JP2019064263A - Heat insulation laminate - Google Patents

Abstract

To provide a heat insulation laminate that is excellent in heat insulation and heat resistance as well as beauty.SOLUTION: A heat insulation laminate has a colored coating put on an organic heat insulation layer containing a phosphorus compound, the colored coating containing an organic binder, a coloring pigment, and a phosphorus compound with a specific refractive index.SELECTED DRAWING: None

Description

  The present invention relates to a heat insulating laminate.

In general, in a building structure, a heat insulating material is applied along with the flame retardant material to enhance the heat insulating performance.
As such a heat insulating material, organic heat insulating materials such as urethane foam, phenol foam, styrene foam and the like are mainly used. For example, urethane foam is widely used because of its features such as excellent heat insulation and relatively low cost of construction.
In recent years, with the improvement in the heat resistance of urethane foam, urethane foam alone can be used, and since it can be used as a surface material, further expansion of applications is expected. (For example, patent documents 1, 2 etc.)

WO 2014/112394 JP 2015-151524

  However, when such a urethane foam is adopted in a place where it can be noticed as the use is expanded, the aesthetic appearance of the surface has come to be regarded as a problem. Moreover, it may discolor by ultraviolet rays etc., and the improvement of the aesthetics of the surface is urgently required for the expansion of applications.

  As a result of intensive studies to solve the above problems, the present inventor laminated a colored coating film containing a binder, a color pigment, and a phosphorus compound having a specific refractive index on an organic thermal insulation layer containing a phosphorus compound. It has been found that the heat insulation laminate has excellent heat insulation and heat resistance as well as excellent aesthetics, and the present invention has been completed.

That is, the present invention has the following features.
1. A thermal insulation laminate in which a colored coating is laminated on an organic thermal insulation layer,
The organic thermal insulation layer contains a phosphorus compound,
The heat insulation laminate characterized in that the colored coating film contains a binder, a color pigment, and a phosphorus compound having a refractive index of 1.4 or more and 1.7 or less.
2. The binder is an organic binder 1. Thermal insulation laminate as described in.
3. The organic heat insulating layer is a urethane foam formed from a polyol composition containing a polyol compound, a phosphorus compound, and a foaming agent, and a polyisocyanate compound. Or 2. Thermal insulation laminate as described in.
4. The compounding ratio of the polyol composition and the polyisocyanate compound is 200 or more and 800 or less in the isocyanate index. Thermal insulation laminate as described in.

  The heat insulation laminate of the present invention is excellent in heat insulation, heat resistance, and aesthetics.

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

  The organic thermal insulation layer of the present invention contains a phosphorus compound, and alone has thermal insulation performance and heat resistance performance.

  Examples of the organic heat insulating layer include foamed organic resin-formed bodies such as urethane foam, phenol foam, polystyrene foam, polyethylene foam, polypropylene foam, polyvinyl chloride foam, cellulose fiber, etc. By blending the phosphorus compound, an organic thermal insulation layer having both thermal insulation performance and heat resistance performance can be obtained.

  Examples of phosphorus compounds include phosphoric acid esters, polyphosphate compounds, phosphinate compounds, halogenated phosphazenes, red phosphorus, phosphorus trichloride, phosphorus pentachloride and the like. Such a phosphorus compound is likely to form a good carbonized layer with the organic heat insulation layer component, and can obtain excellent heat resistance as well as excellent heat insulation.

Specifically, as the phosphoric acid ester, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tris nonyl phenyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl Phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, trixylenyl phosphate, diisopropyl phenyl 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, hydroxide Nonyl diphenyl phosphate, phenyl nonyl phenyl hydroquinonyl phosphate, phenyl dinonyl phenyl phosphate, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphonate, dimethyl -4-hydroxy 3,5-dibromo Examples thereof include benzyl phosphonate, diphenyl-4-hydroxy-3,5-dibromobenzyl phosphonate and the like.
Examples of polyphosphate compounds 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 ethyl methyl phosphinate, ethyl methyl phosphinate Aluminum, zinc ethyl methylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, aluminum tris (diethylphosphinate), aluminum tris (methylethylphosphinate), aluminum tris (dibutylphosphinate), tris Butylethylphosphinic acid) aluminum, tris (diphenylphosphinic acid) aluminum, bis (diethylphos acid) Zinc acid, zinc bis (methylethylphosphinate), zinc bis (diphenylphosphinate), titanyl bis (diethylphosphinate), tetrakis (diethylphosphinate) titanyl, bis (methylethylphosphinate) titanyl, tetrakis Examples thereof include methylethylphosphinic acid) titanyl, bis (diphenylphosphinic acid) titanyl, tetrakis (diphenylphosphinic acid) titanyl and the like, and one or more of these can be used.
The halogenated phosphazenes include, for example, hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene, dodecachlorocyclohexaphosphazene, hexabromocyclotriphosphazene, hexafluorocyclotriphosphazene, octafluorocyclotetraphosphazene, deca Fluorocyclopentaphosphazene, dodecafluorocyclohexaphosphazene, hexamethoxycyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, hexaphenoxycyclotriphosphazene, diethoxytetrafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, methoxypentafluorocyclotriphosphazene Phosphazene, propoxy pentaful B cyclotriphosphazene, butoxy pentafluoro Cyclotriphosphazene the like.

  In the present invention, in particular, it is preferable to use a phosphoric acid ester and a phosphinate salt compound in combination as the phosphorus compound. When the phosphate ester and the phosphinate compound are used in combination, the mixing ratio (weight ratio) of the phosphate ester: phosphinate compound ratio is 99: 1 to 40:60, and further 98: 2 to 50:50. And further preferably 97: 3 to 60:40. With such a mixing ratio, sufficient effects can be obtained in terms of foam formability, strength, heat resistance and the like.

The organic thermal insulation layer of the present invention is particularly preferably a urethane foam.
As a urethane foam, what was formed from the polyol compound, the phosphorus compound, and the polyol composition containing a foaming agent, and a polyisocyanate compound can be used.

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

Among these, as polyester polyols, for example, aromatic polyester polyols, aliphatic polyester polyols, aromatic / aliphatic polyester polyols and the like can be mentioned, and one or more of these can be used.
Specifically, an aromatic polyester polyol is 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 and a polyvalent acid. Examples thereof include condensed polyester polyols obtained by reacting with an alcohol, and phthalic acid-based polyester polyols obtained by decomposing phthalic acid-based polyester moldings such as polyethylene terephthalate. Moreover, as polyhydric alcohol, alcohol with 2 or more valences and its derivative (s), phenols with 2 or more valences, polyols etc. are mentioned, for example.
The aliphatic polyester polyol is a polyol having an aliphatic hydrocarbon in one molecule, and examples thereof include aliphatic polybasic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid and fumaric acid, A condensation polyester polyol obtained by reacting with a polyhydric alcohol can be mentioned.
An aromatic / aliphatic polyester polyol is a polyol having an aliphatic hydrocarbon and an aromatic hydrocarbon in one molecule, which is obtained by reacting an aromatic polybasic acid and an aliphatic polybasic acid with a polyhydric alcohol. Condensation polyester polyols and the like.
In the present invention, it is preferable to include a polyester polyol as the polyol compound.

  Examples of polyether polyols include aromatic polyether polyols, phosphorus-containing polyether polyols, glycerin-based polyether polyols, amino group-containing polyether polyols and the like. Specifically, as the aromatic polyether polyol, for example, a bisphenol A type polyether polyol obtained by adding an alkylene oxide (for example, ethylene oxide, propylene oxide, etc.) using bisphenol A as an initiator, an aromatic amine ( For example, by adding an alkylene oxide using toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, triethanolamine, Mannich condensation product, etc. as an initiator) The aromatic amine-type polyether polyol etc. which are obtained are mentioned. Examples of the phosphorus-containing polyether polyol include dialkyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphonate which is a diol having a phosphoric acid ester structure. Examples of glycerin-based polyether polyols include polyether polyols obtained by adding an alkylene oxide using glycerin as an initiator. Examples of the amino group-containing polyether polyol include those to which an alkylene oxide is added with 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 mg KOH / g or more and 500 mg KOH / g or less.
The hydroxyl value is a value represented by mg of potassium hydroxide equimolar to hydroxyl groups contained in 1 g of the sample, JIS K 1557-1: 2007 Plastics-polyurethane raw material polyol test method-part 1: hydroxyl value It is a value measured based on how to obtain The hydroxyl value of the polyol compound is a value measured for a mixture of all the polyol compounds.

The phosphorus compound may be used as the phosphorus compound, and the mixing amount of the polyol compound of the present invention and the phosphorus compound is preferably 10 parts by weight or more and 1000 parts by weight or less of the phosphorus compound to 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, more preferably 50 parts by weight or more and 400 parts by weight or less. If it is in such a range, it is suitable at points, such as heat resistance.
In the present invention, it is particularly preferable to use a phosphoric acid ester and / or phosphinate compound as the phosphorus compound, and the mixing amount of phosphoric acid ester is 20 parts by weight or more and 900 parts by weight or less with respect to 100 parts by weight of the polyol compound. (Preferably 40 to 600 parts by weight, more preferably 60 to 400 parts by weight) and the mixing amount of the phosphinate compound is 10 to 200 parts by weight (more preferably 20 to 150 parts by weight) It is preferable that it is a part by weight or less, more preferably 40 parts by weight or more and 120 parts by weight or less.
In the present invention, it is particularly preferable to use a phosphoric acid ester and a phosphinate compound in combination as the phosphorus compound. When the phosphate ester and the phosphinate compound are used in combination, the mixing ratio (weight ratio) of the phosphate ester: phosphinate compound ratio is 99: 1 to 40:60, and further 98: 2 to 50:50. And further preferably 97: 3 to 60:40. With such a mixing ratio, sufficient effects can be obtained in terms of foam formability, strength, heat resistance and the like.

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

  Among them, examples of the hydrocarbon include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like. As the hydrochlorofluorocarbon (HCFC), for example, 1,1-dichloro-1-fluoroethane (HCFC-141B), 1-chloro-1,1-difluoroethane (HCFC-142B), chlorodifluoromethane (HCFC-22) Etc. As the hydrofluorocarbon (HFC), for example, difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,1-trifluoroethane (HFC143a), 1,1, 2,2-tetrafluoroethane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), 1,1,1,2,3,3,3-hepta Fluoropropane (HFC 227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluorobutane (HFC 365mfc), 1,1,1,2,2,2, 3,4,5,5,5-decafluoropentane (HFC 4310 mee) and the like.

As hydrofluoroolefin (HFO), for example, pentafluoropropene such as 1,2,3,3,3-pentafluoropropene (HFO 1225ye), 1,3,3,3-tetrafluoropropene (HFO1234ze), 2,2,3 Tetrafluoropropenes such as 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 (H) O1438), nonafluorobutyl pentene (HFO1429), etc., or their isomers (cis isomer, and trans form) and the like. Examples of the hydrochlorofluoroolefin (HCFO) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), Dichlorotrifluoropropene (HCFO 1223) and the like, or isomers thereof (cis form, trans form) and the like can be mentioned.
The foaming agent in the present invention is preferably one or more selected from hydrofluoroolefins, hydrochlorofluoroolefins, and water. For example, hydrofluoroolefins and water, hydrochlorofluoroolefins and water, hydrofluoroolefins and the like Each foaming agent such as hydrochlorofluoroolefin and water can be used in combination.

  The amount of the foaming agent mixed 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, still 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.

  The polyisocyanate compound is not particularly limited. For example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI (c-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, cost advantage and the like. As MDI, for example, monomeric MDI, polymeric MDI (polymethylene polyphenyl isocyanate) and the like can be mentioned.

  The compounding 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 said polyol composition, the said polyisocyanate compound, etc. so that it may become. If the isocyanate index is in such a range, it is preferable in terms of heat resistance and the like. The isocyanate index is represented by 100 times the value obtained by dividing the number of equivalents of the isocyanate group of the polyisocyanate compound by the total number of equivalents of active hydrogen of the active hydrogen-containing component (polyol compound, water, etc.). is there.

  The polyol composition can also contain an ethylenically unsaturated double bond-containing compound in addition to the components described above. The use of the ethylenically unsaturated double bond-containing compound makes it possible to more efficiently obtain the heat resistance and other effects of the phosphorus compound. Examples of the ethylenically unsaturated double bond include (meth) acryloyl group, allyl group, propenyl group and the like.

  As the ethylenically unsaturated double bond-containing compound, in view of the above-mentioned effects and the like, one having an ethylenic unsaturated double bond concentration in one molecule of 0.5 mmol / g or more and 20 mmol / g is preferable, and 5 mmol / g It is more preferable that it is 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 the molecular weight. It is represented by 1000 times (mmol / g) of the value divided by.

  Specific examples of the ethylenically unsaturated double bond-containing compound include, for example, polyhydric alcohols (for example, alcohols having a valence of 2 or more and derivatives thereof, phenols having a valence of 2 or more, polyols etc.) and unsaturated carboxylic acids (( Reactants with (meth) acrylic acid, etc., Reactants with amines (eg, divalent or higher amines, alkanolamines, etc.) and unsaturated carboxylic acids, unsaturated carboxylic acid thioesters of thiols or unsaturated alkyl thioethers, Examples thereof include bisphenol A (meth) acrylate compounds, reaction products of glycidyl group-containing compounds and unsaturated carboxylic acids, (meth) acrylate compounds having a urethane bond in the molecule, and nonylphenoxypolyethylene oxyacrylate. These can be used alone or in combination of two or more.

  Among these, as a reaction product of polyhydric alcohol and unsaturated carboxylic acid, for example, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta ( Meta) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, ditritriol Methylolpropane tetra (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene / poly B propylene glycol di (meth) acrylate, alkylene oxide modified trimethylolpropane tri (meth) acrylate.

  Examples of the above-mentioned bisphenol A (meth) acrylate compounds include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypoly). Propoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane and the like Can be mentioned.

  As the (meth) acrylate compound having a urethane bond in the molecule, an addition reaction product of a hydroxyl group-containing (meth) acrylic monomer and a diisocyanate compound, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, alkylene Oxide modified urethane di (meth) acrylate etc. are mentioned.

  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, more preferably 10 parts by weight with respect to 100 parts by weight of the polyol compound. It is 80 parts by weight or less by weight. When a plurality of hydroxyl groups are contained in the ethylenically unsaturated double bond-containing compound, it is regarded as a polyol compound. In addition, the isocyanate index is calculated in consideration of the active hydrogen-containing component contained in the ethylenically unsaturated double bond-containing compound.

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

  Examples of flame retardants other than the above include halogen flame retardants, organic bromine flame retardants, nitrogen flame retardants, metal hydrate flame retardants, antimony flame retardants, boron flame retardants, silicon flame retardants, etc. It can be mentioned.

Although it does not specifically limit as a catalyst, For example, a nuration catalyst, a resinification catalyst, a foaming catalyst etc. are mentioned, 1 type (s) or 2 or more types of these can be used.
The nuration catalyst is not particularly limited as long as it is a catalyst effective for isocyanuration, and, for example, a hydroxide of tetraalkylammonium such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, trimethylbenzylammonium or the organic acid thereof Salts (as organic acid, for example, acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, lactic acid etc.), trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium , Hydroxides of trialkyl hydroxyalkyl ammonium such as triethyl hydroxyethyl ammonium or organic acid salts thereof (as organic acid, for example, acetic acid, capron Acids (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, lactic acid etc., alkyl carboxylic acids (eg acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid) ), Metal salts of myristic acid, lactic acid, etc., metal chelate compounds of β-diketones such as aluminum acetylacetone, lithium acetylacetone etc., Friedel-Crafts catalysts such as aluminum chloride, boron trifluoride, etc., titanium tetrabutylate, tributylantimony oxide Organic metal compounds such as organic compounds, and aminosilyl group-containing compounds such as hexamethyl silazane etc., and one or more of these can be used.

  As a resinification catalyst, for example, 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' A tertiary amine such as '-pentamethyldipropylene triamine, N, N, N', N'-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine or the like Organic acid salt, bismuth tris (2-ethylhexanoate), bismuth tris (neodecanoate), bismuth tris (palmitate), bis Organometals such as tetratetramethylheptanedioate, bismuth octylate, bismuth naphthenate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, dioctyltin diacetate, tin octylate, 1-methylimidazole, 2-methylimidazole, Imidazole such as 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- (dimethyl) Amino) propyl Imino) bis (2-propanol) and the like, one or two or more of these can be used.

  As a foaming catalyst, for example, N, N, N ′, N ′, N ′ ′-pentamethyldiethylene triamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ′, N ′ ′- Pentamethyldipropylenetriamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethoxyethanol, N, N, N ′, N ′ ′, N ′ ′, N ′ ′ ′, N ′ ′ ′-hexamethyl Triethylenetetramine, N, N, N ′, N ′ ′-Tetramethyl-N ′ ′-(2-hydroxyethyl) triethylenediamine, N, N, N ′, N ′ ′-Tetramethyl- (2-hydroxypropyl) And 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 to 50 parts by weight, more preferably 0.5 to 45 parts by weight, and still more preferably 1 to 40 parts by weight with respect to 100 parts by weight of the polyol compound. Part or less. When the catalyst contains an active hydrogen-containing component, the isocyanate index is calculated in consideration of the active hydrogen-containing component contained in the catalyst.
In the present invention, in particular, it is preferable to include a resinification catalyst and / or a foaming catalyst together with the nuration catalyst, which is advantageous to the formability as well as the workability. 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, and fluorine-containing compound foam stabilizers. These can be used alone or in combination of two or more. Examples of polyether-modified silicone compounds include graft copolymers of polydimethylsiloxane with polyoxyethylene glycol or polyoxyethylene-propylene glycol, and the like.
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 with respect to 100 parts by weight of the polyol compound.

  As a polymerization inhibitor, a hydroquinone type polymerization inhibitor, a benzoquinone type polymerization inhibitor, a catechol type polymerization inhibitor, a piperidine type polymerization inhibitor etc. are mentioned, for example. Such a polymerization inhibitor imparts long-term storage stability in the form of a two-pack type described later, and contributes to the production stability when it is added in 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 impart workability, foam formability, dimensional stability, and the like. In the present invention, fibers may not be used, but when fibers are mixed, the effect can be exhibited with a small amount of fibers.

  As surfactant, nonionic surfactant, anionic surfactant, cationic surfactant etc. are mentioned, for example. Such surfactants can impart storage stability and dispersion stability.

  The colored coating film of the present invention contains a binder, a coloring pigment, and a phosphorus compound having a refractive index of 1.4 or more and 1.7 or less, and maintains adhesion while maintaining the heat insulation and heat resistance of the heat insulation laminate. Can enhance the aesthetics of the surface.

As a binder, an organic binder, an inorganic binder, etc. are mentioned.
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, epoxy Resin, urethane resin, polyester resin, phenol resin, petroleum resin, vinyl chloride resin, epoxy resin, urethane resin, polybutadiene resin, alkyd resin, melamine resin, propylene rubber, chloroprene rubber, butyl rubber, isobutylene rubber, etc., as an inorganic binder And silicon resins, glass, water glass and the like, and one or more of these may be used in combination. The refractive index of the binder is preferably 1.4 or more and 1.7 or less.
The form is not particularly limited, for example, a water-soluble resin, a water-dispersible resin (resin emulsion), a powder resin (re-emulsion type emulsion), and in the present invention, a water-dispersible resin (resin emulsion) is particularly preferable.
In the present invention, it is particularly preferable to use an organic binder, and as the organic binder, it is particularly preferred to use a vinyl chloride resin and / or an acrylic styrene resin, and further, a vinyl chloride resin and an acrylic styrene resin.

The color pigment is not particularly limited, and, for example, titanium oxide, zinc oxide, carbon black, graphite, black iron oxide, copper chromium black, cobalt black, copper manganese iron black, ferric oxide (red iron oxide), lead chromate (Molybdate orange), permanent red, permanent carmine, yellow lead, yellow iron oxide, titanium yellow, chromium green, cobalt green, ultra blue, bitumen, cobalt blue inorganic pigments, azo, naphthol, pyrazolone, anthraquinone, Organic coloring pigments such as perylenes, quinacridones, disazos, isoindolinones, benzimidazoles, phthalocyanines, quinophthalones, dioxazines, pearl pigments, fluorescent pigments, phosphorescent pigments, metallic pigments, etc. Is used in one or more kinds Kill. The color tone of the colored coating film can be appropriately set by adjusting the type, mixing amount, and the like of such a color pigment.
The blending amount of the color 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 is a phosphorus compound having 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 with the binder, and has the effect of not inhibiting the color tone of the color 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 together with the aesthetic appearance.
The phosphorus compound used in the colored coating is not particularly limited as long as it has a refractive index of 1.4 or more and 1.7 or less, and the above-mentioned phosphate ester, polyphosphate compound, phosphinate compound, halogenated phosphazene, red phosphorus One or two or more kinds of phosphorus compounds such as phosphorus trichloride and phosphorus pentachloride can be used. In particular, in the present invention, it is preferable to use a polyphosphate compound such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melem polyphosphate, melam polyphosphate, melon polyphosphate and the like.
The refractive index is a value measured by an Abbe refractometer according to JIS K 0062.

  The compounding 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 more preferably 150 parts by weight or more and 600 parts by weight or less.

  The colored coating film of the present invention is, in addition to the above components, an extender pigment such as calcium carbonate, clay, kaolin, talc, precipitated barium sulfate, barium carbonate, white carbon, diatomaceous earth to the extent that the effect of the present invention is not impaired. Mineral aggregate such as silica sand, cold water stone, mineral lightweight aggregate such as perlite, expanded vermiculite, aluminum hydroxide, magnesium hydroxide, zeolite, endothermic material such as halloysite, allophane, ettringite, melamine, dicyandiamide, azodicarbonamide And other foaming agents, carbonized agents such as pentaerythritol and dipentaerythritol, flame retardants, fibers, reinforcements, plasticizers, preservatives, fungicides, antifoams, antifoaming agents, thickeners, leveling agents, water reducing agents, pigment dispersions It may also contain an agent, an anti-settling agent, an anti-sagging agent, an ultraviolet light absorber, an antioxidant and the like.

The heat insulation laminate of the present invention can be used as a building material, for example, it can be suitably used as a surface material by being laminated on a substrate.
For example, when using as a surface material, as a base material which can be applied, for example, color steel plate, galvanium steel plate, polyvinyl chloride steel plate, stainless steel plate, aluminum plate, copper plate, titanium plate, aluminum plated steel plate, galvanized steel plate, clad steel plate, sandwich A steel plate, concrete, mortar, porcelain tile, fiber mixed cement board, cement calcium silicate board, slag cement perlite board, ALC board, siding board, extrusion molded board, gypsum board, plywood, plastic board, heat insulation board etc. are mentioned.

  When laminating a heat insulation laminated body with respect to such a base material, the heat insulation laminated body by which the colored coating film was laminated | stacked previously on the organic heat insulation layer is produced beforehand, The method of sticking this heat insulation laminated body to a base material Or a method of directly coating a component forming an organic thermal insulation layer on a substrate, forming an organic thermal insulation layer on the substrate, and thereafter laminating a material forming a colored coating film on the organic thermal insulation layer Be

  For example, in the case of urethane foam, the method of obtaining the organic heat insulating layer is preferably in the form of a two-pack type at the time of circulation, and mixed and used at the time of use (at the time of foam layer formation). In such a two-component form, for example, the first liquid may be a polyol compound, a phosphorus compound, a polyol composition containing a foaming agent, and the second liquid may be 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 of the first liquid, handling property, and workability when forming a foam. It is s or less, more preferably 50 mPa · s or more and 250 mPa · s or less. The viscosity is the viscosity at 20 rpm measured at a temperature of 20 ° C. with a BH-type viscometer (the indicator value at the fourth rotation). With such viscosity, it is possible to set the first liquid to a relatively low viscosity while sufficiently securing the storage stability of the first liquid. Thereby, the stirring operation at the time of construction is reduced, and advantageous effects can be obtained also in the handling property, the construction property, the miscibility with the polyisocyanate compound, and the like.
The viscosity of the second liquid is preferably 20 mPa · s to 500 mPa · s, more preferably 30 mPa · s to 350 mPa · s, and still more preferably 50 mPa · s to 250 mPa · s.

When the urethane foam is applied to the substrate, for example, a spray foamer for spraying work (for example, a two-component tip mixed type spray coater or the like) is used to mix the first liquid and the first liquid. It is sufficient to spray a mixture of the two solutions. In this case, it is preferable to set the temperature 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. The first and second liquids thus set at a predetermined temperature are mixed at the spray tip and sprayed toward the substrate to form a foam on the substrate. As a spraying environment, Preferably it can install at 5 degreeC or more and 45 degrees C or less.
It is desirable that the mixing of the first liquid and the second liquid be about 1: 1 in volume ratio. The foam layer formed by such a method can exhibit excellent performance in low thermal conductivity, heat resistance and the like. The thickness of the foam layer is not particularly limited and may be appropriately set according to the required performance etc., but is preferably 10 mm or more, and more preferably about 15 to 500 mm. In addition, such construction can be performed without particular limitation, such as new construction and repair.

In the method of laminating a colored coating film on the surface (surface) of the organic thermal insulation layer, a material (a binder, a coloring pigment, and a phosphorus compound having a refractive index of 1.4 or more and 1.7 or less) for forming a colored coating film is included. A colored film can be formed by applying a colored film-forming material), drying and curing. Under the present circumstances, water etc. can be mixed with a colored coating film formation material as needed.
It is desirable to apply the colored film-forming material directly onto the organic thermal insulation layer. At the time of application of the colored coating film-forming material, coating tools such as iron, spray, roller and brush can be appropriately used, and application can be performed once or plural times.
The thickness of the colored coating film to be formed may be appropriately set according to the application site, application, required performance and the like, 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. Moreover, two or more types of colored coating films can also be formed.

  The following examples are provided to further clarify the features of the present invention.

As a first liquid, a polyol composition in which the following raw materials were uniformly mixed at a weight ratio shown in Table 1 was prepared. In Table 1, the amount of the active ingredient is described for the catalyst.
Moreover, what mixed the following raw material uniformly by the weight ratio shown in Table 2 was prepared as a coloring film formation material.
Polyol compound 1: Aromatic polyester polyol (terephthalic acid polyester polyol, hydroxyl value: 250 mg KOH / g)
Polyol compound 2: Aliphatic polyester polyol (succinic acid polyester polyol, hydroxyl value: 100 mg KOH / g)
Polyol compound 3: aromatic polyether polyol (Mannich modified polyether polyol, hydroxyl value: 350 mg KOH / g)
Phosphorus compound 1: alkylated phosphinate compound (aluminum tris (diethylphosphinate), density 1.35 g / cm ³ , refractive index 1.5)
Phosphorus compound 2: phosphoric 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: 6233 mg KOH / g)
Catalyst 1: Nuration catalyst (ethylene glycol solution of tetraalkyl ammonium organic acid salt, 50% by weight of active ingredient, hydroxyl value: 900 mg KOH / g)
・ Catalyst 2: Resinification catalyst (imidazole-based catalyst (100% by weight of active ingredient))
・ Catalyst 3: Resinification catalyst (bismuth octylate in octylic acid solution)
· Double bond compound 1: compound having ethylenic unsaturated double bond (trimethylolpropane triacrylate, concentration of ethylenic unsaturated double bond: 10 mmol / g, hydroxyl value: 0 mg KOH / g)
Double bond compound 2: compound containing ethylenic unsaturated double bond (pentaerythritol tetraacrylate, concentration of ethylenic unsaturated double bond: 11 mmol / g, hydroxyl value: 0 mg KOH / g)
Double bond compound 3: compound containing ethylenic unsaturated double bond (pentaerythritol triacrylate, concentration of ethylenic unsaturated double bond: 10 mmol / g, hydroxyl value: 25 mg KOH / g)
-Foam control agent: silicone type foam control agent-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)
Color pigment 2: Carbon black Color pigment 3: ferric oxide Blowing agent 4: Melamine Carbonizing agent 1: Pentaerythritol Carbonizing agent 2: Chlorinated paraffin Additive: Glass fiber, calcium carbonate

(Experimental example 1)
Spray a mixed solution prepared by mixing the polyol composition (first liquid) and the polyisocyanate compound (second liquid) prepared in the formulation shown in Table 1 with an isocyanate index shown in Table 3 onto a galvanized steel sheet, It was foamed to form an organic thermal insulation layer.
The resulting organic thermal insulation layer is allowed to stand at normal temperature (temperature 23 ° C., relative humidity 50%) for 24 hours, and then the colored film-forming material prepared by the composition shown in Table 2 is coated with a roller at normal temperature To obtain a test body 1 (adiabatic laminate).
The thickness of the organic thermal insulation layer was 50 mm, and the thickness of the colored coating film was 0.5 mm.
The following test was performed about the obtained heat insulation laminated body. The results are shown in Table 3.

(Examination 1) Aesthetic test The surface of (2) was visually observed and evaluated immediately after obtaining the test body (1) and after 1 week of outdoor exposure (Tochigi city, 45 degrees south). Evaluation is as follows.
◎: had excellent aesthetics.
○: Discoloration was hardly found and had good aesthetics.
X: 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. Evaluation criteria are as follows.
○: Thermal conductivity is 0.03 W / (m · K) or less ×: Thermal conductivity is 0.03 W / (m · K)

(Test 3) Heat resistance test It was carried out using a corn calorimeter specified in ISO 5660. The heating strength was 50 kW / m ² , and the heating time was 5 minutes, 10 minutes, and 20 minutes, respectively. The evaluation items and evaluation criteria are as follows.

(Evaluation item)
(3-1) Dimensional change ◎: The dimensional change in the thickness direction of the organic thermal insulating layer after the test is 10 mm or less ○: The dimensional change in the thickness direction of the organic thermal insulating layer after the test is 10 mm to 20 mm or less ×: Organic thermal insulation after the test The dimensional change of the layer in the thickness direction is more than 20 mm (3-2) the total calorific value ○: the total calorific value is 8 MJ / m ² or less ×: the total calorific value is more than 8 MJ / m ² (3-3) Maximum heating rate is 200 kW / m ² or less ×: Maximum heating rate is more than 200 kW / m ²

(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 │ x │ x │ x │
With regard to heat resistance, excellent A> A ′>B> B ′>C> C ′> D is inferior.

(Experimental example 2-32)
Test bodies 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 thermal insulation layer was 50 mm, and the thickness of the colored coating film was 0.5 mm.
About the obtained heat insulation laminated body, the test similar to Experimental example 1 was done. The results are shown in Table 3.

Claims (4)

A thermal insulation laminate in which a colored coating is laminated on an organic thermal insulation layer,
The organic thermal insulation layer contains a phosphorus compound,
The heat insulation laminate characterized in that the colored coating film contains a binder, a color pigment, and a phosphorus compound having a refractive index of 1.4 or more and 1.7 or less.   The heat insulation laminate according to claim 1, wherein the binder is an organic binder.   The said organic thermal insulation layer is a urethane foam formed from the polyol composition containing a polyol compound, a phosphorus compound, and a foaming agent, and a polyisocyanate compound, The said claim | item 1 or 2 characterized by the above-mentioned. Thermal insulation laminate. The heat insulation laminate according to claim 3, wherein a blending ratio of the polyol composition and the polyisocyanate compound is 200 or more and 800 or less in terms of isocyanate index.