JP2020037260A - 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 having excellent aesthetics as well as excellent heat insulation and heat resistance.

Generally, in a building structure, a heat insulating material is installed together with a flame-retardant material in order to enhance heat insulating performance.
As such a heat insulating material, an organic heat insulating material such as urethane foam, phenol foam and styrene foam is mainly used. For example, urethane foam has been widely used because it has features such as excellent heat insulation properties and relatively low cost.
In recent years, with the improvement in the heat resistance of urethane foam, urethane foam can be used alone and can be used as a surface material, so that further applications are expected. (For example, Patent Documents 1 and 2, etc.)

WO2014 / 112394 JP-A-2015-151524

  However, as such polyurethane foams are used in places where they can be seen with the expansion of applications, the aesthetic appearance of the surface is becoming a problem, and the expansion of applications requires the aesthetics of the surface. Improvement is urgently needed.

  The present inventor has conducted intensive studies to solve the above problems, and as a result, by laminating a colored coating containing a specific binder and a coloring agent on the urethane foam, the urethane foam and the colored coating The inventors have found that a laminate excellent in heat insulation and heat resistance, which has excellent adhesion and can maintain aesthetics over a long period of time, can be obtained, and has completed the present invention.

That is, the present invention has the following features.
1. A laminate in which a colored coating film is laminated on urethane foam,
The colored coating contains a binder and a colorant,
A laminate, wherein the binder comprises a synthetic resin emulsion having a glass transition temperature of 0 ° C. or lower.

  The laminate of the present invention is excellent in heat insulation and heat resistance, and can maintain aesthetics over a long period of time.

  Hereinafter, embodiments for carrying out the present invention will be described.

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

  As the urethane foam, use is made of, for example, a polyol compound, a foaming agent, a catalyst, and a polyisocyanate compound, which use a flame retardant or the like to impart heat resistance.

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

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

  Examples of the polyether polyol include an aromatic polyether polyol, a phosphorus-containing polyether polyol, a glycerin-based polyether polyol, and an amino group-containing polyether polyol. Specifically, as the aromatic polyether polyol, for example, bisphenol A type polyether polyol obtained by adding an alkylene oxide (eg, 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 condensate or the like as an initiator, The resulting aromatic amine-based polyether polyol and the like can be mentioned. Examples of the phosphorus-containing polyether polyol include dialkyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, which is a diol having a phosphate ester structure. Examples of the glycerin-based polyether polyol include a polyether polyol obtained by adding an alkylene oxide using glycerin as an initiator. Examples of the amino group-containing polyether polyol include those obtained by adding an alkylene oxide using a low molecular weight amine (eg, 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 represented by the number of mg of potassium hydroxide in an equimolar amount to the hydroxyl group contained in 1 g of the sample, and is defined by JIS K1557-1: 2007 Plastics-Polyurethane raw material polyol test method-Part 1: Hydroxyl value 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 polyol compounds.

  Examples of the foaming agent include hydrocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, hydrofluoroolefin, hydrochlorofluoroolefin, water, liquefied carbon dioxide, 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. Examples of the hydrochlorofluorocarbon (HCFC) include 1,1-dichloro-1-fluoroethane (HCFC-141B), 1-chloro-1,1-difluoroethane (HCFC-142B), and chlorodifluoromethane (HCFC-22). And the like. Examples of the hydrofluorocarbon (HFC) include difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,1-trifluoroethane (HFC143a), 1,1, 2,2-tetrafluoroethane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), 1,1,1,2,3,3,3-hepta Fluoropropane (HFC227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluorobutane (HFC365mfc), 1,1,1,2,2,2 3,4,5,5,5-decafluoropentane (HFC4310mee) and the like.

Examples of the hydrofluoroolefin (HFO) include pentafluoropropene such as 1,2,3,3,3-pentafluoropropene (HFO1225ye), 1,3,3,3-tetrafluoropropene (HFO1234ze), Tetrafluoropropene such as 3,3,3-tetrafluoropropene (HFO1234yf) and 1,2,3,3-tetrafluoropropene (HFO1234ye) and trifluoropropene such as 3,3,3-trifluoropropene (HFO1243zf) , Tetrafluorobutene (HFO1345), pentafluorobutene (HFO1354), hexafluorobutene (HFO1336), heptafluorobutene (HFO1327), heptafluoropentene (HFO1474), 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), Examples thereof include dichlorotrifluoropropene (HCFO1223) and the like, and isomers thereof (cis-form and trans-form).
As the blowing agent in the present invention, one or more selected from hydrofluoroolefins, hydrochlorofluoroolefins, and water are preferable. For example, hydrofluoroolefins and water, hydrochlorofluoroolefins and water, and hydrofluoroolefins Each blowing agent such as hydrochlorofluoroolefin and water can be used in combination.

  The mixing amount of the foaming agent is preferably 10 parts by weight or more and 200 parts by weight or less, more preferably 20 parts by weight or more and 180 parts by weight or less, further preferably 30 parts by weight or more and 150 parts by weight or less with respect to 100 parts by weight of the polyol compound. It is. When the blowing agent contains hydrofluoroolefin and / or hydrochlorofluoroolefin and water, the mixing ratio (weight ratio) of the hydrofluoroolefin and / or hydrochlorofluoroolefin to water is 100: 0.5 to The ratio is preferably 100: 5 (more preferably 100: 0.8 to 100: 4). When the content is in such a range, a foam having excellent low thermal conductivity, excellent heat resistance, and excellent strength can be obtained.

  Examples of the catalyst include, but are not particularly limited to, a nullation catalyst, a resinification catalyst, a foaming catalyst, and the like, and one or more of these can be used.

  The nullation catalyst is not particularly limited as long as it is a catalyst effective for isocyanuration, and examples thereof include tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, and trimethylbenzylammonium, or organic acids thereof. Salts (eg, acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, lactic acid, etc.), trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium , A trialkylhydroxyalkylammonium hydroxide such as triethylhydroxyethylammonium or an organic acid salt thereof (as an organic acid, for example, acetic acid, caproon, Acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, lactic acid, etc., alkylcarboxylic acid (eg, acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid) ), Myristic acid, lactic acid, etc.), metal chelates of β-diketones such as aluminum acetylacetone and lithium acetylacetone, Friedel-Crafts catalysts such as aluminum chloride and boron trifluoride, titanium tetrabutylate, tributylantimony oxidation And an organosilyl group-containing compound such as hexamethylsilazane. One or more of these can be used.

  Examples of the resination catalyst include triethylenediamine (TEDA), triethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N , N ', N'-tetramethylpropylenediamine, N, N, N', N ", N" -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ', N ", N' Tertiary amines such as '-pentamethyldipropylenetriamine, N, N, N', N'-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, and the like Organic acid salt, bismuth tris (2-ethylhexanoate), bismuth tris (neodecanoate), bismuth tris (palmitate), bis Organic metal such as tetramethylheptane diate, 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.

  Examples of the foaming catalyst include N, N, N ', N', N "-pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N', N"- Pentamethyldipropylenetriamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethoxyethanol, N, N, N ′, N ″, N ′ ″, N ′ ″-hexamethyl Triethylenetetramine, N, N, N ', N "-tetramethyl-N"-(2-hydroxylethyl) triethylenediamine, N, N, N', N "-tetramethyl- (2-hydroxylpropyl ) Tertiary amines such as triethylenediamine or organic acid salts thereof, and 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 48 parts by weight, and still more preferably 1 to 45 parts by weight, based on 100 parts by weight of the polyol compound. Parts by weight, most preferably 3 parts by weight or more and 40 parts by weight or less. When the catalyst contains an active hydrogen-containing component, the isocyanate index is calculated in consideration of the active hydrogen-containing component contained in the catalyst.
In the present invention, it is particularly preferable to include a resin conversion catalyst and / or a foaming catalyst together with the nullation catalyst, which is advantageous in terms of foamability and 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 flame retardant include halogen-based flame retardants, organic bromine-based flame retardants, nitrogen-based flame retardants, phosphorus-based flame retardants, metal hydrate-based flame retardants, antimony-based flame retardants, boron-based flame retardants, and silicon-based flame retardants. And the like. In the present invention, a phosphorus-based flame retardant is particularly preferable. Examples of the phosphorus-based flame retardant include a phosphoric ester, a cyclic phosphate, a polyphosphate compound, a phosphinate compound, a halogenated phosphazene, a phosphoramidate, and a cyclic ester. Examples thereof include phosphoramidate, red phosphorus, phosphorus trichloride, and phosphorus pentachloride, and one or more of these can be used.

  Specifically, examples of the phosphate ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, trisnonylphenyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, and cresyl phenyl. Phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, trixylenyl phosphate, diisopropylphenyl phosphate, tris (2-ethylhexyl) phosphate, resorcinol bisdiphenyl phosphate, bisphenol A bis (diphenyl phosphate), resorcinol bis (dixylenyl phosphate), tris (Chloroethyl) phosphate, tris (chloropropyl) phosphate Phosphate, tris (dichloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate, bis (chloropropyl) monooctyl phosphate, hydroxy Nonyl diphenyl phosphate, phenyl nonyl phenyl hydroquinonyl phosphate, phenyl dinonyl phenyl phosphate, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphate, dimethyl-4-hydroxy-3,5-dibromo Benzylphosphonate, diphenyl-4-hydroxy-3,5-dibromobenzylphosphonate and the like.

  Examples of the cyclic phosphate include 3,9-bis (phenylmethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, -Bis ((2-methylphenyl) methyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ((3-methyl Phenyl) methyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ((4-methylphenyl) methyl) -3, 9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ((2,4-dimethylphenyl) methyl) -3,9-dioxo-2 , 4 8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ((2,6-dimethylphenyl) methyl) -3,9-dioxo-2,4,8,10-tetraoxa -3,9-Diphosphaspiro [5.5] undecane, 3,9-bis ((3,5-dimethylphenyl) methyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9- Diphosphaspiro [5.5] undecane, 3,9-bis ((2,4,6-trimethylphenyl) methyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5 .5] undecane, 3,9-bis ((2-sec-butylphenyl) methyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] unde 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- Screw ((2-tert-bu Tylphenyl) methyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ((4-tert-butylphenyl) methyl)- 3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ((2,4-di-tert-butylphenyl) methyl) -3 , 9-Dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ((2,6-di-tert-butylphenyl) methyl) -3, 9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ((2,4,6-tri-tert-butylphenyl) methyl) -3 , -Dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ((4-biphenyl) methyl) -3,9-dioxo-2,4,8 , 10-Tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ((1-naphthyl) methyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9 -Diphosphaspiro [5.5] undecane, 3,9-bis ((2-naphthyl) methyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane , 3,9-bis ((1-anthryl) methyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (( 2-ant M))-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 -Screw (Triphenylmethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3-phenylmethyl-9-((2,6-dimethylphenyl) Methyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3-phenylmethyl-9-((2,4-di-tert-butylphenyl) ) Methyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3-phenylmethyl-9- (1-phenylethyl) -3,9- Dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3-phenylmethyl-9-diphenylmethyl-3,9-dioxo-2,4,8 10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3-((2,6-dimethylphenyl) methyl) -9- (1-phenylethyl) -3,9-dioxo-2,4,8 , 10-Tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3-((2,4-di-tert-butylphenyl) methyl) -9- (1-phenylethyl) -3,9-dioxo- 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3-diphenylmethyl-9- (1-phenylethyl) -3,9-dioxo-2,4,8,10- Tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3-diphenylmethyl-9-((2,6-dimethylphenyl) methyl) -3,9-dioxo-2,4,8,10-te Laoxa-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;

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

  Examples of the phosphinate compound include sodium phosphinate, calcium phosphinate, aluminum phosphinate, zinc phosphinate, calcium dimethyl phosphinate, aluminum dimethyl phosphinate, zinc dimethyl phosphinate, calcium ethyl methyl phosphinate, and ethyl methyl phosphinate. Aluminum, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, aluminum tris (diethylphosphinate), aluminum tris (methylethylphosphinate), aluminum tris (dibutylphosphinate), tris ( Aluminum (butylethylphosphinate), aluminum tris (diphenylphosphinate), bis (diethylphosphinic acid) Zinc acid, zinc bis (methylethylphosphinate), zinc bis (diphenylphosphinate), titanyl bis (diethylphosphinate), titanyl tetrakis (diethylphosphinate), titanyl bis (methylethylphosphinate), tetrakis ( Methyl ethyl phosphinic acid) titanyl, bis (diphenyl phosphinic acid) titanyl, tetrakis (diphenyl phosphinic acid) titanyl and the like can be used, and one or more of these can be used.

  Examples of halogenated phosphazenes include, for example, hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene, dodecachlorocyclohexaphosphazene, hexabromocyclotriphosphazene, hexafluorocyclotriphosphazene, octafluorocyclotetraphosphazene, deca Fluorocyclopentaphosphazene, dodecafluorocyclohexaphosphazene, hexamethoxycyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, hexaphenoxycyclotriphosphazene, diethoxytetrafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, methoxypentafluorocyclotriazene Phosphazene, propoxypentaful B cyclotriphosphazene, butoxy pentafluoro Cyclotriphosphazene the like.

Examples of the phosphoramidate include compounds described in Formula 1 or Formula 2.
(Equation 1)
O-R1
│
O = P-N (R2) ₂
│
O-R1
(Equation 2)
O-R1 O-R1
│ │
O = PN (R2) -R3- (R2) NP = O
│ │
O-R1 O-R1
R1 may be the same or different and may be an alkyl group having 1 to 12 carbon atoms, R2 may be the same or different and may be a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R3 may have 1 to 12 carbon atoms. It represents an alkylene group, and N (R2) ₂ and N (R2) -R3- (R2) N may have a nitrogen-containing heterocyclic structure.

Examples of the cyclic phosphoramidate include the compounds described in Formula 3 and Formula 4.
(Equation 3)
R2 R1-O
＼ / ＼
CP = O
/ ＼ / ＼
R2 R1-ON (R3) ₂
(Equation 4)
R2 R1-OO-R1 R2
＼ / ＼ / ＼ /
C P = O O = P C
/ ＼ / ＼ / ＼ / ＼
R2 R1-ON (R3) -R4- (R3) NO-R1 R2
R1 may be the same or different, an alkylene group having 1 to 3 carbon atoms, R2 may be the same or different, an alkyl group having 1 to 12 carbon atoms, R3 may be the same or different, and may be a hydrogen atom or An alkyl group having 1 to 12 carbon atoms, R4 represents an alkylene group having 1 to 12 carbon atoms, and N (R3) ₂ , N (R3) -R4- (R3) N may have a nitrogen-containing heterocyclic structure. Good.

In the present invention, the mixing amount of the flame retardant is preferably 1 part by weight or more and 1000 parts by weight or less, more preferably 5 parts by weight or more and 600 parts by weight or less, and still more preferably 10 parts by weight or more based on 100 parts by weight of the polyol compound. It is 400 parts by weight or less.
In the present invention, as the flame retardant, at least one selected from a cyclic phosphate ester, a phosphinate compound, a phosphoramidate, and a cyclic phosphoramidate, and further selected from a phosphinate compound and a cyclic phosphoramidate It is preferable to include at least one kind, and it is possible to improve the workability and further improve the heat resistance.
In particular, when a phosphinate compound is contained, it is preferable to use a phosphate ester and a phosphinate compound in the present invention. When a phosphate ester and a phosphinate compound are used in combination, the phosphate ester is used in an amount of 30 parts by weight or more and 900 parts by weight or less (preferably 40 parts by weight or more and 600 parts by weight or less, more preferably 50 parts by weight or less with respect to 100 parts by weight of the polyol compound). Weight parts or more and 400 weight parts or less, and the phosphinate compound is 10 weight parts or more and 200 weight parts or less (more preferably 20 weight parts or more and 120 weight parts or less, further preferably 25 weight parts or more and 100 weight parts or less, and most preferably 30 parts by weight or more and 70 parts by weight or less). The mixing ratio (weight ratio) of the phosphate ester and the phosphinate compound is 90:10 to 50:50, more preferably 85:15 to 55:45, and more preferably a phosphate ester: phosphinate compound ratio. The ratio is preferably from 80:20 to 60:40. By being in such a range, the workability is excellent and the heat resistance can be further improved.
In particular, when a cyclic phosphoramidate is contained, the cyclic phosphoramidate is used in an amount of 1 part by weight or more and 100 parts by weight or less (more preferably 5 parts by weight or more and 70 parts by weight or less, still more preferably 100 parts by weight of the polyol compound). 10 parts by weight or more and 50 parts by weight or less). By being in such a range, the workability is excellent and the heat resistance can be further improved.

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

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

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

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

  As the ethylenically unsaturated double bond-containing compound, those having an ethylenically unsaturated double bond concentration of 0.5 mmol / g or more and 20 mmol / g in one molecule are preferable from the viewpoint of the above-mentioned effects and the like. More preferably, it is not less than g and not more than 15 mmol / g. The concentration of the ethylenically unsaturated double bond in the molecule is represented by the number of moles of the ethylenically unsaturated double bond in the molecule. It is expressed by 1000 times (mmol / g) of the numerical value divided by.

  Specific examples of the ethylenically unsaturated double bond-containing compound include, for example, polyhydric alcohols (eg, dihydric or higher alcohols and derivatives thereof, dihydric or higher phenols, polyols, etc.) and unsaturated carboxylic acids (( (Meth) acrylic acid or the like), an amine (for example, divalent or higher valent amine, alkanolamine or the like) and an unsaturated carboxylic acid, a thiol unsaturated carboxylic acid thioester or unsaturated alkylthioether, Examples include bisphenol A-based (meth) acrylate compounds, reaction products of a glycidyl group-containing compound with an unsaturated carboxylic acid, (meth) acrylate compounds having a urethane bond in the molecule, and nonylphenoxy polyethyleneoxy acrylate. These can be used alone or in combination of two or more.

  Among them, as a reaction product of the polyhydric alcohol and the unsaturated carboxylic acid, for example, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolpropanetri (meth) acrylate, trimethylolpropanedi (meth) acrylate, ditri 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 bisphenol A-based (meth) acrylate compound 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, etc. Is mentioned.

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

  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, further preferably 10 parts by weight or less, based on 100 parts by weight of the polyol compound. Not less than 80 parts by weight. When the ethylenically unsaturated double bond-containing compound contains a plurality of hydroxyl groups, it is regarded as a polyol compound. The isocyanate index is calculated in consideration of the active hydrogen-containing component contained in the ethylenically unsaturated double bond-containing compound.

In the urethane foam of the present invention, for example, a colorant, a surfactant, a polymerization inhibitor, a fiber and the like can be mixed in addition to the above components.
Examples of the colorant include a pigment and a dye.
Examples of the surfactant include a nonionic surfactant, an anionic surfactant, and a cationic surfactant. Such a surfactant can provide storage stability and dispersion stability.
Examples of the polymerization inhibitor include a hydroquinone-based polymerization inhibitor, a benzoquinone-based polymerization inhibitor, a catechol-based polymerization inhibitor, and a piperidine-based polymerization inhibitor. Such a polymerization inhibitor imparts long-term storage stability and, when added during the polyol production process, contributes to production stability.
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.

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

  The colored coating film contains a binder and a colorant.

The binder includes a synthetic resin emulsion having a glass transition temperature of 0 ° C. or lower (preferably −40 ° C. to −5 ° C., more preferably −30 ° C. to −10 ° C.). 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 aesthetics over a long period of time.
When the glass transition temperature is higher than 0 ° C., the adhesion to urethane foam may be poor, and the aesthetics may not be maintained for a long period of time.
In addition, the glass transition temperature is a value obtained by a calculation formula of FOX.

  Such synthetic resin emulsions include, for example, acrylic resin, acrylic silicone resin, vinyl acetate resin, acryl 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, fluorine resin, polyester resin, phenol resin, petroleum resin, polybutadiene resin, alkyd resin, melamine resin, and one or more of these can be used. .

  In the present invention, it is particularly preferable that the polymer is a polymer polymerized from a monomer group containing an acrylic monomer (preferably at least one selected from acrylic resins, acrylic silicone resins, acrylic vinyl acetate resins, and acrylic styrene resins). Excellent in adhesion to foam.

As the acrylic monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) A) 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 Alkyl (meth) acrylic monomers such as (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, N- (2-dimethylaminoethyl) methacrylamide ;
Hydroxyl-containing (meth) acrylic monomers such as 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate;
Nitrile group-containing (meth) acrylic monomers such as (meth) acrylonitrile, etc. Amide group-containing (meth) acrylic monomers such as (meth) acrylamide, N-methylol (meth) acrylamide and diacetoneacrylamide;
(Meth) acrylic monomers containing a carbonyl group such as acrolein, diacetone (meth) acrylamide, vinyl methyl ketone, vinyl ethyl ketone, and vinyl butyl ketone;
And the like, and one or more of these can be used.
In addition to the above acrylic monomers, aromatic monomers such as styrene, 2-methylstyrene, vinyltoluene, chlorostyrene, vinylanisole, vinylnaphthalene, and divinylbenzene, ethylene, propylene, isoprene, butadiene, vinyl acetate, and vinyl propionate Further, other monomers such as vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl ether and vinyl ketone can also be copolymerized.

Examples of the coloring agent include pigments and dyes, and one or more of these can be used.
Examples of the pigment include, but are not particularly limited to, for example, titanium oxide, zinc oxide, carbon black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, ferric oxide (bengala), and lead chromate ( Molybdate orange), permanent red, permanent carmine, graphite, yellow iron oxide, titanium yellow, chrome green, cobalt green, ultramarine, navy blue, cobalt blue inorganic pigments, azo, naphthol, pyrazolone, anthraquinone, perylene System, quinacridone system, disazo system, isoindolinone system, benzimidazole system, phthalocyanine system, quinophthalone system, organic color pigment such as dioxazine system, pearl pigment, fluorescent pigment, luminous pigment, metallic pigment, and the like. Can be used with one or more types .
The color tone of the colored coating film can be appropriately set by adjusting the types and the mixing amounts of such pigments and dyes.
The compounding amount of the coloring agent in the colored coating film is preferably from 10 parts by weight to 500 parts by weight, more preferably from 20 parts by weight to 300 parts by weight, based on 100 parts by weight of the solid content of the binder.

  The colored coating film of the present invention, in addition to the above-described components, may be an extender such as heavy calcium carbonate, clay, kaolin, talc, precipitated barium sulfate, barium carbonate, white carbon, and diatomaceous earth to the extent that the effects of the present invention are not impaired. , Silica sand, mineral aggregates such as dolomite, pearlite, inorganic lightweight aggregates such as expanded vermiculite, aluminum hydroxide, magnesium hydroxide, zeolite, halloysite, allophane, endotherm such as ettringite, melamine, dicyandiamide, azodicarbonamide Etc., carbonizing agents such as pentaerythritol and dipentaerythritol, flame retardants, fibers, reinforcing materials, plasticizers, preservatives, fungicides, defoamers, thickeners, leveling agents, water reducing agents, pigment dispersion Additives such as anti-settling agents, anti-settling agents, anti-sagging agents, ultraviolet absorbers, and antioxidants.

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 being laminated on a base material.
For example, when used as a surface material, applicable substrates include, for example, color steel sheets, galvanium steel sheets, PVC steel sheets, stainless steel sheets, aluminum sheets, copper sheets, titanium sheets, aluminum-plated steel sheets, galvanized steel sheets, clad steel sheets, sandwiches Examples include steel plate, concrete, mortar, porcelain tile, fiber-mixed cement plate, cement calcium silicate plate, slag cement perlite plate, ALC plate, siding plate, extruded plate, gypsum board, plywood, plastic plate, heat insulating plate and the like.

  For such a substrate, when laminating the laminate of the present invention, a laminate in which a colored coating film is laminated on urethane foam in advance, and a method of attaching the laminate to the substrate, Alternatively, there may be mentioned a method in which a component for forming a urethane foam is directly applied to a substrate, a urethane foam is formed on the substrate, and then a material for forming a colored coating film is laminated on the urethane foam.

  As a method of obtaining urethane foam, for example, it is preferable to use a two-pack type at the time of distribution and to mix and use it at the time of use (at the time of foam formation). In such a two-liquid type, for example, the first liquid may be a form containing a polyol compound (a blowing agent, a catalyst, and a flame retardant), and the second liquid may be a form containing 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 viewpoints of storage stability of the first liquid, handleability, workability at the time of foam formation, and the like. s or less, more preferably 50 mPa · s or more and 250 mPa · s or less. Note that the viscosity is a viscosity at 20 rpm measured at 20 ° C. by a BH type viscometer (a guideline value at the fourth rotation). With such a viscosity, the curable composition can be set to a relatively low viscosity while sufficiently ensuring the storage stability of the curable composition. Thereby, the stirring work or the like at the time of construction is reduced, and advantageous effects can be obtained also in handleability, workability, miscibility with the polyisocyanate compound, and the like.
The viscosity of the second liquid is preferably from 20 mPa · s to 500 mPa · s, more preferably from 30 mPa · s to 350 mPa · s, and still more preferably from 50 mPa · s to 250 mPa · s.

When applying urethane foam to a substrate, for example, the first liquid and the first liquid are sprayed using a spray foaming machine or the like for spraying work (for example, a two-liquid tip mixing type spray coating machine or the like). What is necessary is just to spray and mix the mixture with two liquids. In this case, it is preferable that the first liquid and the second liquid are each set to have a temperature of 20 ° C. or more and 60 ° C. or less, more preferably 30 ° C. or more and 50 ° C. or less. The first liquid and the second liquid thus set at a predetermined temperature are mixed at the tip of the spray gun, sprayed toward the base material, and form a foam on the base material. As the spraying environment, the work can be preferably performed at 5 ° C. or more and 45 ° C. or less.
The mixing of the first liquid and the second liquid is preferably about 1: 1 by volume. The foam formed by such a method can exhibit excellent performance in low thermal conductivity, heat resistance, and the like. The thickness of the foam is not particularly limited and may be appropriately set according to the required performance and the like, 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 on urethane foam (surface), a material for forming the colored coating (a material for forming a colored coating containing a binder, a coloring agent, etc.) is applied, dried and cured. Thereby, a colored coating film can be formed. At this time, an additive, water, and the like can be mixed with the colored coating film forming material as necessary.
It is desirable that the colored coating film forming material is applied directly on the urethane foam. At the time of applying the colored coating film forming material, coating equipment such as a trowel, a spray, a roller, and a brush can be appropriately used. The thickness of the formed colored coating film 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.

  Examples are shown below to further 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 at the weight ratio shown in Table 1. A liquid composed of polymeric MDI was prepared as the second liquid.
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 mPas, acid value: 0 mgKOH / g, hydroxyl value: 350 mgKOH / g)
-Polyol compound 3: aliphatic polyester polyol (fumaric acid-based polyester polyol, viscosity 6000 mPa-s, acid value: 0 mgKOH / g, hydroxyl value: 150 mgKOH / g)
-Blowing agent 1: Hydrochlorofluoroolefin-Blowing agent 2: Water (hydroxyl value: 6233 mgKOH / g)
・ Catalyst 1: Nullation catalyst (glycol solution of tetraalkylammonium 2-ethylhexanoate)
・ Catalyst 2: Resinification catalyst (octylic acid solution of bismuth octylate)
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 (R1: all methylene groups, R2: all methyl groups, R3: all hydrogen atoms, R4: butylene group cyclic phosphoramidate in formula 4, average particle size 3 μm)
Flame retardant 5: cyclic phosphoramidate (R1: all methylene groups in formula 4, R2: all methyl groups, N (R3) -R4- (R3) N: nitrogen-containing 6-membered cyclic structure (piperidine structure) Phosphoramidate, 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 foam stabilizer (colored coating film)
As a colored coating film forming material, a material in which the following raw materials were uniformly mixed at a weight ratio shown in Table 2 was prepared.
-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: thickeners, defoamers

(Examples 1 to 17, Comparative Example 1)
The first liquid and the second liquid are each heated to 40 ° C., and they are mixed so as to have an isocyanate index shown in Table 1, and the obtained mixed liquid is applied to a substrate (slate plate) under a 5 ° C. atmosphere. It was sprayed with a spray gun and foamed to obtain a urethane foam (thickness: 50 mm) in which the entire surface of the substrate was covered with the foam.
After standing at room temperature (temperature 23 ° C., relative humidity 50%) for 24 hours, a colored film-forming material prepared in the composition shown in Table 2 is applied by spraying at room temperature to form a colored film (0.1 mm thick). A specimen was formed.
Each test was performed on the obtained test body by the following method. The results are shown in Tables 1 and 3.

(1) Formability The state of the formed foam was visually observed. The evaluation criteria are as follows.
A: A uniform foam was formed.
：: A substantially homogeneous foam was formed.
C: Some abnormalities (embrittlement, uneven foaming, poor adhesion, etc.) were observed in the foam.
X: Abnormality was recognized in the foam.

(2) Thermal conductivity The foam part of the test body was cut out, and the thermal conductivity was measured using a thermal conductivity meter. The evaluation criteria are as follows.
：: Thermal conductivity of 0.03 W / (m · K) or less ×: Thermal conductivity of more than 0.03 W / (m · K)

(3) Aesthetics test Immediately after obtaining the test specimen (1) and after standing for 14 days at normal temperature (temperature 23 ° C., relative humidity 50%) (2), the surface of the test specimen is visually observed and evaluated. did. The evaluation is as follows.
：: No crack was found, and excellent aesthetics were observed.
：: Cracks were hardly found, and the appearance was good.
X: Cracks were conspicuous and the appearance was impaired.

Claims (1)

A laminate in which a colored coating film is laminated on urethane foam,
The colored coating contains a binder and a colorant,
A laminate, wherein the binder comprises a synthetic resin emulsion having a glass transition temperature of 0 ° C. or lower.