JP2024086922A - Laminate - Google Patents

Abstract

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

Description

The laminate of the present invention can form a foam that has excellent heat insulation and heat resistance as well as excellent aesthetics.

In general, in building structures, heat insulating materials are used in addition to fire retardant materials to improve heat insulating performance.
As such heat insulating materials, organic heat insulating materials such as urethane foam, phenol foam, styrene foam, etc. For example, urethane foam is widely used because of its characteristics such as excellent heat insulating properties and relatively low cost application.
In recent years, with the improvement in the heat resistance of urethane foam, it has become possible to use urethane foam alone, and also as a surface material, and further expansion of its applications is expected (for example, Patent Documents 1 and 2, etc.).

WO2014/112394 Patent Publication 2015-151524

However, as the uses of this type of urethane foam expand and it is being used in places where it is visible to the public, the aesthetic appearance of the surface has become an issue, and improving the aesthetic appearance of the surface is an urgent task in order to expand its uses.

As a result of extensive research into solving the above problems, the inventors discovered that by laminating a colored coating film containing a specific binder and colorant on top of urethane foam, it is possible to obtain a laminate that has excellent adhesion between the urethane foam and the colored coating film, can maintain its aesthetic appearance for a long period of time, and has excellent insulation and heat resistance, leading to the completion of the present invention.

That is, the present invention has the following features.
1. A laminate in which a colored coating film is laminated on a urethane foam,
The urethane foam is formed from a polyol compound, a blowing agent, a catalyst, a polyisocyanate compound, and a flame retardant;
The color coating comprises a binder and a colorant;
the binder is a synthetic resin emulsion of an acrylic resin or an acrylic-styrene copolymer resin having a glass transition temperature of 0° C. or lower,
The colorant is contained in the colored coating film in an amount of 98 parts by weight to 500 parts by weight per 100 parts by weight of the solid content of the binder .
2. The laminate according to 1., wherein the flame retardant comprises at least one selected from the group consisting of cyclic phosphate esters, phosphinate compounds, phosphoramidates, and cyclic phosphoramidates.
3. The laminate according to 1., wherein the binder is a synthetic resin emulsion of an acrylic resin or an acrylic-styrene copolymer resin having a glass transition temperature of -30°C or higher and -5°C or lower.

The laminate of the present invention has excellent heat insulation and heat resistance, and can maintain its aesthetic appearance for a long period of time.

The following describes how to implement the present invention.

The laminate of the present invention is a colored coating film laminated on top of a urethane foam.

The urethane foam used is, for example, made from a polyol compound, a blowing agent, a catalyst, and a polyisocyanate compound, and contains a flame retardant to impart heat resistance.

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

Among these, examples of the polyester polyol include aromatic polyester polyols, aliphatic polyester polyols, and aromatic/aliphatic polyester polyols, and one or more of these can be used.
Specifically, aromatic polyester polyol refers to a polyol having an aromatic hydrocarbon in one molecule, and examples thereof include condensed polyester polyols obtained by reacting an aromatic polybasic acid such as orthophthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, etc. with a polyhydric alcohol, and phthalic acid-based polyester polyols obtained by decomposing a phthalic acid-based polyester molded product such as polyethylene terephthalate, etc. In addition, examples of polyhydric alcohols include dihydric or higher alcohols and derivatives thereof, dihydric or higher phenols, polyols, etc.
Aliphatic polyester polyols are polyols having an aliphatic hydrocarbon in one molecule, and examples thereof include condensation polyester polyols obtained by reacting an aliphatic polybasic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, or fumaric acid with a polyhydric alcohol.
The aromatic/aliphatic polyester polyol is a polyol having an aliphatic hydrocarbon and an aromatic hydrocarbon in one molecule, and examples thereof include condensation polyester polyols obtained by reacting an aromatic polybasic acid or an aliphatic polybasic acid with a polyhydric alcohol.
In the present invention, it is preferable that the polyol compound contains a polyester polyol.

Examples of polyether polyols include aromatic polyether polyols, phosphorus-containing polyether polyols, glycerin-based polyether polyols, and amino group-containing polyether polyols. Specifically, examples of aromatic polyether polyols include bisphenol A-type polyether polyols obtained by adding alkylene oxides (e.g., ethylene oxide, propylene oxide, etc.) to bisphenol A as an initiator, and aromatic amine-based polyether polyols obtained by adding alkylene oxides to aromatic amines (e.g., toluene diamine, diethyl toluene diamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, triethanolamine, Mannich condensation products, etc.) as initiators. Examples of phosphorus-containing polyether polyols include dialkyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate, which is a diol having a phosphoric acid ester structure. Examples of glycerin-based polyether polyols include polyether polyols obtained by adding alkylene oxides to glycerin as an initiator. Examples of amino group-containing polyether polyols include those obtained by adding alkylene oxide to a low molecular weight amine (e.g., ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, etc.) as an initiator.

The hydroxyl value of the polyol compound in the present invention is not particularly limited, but is preferably from 50 mgKOH/g to 500 mgKOH/g.
The hydroxyl value is a value expressed in mg of potassium hydroxide equivalent to the moles of hydroxyl groups contained in 1 g of sample, and is a value measured based on JIS K 1557-1:2007 Plastics - Test method for polyurethane raw material polyols - Part 1: Determination of hydroxyl value. The hydroxyl value of a polyol compound is a value measured for a mixture of all polyol compounds.

Examples of foaming agents include hydrocarbons, hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, water, liquefied carbon dioxide gas, etc., 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, etc. Examples of hydrochlorofluorocarbons (HCFCs) include 1,1-dichloro-1-fluoroethane (HCFC-141B), 1-chloro-1,1-difluoroethane (HCFC-142B), 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-heptafluoropropane (HFC227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluorobutane (HFC365mfc), 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC4310mee), and the like.

Examples of hydrofluoroolefins (HFOs) include pentafluoropropenes such as 1,2,3,3,3-pentafluoropropene (HFO1225ye), tetrafluoropropenes such as 1,3,3,3-tetrafluoropropene (HFO1234ze), 2,3,3,3-tetrafluoropropene (HFO1234yf), and 1,2,3,3-tetrafluoropropene (HFO1234ye), and 3,3,3-trifluoropropene ( Examples of the hydrochlorofluoroolefins (HCFOs) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), dichlorotrifluoropropene (HCFO1223), and the like, and the like, and the like, trifluoropropenes such as tetrafluorobutene (HFO1345), pentafluorobutene (HFO1354), hexafluorobutene (HFO1336), heptafluorobutene (HFO1327), heptafluoropentene (HFO1447), octafluoropentene (HFO1438), nonafluoropentene (HFO1429), and the like, and the like, and the like, and the like, and the like, and the like, and the like, and the like, and the like, and the like, and the like, and the like, and the like, and the like, and the like, and the like, and the like,
The blowing agent in the present invention is preferably one or more selected from hydrofluoroolefins, hydrochlorofluoroolefins, and water. For example, each blowing agent can be used in combination, such as hydrofluoroolefin and water, hydrochlorofluoroolefin and water, or hydrofluoroolefin, hydrochlorofluoroolefin and water.

The amount of the blowing 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, and even more preferably 30 parts by weight or more and 150 parts by weight or less, relative to 100 parts by weight of the polyol compound. Furthermore, when hydrofluoroolefin and/or hydrochlorofluoroolefin and water are contained as the blowing agent, the mixing ratio (weight ratio) of the hydrofluoroolefin and/or hydrochlorofluoroolefin to water is preferably 100:0.5 to 100:5 (or more preferably 100:0.8 to 100:4). By being in such a range, it is possible to obtain a foam having excellent low thermal conductivity, heat resistance, and further excellent strength.

The catalyst is not particularly limited, but examples include nurate catalysts, resinification catalysts, and foaming catalysts, and one or more of these can be used.

The isocyanuration catalyst is not particularly limited as long as it is an effective catalyst for isocyanuration, and examples thereof include tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, and trimethylbenzylammonium, or organic acid salts thereof (organic acids include, for example, acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, and lactic acid), trialkylhydroxyalkylammonium hydroxides such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, and triethylhydroxyethylammonium. oxides or their organic acid salts (organic acids include, for example, acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, lactic acid, etc.), metal salts of alkyl carboxylic acids (for example, acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, lactic acid, etc.), metal chelate compounds of β-diketones such as aluminum acetylacetone and lithium acetylacetone, Friedel-Crafts catalysts such as aluminum chloride and boron trifluoride, organometallic compounds such as titanium tetrabutylate and tributylantimony oxide, and aminosilyl group-containing compounds such as hexamethylsilazane, and one or more of these can be used.

Examples of resinification catalysts include tertiary amines or organic acid salts thereof such as triethylenediamine (TEDA), triethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'',N''-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N'',N''-pentamethyldipropylenetriamine, N,N,N',N''-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, bismuth tris(2-ethylhexanoate), bismuth tris(neodecanoate), bismuth tris(palmitate), bismuth tetramethylheptanedioate, octyl Examples of suitable organic compounds include bismuth acid, bismuth naphthenate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, dioctyltin diacetate, and tin octylate; imidazoles such as 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, and 1-isobutyl-2-methylimidazole; and N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, N-methylpiperazine, N-methylmorpholine, N-ethylmorpholine, 1,8-diazabicyclo[5.4.0]undecene-7, and 1,1'-(3-(dimethylamino)propyl)imino)bis(2-propanol). One or more of these compounds may be used.

Examples of foaming catalysts include tertiary amines or organic acid salts such as N,N,N',N',N''-pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl)ether, N,N,N',N',N''-pentamethyldipropylenetriamine, N,N-dimethylaminoethoxyethanol, N,N,N'-trimethylaminoethoxyethanol, N,N,N',N'',N''',N''-hexamethyltriethylenetetramine, N,N,N',N''-tetramethyl-N''-(2-hydroxyethyl)triethylenediamine, and N,N,N',N''-tetramethyl-(2-hydroxypropyl)triethylenediamine, and one or more of these can be used.

The amount of the catalyst mixed 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 48 parts by weight or less, still more preferably 1 part by weight or more and 45 parts by weight or less, and most preferably 3 parts by weight or more and 40 parts by weight or less, relative to 100 parts by weight of the polyol compound. When the catalyst contains an active hydrogen-containing component, the isocyanate index is calculated taking into account the active hydrogen-containing component contained in the catalyst.
In the present invention, it is particularly preferable to contain a resinification catalyst and/or a foaming catalyst together with the nurate catalyst, which is advantageous in terms of workability as well as foam formability, etc. When the catalyst contains an active hydrogen-containing component, the isocyanate index is calculated taking into account the active hydrogen-containing component contained in the catalyst.

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

Specific examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, trisnonylphenyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, trixylenyl phosphate, diisopropyl phenyl phosphate, tris(2-ethylhexyl)phosphate, resorcinol bisdiphenyl phosphate, bisphenol A bis(diphenyl phosphate), resorcinol bisdixylenyl phosphate, tris(chloroethyl ) phosphate, tris(chloropropyl)phosphate, tris(dichloropropyl)phosphate, bis(2,3-dibromopropyl)-2,3-dichloropropyl phosphate, tris(2,3-dibromopropyl)phosphate, bis(chloropropyl)monoctyl phosphate, hydroquinonyl 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-dibromobenzyl phosphonate, diphenyl-4-hydroxy-3,5-dibromobenzyl phosphonate, etc.

Examples of cyclic phosphate esters include 3,9-bis(phenylmethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2-methylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((3-methylphenyl)methyl) )-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((4-methylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4-dimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3, 9-diphosphaspiro[5.5]undecane, 3,9-bis((2,6-dimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((3,5-dimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bi Bis((2,4,6-trimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2-sec-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((4-sec-butylphenyl)methyl)-3 ,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4-di-sec-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,6-di-sec-butylphenyl)methyl)-3,9-dioxo-2,4,8,10 -Tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4,6-tri-sec-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphospha Spiro[5.5]undecane, 3,9-bis((4-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4-di-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9- Bis((2,6-di-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4,6-tri-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((4-biphenyl) 3,9-bis((1-naphthyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((1-naphthyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2-naphthyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphospha phosphaspiro[5.5]undecane, 3,9-bis((1-anthryl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2-anthryl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((9-anthryl)methyl)- 3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(1-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2-methyl-2-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-bis(diphenylmethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(triphenylmethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-phenylmethyl-9-((2,6-dimethylphenyl)methyl)- 3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-phenylmethyl-9-((2,4-di-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-phenylmethyl-9-(1-phenylethyl)-3,9-dioxo-2,4,8,1 0-Tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-phenylmethyl-9-diphenylmethyl-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-((2,6-dimethylphenyl)methyl)-9-(1-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[ 5.5]undecane, 3-((2,4-di-tert-butylphenyl)methyl)-9-(1-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-diphenylmethyl-9-(1-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3 -Diphenylmethyl-9-((2,6-dimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-diphenylmethyl-9-((2,4-di-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, etc.

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 ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, aluminum tris(diethylphosphinate), aluminum tris(methylethylphosphinate), tris(dibutylphosphinate), Examples of the phosphinic acid include aluminum tris(butylethylphosphinic acid), aluminum tris(diphenylphosphinic acid), zinc bis(diethylphosphinic acid), zinc bis(methylethylphosphinic acid), zinc bis(diphenylphosphinic acid), titanyl bis(diethylphosphinic acid), titanyl tetrakis(diethylphosphinic acid), titanyl bis(methylethylphosphinic acid), titanyl tetrakis(methylethylphosphinic acid), titanyl bis(diphenylphosphinic acid), titanyl tetrakis(diphenylphosphinic acid), and the like. One or more of these may be used.

Examples of halogenated phosphazenes include hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene, dodecachlorocyclohexaphosphazene, hexabromocyclotriphosphazene, hexafluorocyclotriphosphazene, octafluorocyclotetraphosphazene, decafluorocyclopentaphosphazene, dodecafluorocyclohexaphosphazene, hexamethoxycyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, hexaphenoxycyclotriphosphazene, diethoxytetrafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, methoxypentafluorocyclotriphosphazene, propoxypentafluorocyclotriphosphazene, butoxypentafluorocyclotriphosphazene, etc.

Examples of phosphoramidates include compounds represented by formula 1 or 2.
(Equation 1)
O-R1
│
O=P-N(R2) ₂
│
O-R1
(Equation 2)
O-R1 O-R1
│ │
O=P-N(R2)-R3-(R2)N-P=O
│ │
O-R1 O-R1
R1 may be the same or different and is an alkyl group having 1 to 12 carbon atoms; R2 may be the same or different and is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R3 is an alkylene group having 1 to 12 carbon atoms; and N(R2) ₂ and N(R2)-R3-(R2)N may be a nitrogen-containing heterocyclic structure.

Examples of the cyclic phosphoramidate include compounds represented by formula 3 or 4.
(Equation 3)
R2 R1-O
\ / \
C P = O
／ ＼ ／ ＼
R2 R1-ON (R3) ₂
(Equation 4)
R2 R1-O O-R1 R2
＼ ／ ＼ ／ ＼ ／
C P = O O = P C
／ ＼ ／ ＼ ／ ＼ ／ ＼
R2 R1-O N(R3)-R4-(R3)N O-R1 R2
R1 may be the same or different and is an alkylene group having 1 to 3 carbon atoms; R2 may be the same or different and is an alkyl group having 1 to 12 carbon atoms; R3 may be the same or different and is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; R4 may be an alkylene group having 1 to 12 carbon atoms; and N(R3) ₂ and N(R3)-R4-(R3)N may be a nitrogen-containing heterocyclic structure.

In the present invention, the amount of the flame retardant mixed is preferably 1 part by weight or more and 1,000 parts by weight or less, more preferably 5 parts by weight or more and 600 parts by weight or less, and even more preferably 10 parts by weight or more and 400 parts by weight or less, based on 100 parts by weight of the polyol compound.
In the present invention, it is preferable that the flame retardant contains one or more selected from a cyclic phosphate ester, a phosphinate compound, a phosphoramidate, and a cyclic phosphoramidate, and further contains one or more selected from a phosphinate compound and a cyclic phosphoramidate, which can provide excellent workability and further improve heat resistance.
In particular, when a phosphinic acid salt compound is included, in the present invention, it is preferable to use a phosphate ester and a phosphinic acid salt compound in combination. When a phosphate ester and a phosphinic acid salt compound are used in combination, the phosphate ester is 30 parts by weight or more and 900 parts by weight or less (preferably 40 parts by weight or more and 600 parts by weight or less, more preferably 50 parts by weight or more and 400 parts by weight or less), and the phosphinic acid salt compound is 10 parts by weight or more and 200 parts by weight or less (more preferably 20 parts by weight or more and 120 parts by weight or less, more preferably 25 parts by weight or more and 100 parts by weight or less, most preferably 30 parts by weight or more and 70 parts by weight or less) relative to 100 parts by weight of the polyol compound. In addition, the mixing ratio (weight ratio) of the phosphate ester and the phosphinic acid salt compound is preferably 90:10 to 50:50, further 85:15 to 55:45, and further 80:20 to 60:40 in terms of the phosphate ester:phosphinic acid salt compound ratio. By being in such a range, it is possible to improve the workability and heat resistance.
In particular, when a cyclic phosphoramidate is contained, the cyclic phosphoramidate is preferably 1 part by weight or more and 100 parts by weight or less (more preferably 5 parts by weight or more and 70 parts by weight or less, and even more preferably 10 parts by weight or more and 50 parts by weight or less) relative to 100 parts by weight of the polyol compound. By being in such a range, it is possible to obtain excellent workability and further improve heat resistance.

As the polyisocyanate compound, various polyisocyanate compounds known in the technical field of polyurethane can be used. Examples of polyisocyanate compounds include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), etc. In the present invention, MDI is preferred in terms of ease of handling, reaction speed, physical properties of the resulting foam, and cost advantages. Examples of MDI include monomeric MDI and polymeric MDI (polymethylene polyphenylisocyanate).

The isocyanate index is preferably 130 or more and 500 or less (more preferably 150 or more and 480 or less, and even more preferably 170 or more and 450 or less).
By mixing the polyol compound and the polyisocyanate compound within such ranges, excellent heat resistance can be obtained.
When a phosphinate compound is contained as the flame retardant, the isocyanate index is preferably 250 or more and 500 or less (more preferably 280 or more and 480 or less, and even more preferably 300 or more and 450 or less).
The isocyanate index is expressed as 100 times the value obtained by dividing the number of equivalents of isocyanate groups in a polyisocyanate compound by the total number of equivalents of active hydrogen in active hydrogen-containing components (polyol compound, water, etc.).

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

In addition to the above-mentioned components, the urethane foam of the present invention can also contain an ethylenically unsaturated double bond-containing compound. Examples of the ethylenically unsaturated double bond include (meth)acryloyl group, allyl group, and propenyl group. In the present invention, the use of such an ethylenically unsaturated double bond-containing compound can further improve heat resistance, storage stability, workability, etc.
In particular, in the present invention, when a phosphinate compound is contained as a flame retardant together with an ethylenically unsaturated double bond-containing compound, the flame retardant effect is enhanced and better heat resistance can be imparted. Also, when a cyclic phosphoramidate is contained as a flame retardant, the flame retardant effect is enhanced and better heat resistance can be imparted.

From the viewpoint of the above-mentioned effects, the ethylenically unsaturated double bond-containing compound is preferably one having an ethylenically unsaturated double bond concentration in one molecule of 0.5 mmol/g to 20 mmol/g, and more preferably one having an ethylenically unsaturated double bond concentration in one molecule of 5 mmol/g to 15 mmol/g. The ethylenically unsaturated double bond concentration in a molecule is expressed as the number of moles of ethylenically unsaturated double bonds in the molecule, and is expressed as 1000 times (mmol/g) the value obtained by dividing the number of ethylenically unsaturated double bonds in the molecule by the molecular weight.

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

Among these, examples of reaction products between polyhydric alcohols and unsaturated carboxylic acids include pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene-polypropylene glycol di(meth)acrylate, and alkylene oxide-modified trimethylolpropane tri(meth)acrylate.

Examples of the bisphenol A (meth)acrylate compounds include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane, and the like.

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

The amount of the ethylenically unsaturated double bond-containing compound mixed is preferably 1 part by weight to 100 parts by weight, more preferably 5 parts by weight to 90 parts by weight, and even more preferably 10 parts by weight to 80 parts by weight, relative to 100 parts by weight of the polyol compound. When the ethylenically unsaturated double bond-containing compound contains multiple hydroxyl groups, it is considered to be a polyol compound. The isocyanate index is calculated taking into account the active hydrogen-containing components contained in the ethylenically unsaturated double bond-containing compound.

In addition to the above components, the urethane foam of the present invention may contain, for example, colorants, surfactants, polymerization inhibitors, fibers, etc.
Examples of colorants include pigments and dyes.
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, etc. Such surfactants can impart storage stability and dispersion stability.
Examples of the polymerization inhibitor include hydroquinone-based polymerization inhibitors, benzoquinone-based polymerization inhibitors, catechol-based polymerization inhibitors, piperidine-based polymerization inhibitors, etc. Such polymerization inhibitors impart long-term storage stability and also contribute to production stability when added during the polyol production process.
Examples of fibers include organic fibers such as cellulose fibers, polyester fibers, polyethylene fibers, polypropylene fibers, wood fibers, and polyamide fibers, and inorganic fibers such as glass fibers and ceramic fibers. Such fibers can impart workability, foam formability, dimensional stability, etc. In the present invention, it is not necessary to use fibers, but when fibers are mixed, the effect can be achieved with a small amount of fibers.

The laminate of the present invention is a colored coating film laminated on the urethane foam.

The colored coating contains a binder and a colorant.

The binder contains a synthetic resin emulsion having a glass transition temperature of 0° C. or lower (preferably, −40° C. or higher and −5° C. or lower, and more preferably, −30° C. or higher and −10° C. or lower). Such a synthetic resin emulsion has excellent adhesion to urethane foam, and a colored coating film containing the synthetic resin emulsion has excellent adhesion to urethane foam and can maintain its aesthetic appearance for a long period of time.
If the glass transition temperature is higher than 0° C., the adhesion to the urethane foam may be poor, and the aesthetic appearance may not be maintained for a long period of time.
The glass transition temperature is a value calculated by the FOX formula.

Examples of such synthetic resin emulsions include acrylic resin, acrylic silicone resin, vinyl acetate resin, acrylic vinyl acetate resin, polyethylene resin, styrene resin, acrylic styrene resin, vinyl propionate resin, vinyl versatate resin, ethylene vinyl acetate resin, vinyl chloride resin, epoxy resin, urethane resin, fluororesin, polyester resin, phenolic resin, petroleum resin, polybutadiene resin, alkyd resin, and melamine resin, and one or more of these can be used.

In the present invention, it is particularly preferred that the polymer is a polymer made from a monomer group containing an acrylic monomer (preferably one or more selected from acrylic resin, acrylic silicone resin, acrylic vinyl acetate resin, and acrylic styrene resin), which has superior adhesion to urethane foam.

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

Examples of the colorant include pigments and dyes, and one or more of these may be used.
The pigment is not particularly limited, but examples thereof include inorganic pigments such as titanium oxide, zinc oxide, carbon black, graphite, black iron oxide, copper chromium black, cobalt black, copper manganese iron black, ferric oxide (red oxide), lead chromate (molybdate orange), permanent red, permanent carmine, yellow lead, yellow iron oxide, titanium yellow, chrome green, cobalt green, ultramarine, Prussian blue, and cobalt blue; organic color pigments such as azo-based, naphthol-based, pyrazolone-based, anthraquinone-based, perylene-based, quinacridone-based, disazo-based, isoindolinone-based, benzimidazole-based, phthalocyanine-based, quinophthalone-based, and dioxazine-based; pearl pigments, fluorescent pigments, phosphorescent pigments, and metallic pigments, and these 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 types and mixing amounts of such pigments and dyes.
The amount of colorant in the colored coating film is preferably 10 parts by weight to 500 parts by weight, more preferably 20 parts by weight to 300 parts by weight, per 100 parts by weight of the solid content of the binder.

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

The laminate of the present invention can be used as a building material, for example, it can be suitably used as a surface material by laminating it on a substrate.
For example, when used as a surface material, applicable substrates include, for example, color steel plate, galvalume steel plate, PVC steel plate, stainless steel plate, aluminum plate, copper plate, titanium plate, aluminum-plated steel plate, zinc-plated steel plate, clad steel plate, sandwich 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-insulating board, etc.

When laminating the laminate of the present invention to such a substrate, the following methods can be used: a laminate in which a colored coating film is laminated on a urethane foam is first prepared, and the laminate is then attached to the substrate; or, alternatively, the components that form the urethane foam are directly applied to the substrate, urethane foam is formed on the substrate, and then a material that forms the colored coating film is laminated on the urethane foam.

A method for obtaining urethane foam is, for example, to prepare it in a two-liquid form during distribution and mix it when used (when forming foam). In such a two-liquid form, for example, the first liquid may contain a polyol compound (a blowing agent, a catalyst, and a flame retardant), and the second liquid may contain a polyisocyanate compound.

The viscosity of the first liquid is preferably 20 mPa·s or more and 500 mPa·s or less, more preferably 30 mPa·s or more and 350 mPa·s or less, and even more preferably 50 mPa·s or more and 250 mPa·s or less, from the viewpoints of storage stability, handling property, and workability during foam formation of the first liquid. The viscosity is the viscosity at 20 rpm (the indicator value at the fourth rotation) measured with a BH type viscometer at a temperature of 20°C. By using such a viscosity, the curable composition can be set to a relatively low viscosity while sufficiently ensuring the storage stability of the curable composition. This reduces the stirring work during application, and advantageous effects are obtained in terms of handling property, workability, and miscibility with polyisocyanate compounds.
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 a substrate, for example, a spray foaming machine for spraying work (for example, a two-liquid tip-mixing spray coating machine, etc.) may be used to spray the mixture of the first and second liquids. In this case, it is preferable to set the temperatures of the first and second liquids to 20°C or higher and 60°C or lower, more preferably 30°C or higher and 50°C or lower. The first and second liquids thus set to a predetermined temperature are mixed at the tip of a spray gun and sprayed toward the substrate to form a foam on the substrate. The spraying environment can be preferably 5°C or higher and 45°C or lower.
The first liquid and the second liquid are preferably mixed at a volume ratio of about 1:1. The foam formed by such a method can exhibit excellent performance in terms of low thermal conductivity, heat resistance, etc. The thickness of the foam is not particularly limited and may be appropriately set depending on the required performance, etc., but is preferably 10 mm or more, more preferably 15 mm or more and 500 mm or less.

In the method of laminating a colored coating film on the surface of a urethane foam, a material for forming a colored coating film (a colored coating film-forming material containing a binder, a colorant, etc.) is applied, and then dried and cured to form a colored coating film. In this case, the colored coating film-forming material may be mixed with additives, water, etc., as necessary.
The colored coating film forming material is preferably applied directly onto the urethane foam. When applying the colored coating film forming material, a coating tool such as a trowel, a spray, a roller, or a brush can be used as appropriate. The thickness of the colored coating film formed may be appropriately set depending on the application site, the purpose, the 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.

The following examples will clarify the features of the present invention.

(Urethane foam)
As the first liquid, a polyol composition was prepared by uniformly mixing the following raw materials in the weight ratio shown in Table 1. As the second liquid, a liquid made of polymeric MDI was prepared.
Polyol compound 1: aromatic polyester polyol (terephthalic acid-based polyester polyol, viscosity 1900 mPa·s, acid value: 0 mgKOH/g, hydroxyl value: 250 mgKOH/g)
Polyol compound 2: aromatic/aliphatic polyester polyol (phthalic acid/adipic acid-based polyester polyol, viscosity 900 mPa·s, acid value: 0 mgKOH/g, hydroxyl value: 350 mgKOH/g)
Polyol compound 3: Aliphatic polyester polyol (fumaric acid-based polyester polyol, viscosity 6000 mPa·s, acid value: 0 mgKOH/g, hydroxyl value: 150 mgKOH/g)
Blowing agent 1: hydrochlorofluoroolefin Blowing agent 2: water (hydroxyl value: 6233 mg KOH/g)
Catalyst 1: Nurate catalyst (a glycol solution of tetraalkylammonium 2-ethylhexanoate)
Catalyst 2: Resinification catalyst (bismuth octylate in octylic acid solution)
Flame retardant 1: phosphinate compound (aluminum tris(diethylphosphinate), average particle size 4 μm, density 1.35 g/cm ³ )
Flame retardant 2: phosphinate compound (sodium phosphinate, average particle size 8 μm, density 1.39 g/cm ³ )
Flame retardant 3: organic phosphate compound (tris(chloropropyl)phosphate, density 1.29 g/cm ³ )
Flame retardant 4: cyclic phosphoramidate (in formula 4, R1: all methylene groups, R2: all methyl groups, R3: all hydrogen atoms, R4: cyclic phosphoramidate of butylene groups, average particle size 3 μm)
Flame retardant 5: cyclic phosphoramidate (R1 in formula 4: all methylene groups, R2: all methyl groups, N(R3)-R4-(R3)N: cyclic phosphoramidate with a nitrogen-containing 6-membered ring structure (piperidine structure), average particle size 3 μm)
Double bond compound 1: ethylenically unsaturated double bond-containing compound (trimethylolpropane triacrylate, ethylenically unsaturated double bond concentration 10 mmol/g, hydroxyl value: 0 mgKOH/g)
・Foam stabilizer: Silicone-based foam stabilizer (colored coating)
As a colored coating film forming material, the following raw materials were uniformly mixed in the weight ratios shown in Table 2 to prepare a colored coating film forming material.
Organic binder 1: Acrylic resin (glass transition temperature -15°C, solid content 50% by weight)
Organic binder 2: Acrylic-styrene copolymer resin (glass transition temperature 15°C, solid content 50% by weight)
Organic binder 3: Acrylic-styrene copolymer resin (glass transition temperature -3°C, solid content 50% by weight)
・Coloring pigment 1: Titanium oxide ・Coloring pigment 2: Carbon black ・Coloring pigment 3: Ferric oxide ・Additives: Thickener, defoamer

(Examples 1 to 17, Comparative Example 1)
The first and second liquids were each heated to 40°C and mixed to obtain the isocyanate index shown in Table 1. The resulting mixture was sprayed with a spray gun onto a substrate (slate board) in an atmosphere of 5°C and allowed to foam, yielding a urethane foam (thickness 50 mm) in which one entire side of the substrate was covered with foam.
After leaving the sample to stand for 24 hours at room temperature (temperature 23°C, relative humidity 50%), a colored coating film forming material prepared according to the formulation shown in Table 2 was sprayed onto the sample at room temperature to form a colored coating film (thickness 0.1 mm) to obtain a test specimen.
The obtained specimens were subjected to the following tests. The results are shown in Tables 1 and 3.

(1) Foam Formability The state of the formed foam was visually observed and the evaluation criteria were as follows:
A: A homogeneous foam was formed.
A: A nearly homogeneous foam was formed.
△: Some abnormalities were observed in the foam (embrittlement, non-uniform foaming, poor adhesion, etc.).
×: Abnormalities were observed in the form.

(2) Thermal Conductivity The foam portion of the test specimen 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 is over 0.03 W/(m.K)

(3) Aesthetics Test The surfaces of the test specimens were visually observed and evaluated immediately after obtaining them (1) and after leaving them to stand at room temperature (temperature 23° C., relative humidity 50%) for 14 days (2). The evaluation was as follows:
⊚: No cracks were found, and the appearance was excellent.
◯: Almost no cracks were observed, and the appearance was good.
×: Cracks were noticeable and the appearance was impaired.

Claims (3)

A laminate in which a colored coating film is laminated on a urethane foam,
The urethane foam is formed from a polyol compound, a blowing agent, a catalyst, a polyisocyanate compound, and a flame retardant;
The color coating comprises a binder and a colorant;
the binder is a synthetic resin emulsion of an acrylic resin or an acrylic-styrene copolymer resin having a glass transition temperature of 0° C. or lower,
The colorant is contained in the colored coating film in an amount of 98 parts by weight to 500 parts by weight per 100 parts by weight of the solid content of the binder . 2. The laminate according to claim 1, wherein the flame retardant comprises at least one selected from the group consisting of cyclic phosphate esters, phosphinate compounds, phosphoramidates, and cyclic phosphoramidates. 2. The laminate according to claim 1, wherein the binder is a synthetic resin emulsion of an acrylic resin or an acrylic-styrene copolymer resin having a glass transition temperature of -30 to -5°C.