphatic polyester polyol (succinic acid polyester polyol, hydroxyl value: 100 mgKOH/g)
・Polyol compound 3: Aromatic polyether polyol (Mannich modified polyether polyol, hydroxyl value: 350 mgKOH/g)
- Phosphorus compound 1: Alkylated phosphinate compound (tris(diethylphosphinic acid) aluminum, density 1.35 g/cm ³ , refractive index 1.5)
・Phosphorus compound 2: Phosphoric acid ester (tris (β-chloropropyl) phosphate, density 1.29 g/cm ³ , refractive index 1.5)
- Phosphorus compound 3: ammonium polyphosphate (density 1.9 g/cm ³ , refractive index 1.6)
・Phosphorus compound 4: Sodium phosphinate (density 1.39 g/cm ³ , refractive index 1.5)
・Blowing agent 1: Hydrochlorofluoroolefin ・Blowing agent 2: Hydrofluoroolefin ・Blowing agent 3: Water (hydroxyl value: 6233mgKOH/g)
・Catalyst 1: Nurate catalyst (ethylene glycol solution of tetraalkylammonium organic acid salt, active ingredient 50% by weight, hydroxyl value: 900mgKOH/g)
・Catalyst 2: Resinization catalyst (imidazole catalyst (active ingredient 100% by weight))
・Catalyst 3: Resinization catalyst (octylic acid solution of bismuth octylate)
・Double bond compound 1: Ethylenically unsaturated double bond-containing compound (trimethylolpropane triacrylate, ethylenically unsaturated double bond concentration: 10 mmol/g, hydroxyl value: 0 mgKOH/g)
・Double bond compound 2: Ethylenically unsaturated double bond-containing compound (pentaerythritol tetraacrylate, ethylenically unsaturated double bond concentration: 11 mmol/g, hydroxyl value: 0 mgKOH/g)
・Double bond compound 3: Ethylenically unsaturated double bond-containing compound (pentaerythritol triacrylate, ethylenically unsaturated double bond concentration: 10 mmol/g, hydroxyl value: 25 mgKOH/g)
・Foam stabilizer: Silicone foam stabilizer ・Polyisocyanate compound: Polymeric MDI
・Organic binder 1: Acrylic-styrene copolymer resin (solid content 50% by weight)
・Organic binder 2: Vinyl chloride resin (solid content 50% by weight)
・Organic binder 3: Vinyl acetate-ethylene copolymer resin (solid content 50% by weight)
・Organic binder 4: Acrylic resin (solid content 50% by weight)
・Coloring pigment 1: Titanium oxide (TiO ₂ , rutile type, average particle size 0.3 μm)
・Coloring pigment 2: Carbon black ・Coloring pigment 3: Ferric oxide ・Blowing agent 4: Melamine ・Carbonizing agent 1: Pentaerythritol ・Carbonizing agent 2: Chlorinated paraffin ・Additives: Glass fiber, calcium carbonate

(Experiment example 1)
A mixed solution prepared by mixing a polyol composition (first liquid) prepared with the formulation shown in Table 1 and a polyisocyanate compound (second liquid) with an isocyanate index shown in Table 3 is sprayed onto a galvanized steel sheet, It was foamed to form an organic heat insulating layer.
After leaving the obtained organic heat insulating layer at room temperature (temperature 23°C, relative humidity 50%) for 24 hours, a colored film-forming material prepared with the formulation shown in Table 2 was applied with a roller at room temperature to form a colored film. was formed to obtain test body 1 (insulating laminate).
The thickness of the organic heat insulating layer was 50 mm, and the thickness of the colored coating film was 0.5 mm.
The following tests were conducted on the obtained heat insulating laminate. The results are shown in Table 3.

(Test 1) Aesthetics Test The surfaces of the test specimens were visually observed and evaluated immediately after obtaining them (1) and after being exposed outdoors for one week (facing 45 degrees south in Ibaraki City) (2). The evaluation is as follows.
◎: Excellent aesthetic appearance.
◯: Almost no discoloration was observed, and good aesthetic appearance was observed.
×: The surface was discolored.

(Test 2) Thermal conductivity A part of the obtained test body 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)

(Test 3) Heat resistance test A cone calorimeter specified in ISO 5660 was used. The heating intensity was 50 kW/m ² and the heating time was 5 minutes, 10 minutes, and 20 minutes. The evaluation items and criteria are as follows.

(Evaluation item)
(3-1) Dimensional change ◎: Dimensional change in the thickness direction of the organic heat insulating layer after the test is 10 mm or less ○: Dimensional change in the thickness direction of the organic heat insulating layer after the test is more than 10 mm and less than 20 mm ×: Organic heat insulating layer after the test Dimensional change in the thickness direction of the layer is more than 20 mm (3-2) Total heat generation ○: Total heat generation is 8 MJ/m ² or less ×: Total heat generation is more than 8 MJ/m ² (3-3) Maximum heat generation rate ○: Maximum heat generation rate is 200kW/ ^m2 or less ×: Maximum heat generation rate is over 200kW/ ^m2

(Evaluation criteria)
│ │Heating time │ 3-1 │ 3-2 │ 3-3 │
│A │ 20 minutes│ ◎ │ ○ │ ○ │
│A'│ 20 minutes│ ○ │ ○ │ ○ │
│B │ 10 minutes│ ◎ │ ○ │ ○ │
│B'│ 10 minutes│ ○ │ ○ │ ○ │
│C │ 5 minutes│ ◎ │ ○ │ ○ │
│C'│ 5 minutes│ ○ │ ○ │ ○ │
│D │ 5 minutes │ × │ × │ × │
Regarding heat resistance, excellent A>A'>B>B'>C>C'>D poor.

(Experiment Examples 2 to 32)
Test specimens 2 to 32 were obtained in the same manner as in Experimental Example 1 except for the formulations shown in Tables 1, 2, and 3.
The thickness of the organic heat insulating layer was 50 mm, and the thickness of the colored coating film was 0.5 mm.
A test similar to Experimental Example 1 was conducted on the obtained heat insulating laminate. The results are shown in Table 3.

Claims (5)

A heat insulating laminate in which a colored coating film is laminated on an organic heat insulating layer,
The organic heat insulating layer contains a phosphorus compound,
The phosphorus compound includes a phosphate ester and a phosphinate compound,
A heat insulating laminate, wherein the colored coating film contains a binder, a colored pigment, and a phosphorus compound having a refractive index of 1.4 or more and 1.7 or less. The heat insulating laminate according to claim 1, wherein a mixing ratio (weight ratio) of the phosphoric acid ester and the phosphinate compound is from 99:1 to 40:60. The heat insulating laminate according to claim 1, wherein the binder is an organic binder. The heat-insulating laminate according to claim 1, wherein the organic heat-insulating layer is a urethane foam formed from a polyol composition containing a polyol compound, a phosphorus compound, and a blowing agent, and a polyisocyanate compound. The heat insulating laminate according to claim 4, wherein the blending ratio of the polyol composition and the polyisocyanate compound is 200 or more and 800 or less in terms of isocyanate index.