JP7085379B2 - Laminate - Google Patents

Description

The present invention relates to a novel laminate. The laminate of the present invention is excellent in low thermal conductivity, heat resistance, aesthetics and the like.

Generally, in a building or the like, heat is suppressed from entering and exiting between indoors and outdoors by providing foam on a wall surface, a ceiling surface, a floor surface, or the like. Such foam is a material having low thermal conductivity, and as a typical example thereof, organic foam such as urethane foam, phenol foam, and styrene foam is used. Of these, urethane foam is frequently used because it has excellent low thermal conductivity of about 0.025 W / (m · K) and can be constructed at a relatively low cost. Has been done. However, since organic foams such as urethane foams are mainly composed of organic substances, it tends to be difficult to obtain high performance in resistance to flames and high heat, that is, heat resistance.

Special Table 2016-531966 Gazette Japanese Unexamined Patent Publication No. 2011-195703

In Patent Document 1 (Japanese Patent Laid-Open No. 2016-531966) and the like, an attempt is made to impart heat resistance and the like to a foam having low thermal conductivity by a composition containing a polyol-based compound, an isocyanate-based compound, and a solid flame retardant. ing. As the solid flame retardant, a phosphorus flame retardant such as triphenyl phosphate, a halogen flame retardant such as decabromodiphenyl oxide, a metal hydrate flame retardant such as aluminum hydroxide and magnesium hydroxide, etc. are described. There is.

However, in the foam formed by the composition of the above patent documents and the like, there is room for improvement in terms of heat resistance. Further, in such a foam, discoloration occurs over time, and the aesthetic appearance is apt to be impaired.

Patent Document 2 (Japanese Unexamined Patent Publication No. 2011-195703) describes a paint for foam. By painting the surface of the foam with such a paint, it is possible to impart aesthetic appearance to the foam. However, covering the foam with such a paint is disadvantageous in terms of heat resistance.

The present invention has been made in view of such problems, and a main object of the present invention is to provide a foam laminate having excellent performance in low thermal conductivity, heat resistance, aesthetics and the like.

As a result of diligent studies to solve the above problems, the present inventors have come up with the idea of laminating a specific foam layer and a covering material layer, respectively, and have completed the present invention.

（式２）

（Ｒ ^１、Ｒ ^２は、同一であるかまたは異なるものであり、線状または分枝状の炭素数１～６のアルキルである。Ｒ ^３は、線状または分枝状の炭素数１～１０のアルキレン、炭素数６～１０のアリーレン、炭素数７～２０のアルキルアリーレン、または炭素数７～２０のアリールアルキレンである。Ｍは、Ｍｇ、Ｃａ、Ａｌ、Ｓｂ、Ｓｎ、Ｇｅ、Ｔｉ、Ｚｎ、Ｆｅ、Ｚｒ、Ｃｅ、Ｂｉ、Ｓｒ、Ｍｎ、Ｌｉ、Ｎａ、Ｋ、またはプロトン化窒素塩基である。ｍは１～４、ｎは１～４、ｘは１～４である。）
３．上記硬化性組成物のイソシアネート指数が１５０～８００であることを特徴とする１．または２．記載の積層体。
４．上記フォーム層の厚みが１０ｍｍ～５００ｍｍであることを特徴とする１．から３．のいずれかに記載の積層体。
That is, the present invention has the following features.
1. 1. A laminate having a dressing layer on top of the foam layer.
The foam layer contains a polyol compound, a foaming agent, a catalyst, a foam stabilizer, a phosphorus compound, and a polyisocyanate compound, and is formed of a curable composition containing the phosphinate compound as the phosphorus compound. can be,
The coating material layer is a laminate characterized in that it is formed of an inorganic coating material containing an inorganic binder.
2. 2. 1. The phosphorus compound contains an alkylphosphinic acid metal salt compound represented by the following (formula 1) or the following (formula 2). The laminate described.
(Equation 1)

(Equation 2)

(R ¹ and R ² are the same or different, and are linear or branched alkyls having 1 to 6 carbon atoms. R ³ is linear or branched carbon atoms 1 to 6. It is an alkylene having 10 carbon atoms, an arylene having 6 to 10 carbon atoms, an alkyl arylene having 7 to 20 carbon atoms, or an arylalkylene having 7 to 20 carbon atoms. M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base. M is 1 to 4, n is 1 to 4, and x is 1 to 4.)
3. 3. 1. The curable composition has an isocyanate index of 150 to 800. Or 2. The laminate described.
4. 1. The thickness of the foam layer is 10 mm to 500 mm. From 3. The laminate described in any of.

The laminate of the present invention can exhibit excellent performance in terms of low thermal conductivity, heat resistance, aesthetics and the like.

Hereinafter, embodiments for carrying out the present invention will be described.
The laminate of the present invention has a coating material layer on the foam layer, the foam layer is formed by a specific curable composition, and the coating material layer is formed by a specific inorganic coating material.

In conventional general urethane foam or the like, the entire foam burns and shrinks due to flame or high heat, a healthy part (non-carbonized part) is lost, and the dimensions of the foam may change significantly. On the other hand, in the laminated body of the present invention, when exposed to flame or high heat, combustion, shrinkage, dimensional change and the like of the foam are suppressed, and the progress of thermal decomposition in the foam is also suppressed. As a result, even if the laminated body is exposed to flame or high heat, a healthy portion tends to remain in the foam layer. As described above, the laminated body of the present invention can obtain a remarkable effect in heat resistance and the like as compared with the prior art. Further, in the laminated body of the present invention, a desired color or the like can be imparted by the coating material layer formed from the inorganic coating material, and the aesthetic appearance can be enhanced. And the aesthetics can be maintained for a long time.

[Cursable composition]
In the present invention, the curable composition forming the foam layer contains a polyol compound, a foaming agent, a catalyst, a defoaming agent, a phosphorus compound, and a polyisocyanate compound as essential components.

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

Among these, examples of the polyester polyol include aromatic polyester polyols, aliphatic polyester polyols, aromatic / aliphatic polyester polyols, and one or more of these can be used. Specifically, examples of the aromatic polyester polyol include a condensed polyester polyol obtained by reacting an aromatic polybasic acid such as orthophthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride with a polyhydric alcohol, polyethylene terephthalate, and the like. Examples thereof include a phthalic acid-based polyester polyol obtained by decomposing a phthalic acid-based polyester molded product. Examples of the aliphatic polyester polyol include a condensed polyester polyol obtained by reacting an aliphatic polybasic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, and fumaric acid with a polyhydric alcohol. Be done. Examples of the aromatic / aliphatic polyester polyol include aromatic polybasic acids and condensed polyester polyols obtained by reacting an aliphatic polybasic acid with a polyhydric alcohol.
In the present invention, it is desirable to include a polyester polyol as the polyol compound, an aromatic polyester polyol from the viewpoint of heat resistance, an aliphatic polyester polyol from the viewpoint of adhesiveness, or an aromatic polyester from the viewpoint of heat resistance, adhesiveness, etc. / Aliphatic polyester polyol or the like can be used alone or in a blend. In the present invention, it is particularly preferable to include an aromatic / aliphatic polyester polyol.

Examples of the polyether polyol include aromatic polyether polyols, phosphorus-containing polyether polyols, glycerin-based polyether polyols, and amino group-containing polyether polyols. Specifically, as the aromatic polyether polyol, for example, a bisphenol A type polyether polyol obtained by adding an alkylene oxide (for example, ethylene oxide, propylene oxide, etc.) using bisphenol A as an initiator, an aromatic amine ( For example, by adding an alkylene oxide using toluenediamine, diethyltoludiamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, triethanolamine, Mannig condensate, etc.) as an initiator. Examples thereof include the obtained aromatic amine-based polyether polyol. Examples of the phosphorus-containing polyether polyol include dialkyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, which is a diol having a phosphoric acid 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 to a low molecular weight amine (for example, 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 50 mgKOH / g or more and 500 mgKOH / g or less.
The hydroxyl value is a value represented by the number of mg of potassium hydroxide equivalent to the hydroxyl group contained in 1 g of the sample, and is JIS K 1557-1: 2007 Plastic-Polyurethane Raw Material Polyurethane Test Method-Part 1: Hydroxy Group Value. It is a value measured based on the method of obtaining. The hydroxyl value of the component (A) is a value measured with a mixture of all the components (A).

Further, the polyol compound in the present invention preferably contains a polyol having an acid value, particularly a polyester polyol having an acid value, from the viewpoint of storage stability and the like. The acid value is not particularly limited, but is preferably 10 mgKOH / g or more and 300 mgKOH / g or less (further, 20 mgKOH / g or more and 250 mgKOH / g or less). The acid value is the number of mg of potassium hydroxide required to neutralize the acid component present in 1 g of the sample. JIS K 5601-2-1: 1999 Paint component test method "Acid value (titration method)" It is a value measured based on.
The ratio of the polyol having an acid value contained in the polyol compound is preferably 0.1% by weight or more and 20% by weight or less, and more preferably 0.5% by weight or more and 15% by weight or less.

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

Among these, examples of the hydrocarbon include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptan 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 so on. Examples of the hydrofluorocarbon (HFC) include difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,1-trifluoroethane (HFC143a), 1,1,1. 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 3,4,5,5,5-decafluoropentane (HFC4310mee) and the like can be mentioned.

Examples of the hydrofluoroolefin (HFO) include pentafluoropropene such as 1,2,3,3,3-pentafluoropropene (HFO1225ye), 1,3,3,3-tetrafluoropropene (HFO1234ze), 2, Tetrafluoropropene such as 3,3,3-tetrafluoropropene (HFO1234yf), 1,2,3,3-tetrafluoropropene (HFO1234ye), trifluoropropene such as 3,3,3-trifluoropropene (HFO1243zf) , Tetrafluorobutene (HFO1345), pentafluorobutene (HFO1354), hexafluorobutene (HFO1336), heptafluorobutene (HFO1327), heptafluoropentene (HFO1447), octafluoropentene (HFO1438), nonafluoropentene (HFO1429), etc. , Or these isomers (cis form, 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), and the like. Dichlorotrifluoropropene (HCFO1223) and the like, or isomers thereof (cis form, trans form) and the like can be mentioned.
As the foaming agent in the present invention, one or more selected from hydrofluoroolefins, hydrochlorofluoroolefins, and waters are suitable, and for example, hydrofluoroolefins and water, hydrochlorofluoroolefins and water, and hydrofluoroolefins. A foaming agent such as hydrochlorofluoroolefin and water can be used in combination.

The mixing amount of the foaming agent is preferably 10 to 200 parts by weight, more preferably 20 to 180 parts by weight, and further preferably 30 to 150 parts by weight with respect to 100 parts by weight of the polyol compound.

The catalyst is not particularly limited, and examples thereof include a nurateization catalyst, a foaming catalyst, a resinification catalyst, and the like, and one or more of these can be used.
The nurateization catalyst is not particularly limited as long as it is a catalyst effective for isocyanurate formation, and is, for example, a tetraalkylammonium hydroxide such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, or trimethylbenzylammonium, or an organic acid thereof. Salts (as organic acids such as acetic acid, caproic acid, octyl acid, myristic acid, lactic acid, etc.), trialkylhydroxyalkylammoniums such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, triethylhydroxyethylammonium, etc. Hydrooxides or organic acid salts thereof, metal salts of alkylcarboxylic acids (eg acetic acid, caproic acid, octyl acid, myristic acid, lactic acid, etc.), β-diketone metal chelate compounds such as aluminum acetylacetone, lithium acetylacetone, aluminum chloride, Examples thereof include Friedel-crafts catalysts such as boron trifluoride, organic metal compounds such as titanium tetrabutyrate and tributylantimon oxide, and aminosilyl group-containing compounds such as hexamethylsilazane, and one or more of these may be used. 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 can be mentioned, and one or more of these can be used.
Examples of the resinification 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, 135-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, or organic acid salts thereof, Bismastris (2-ethylhexanoate), Bismastris (neodecanoate), Bismastris (palmitate), Bismastetramethylheptanedioate, Bismus naphthenate, Dibutyltin dilaurate, Dibutyltin dimalate, Dibutyltin diacetate, Dioctyltin diacetate , Organic metals such as tin octylate, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 1-isobutyl-2-methylimidazole, etc. Imidazole or N-methyl-N'-(2-dimethylaminoethyl) piperazine, N, N'-dimethylpiperazine, N-methylpiperazine, N-methylmorpholin, N-ethylmorpholin, 1,8-diazabicyclo [5] 4.0] Undecene-7, 1,1'-(3- (dimethylamino) propyl) imino) bis (2-propanol) and the like, and one or more of these can be used.

The mixing amount (in terms of active ingredient) of the catalyst is preferably 0.1 to 40 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the polyol compound. 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 desirable to include a foaming catalyst and / or a resinification catalyst together with the nurateization catalyst as a catalyst, and it is particularly desirable to include a foaming catalyst and a resinification catalyst together with the nurateization catalyst.

Examples of the defoaming agent include a silicone-based defoaming agent such as a polyether-modified silicone compound, a fluorine-containing compound-based defoaming agent, and the like. These can be used in one type or two or more types. 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 0.1 to 40 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the polyol compound.

The curable composition in the present invention contains a phosphinate compound as a phosphorus compound. In the present invention, the heat resistance and the like of the foam layer can be dramatically improved by containing such a phosphinate compound.

（式２）

（Ｒ^１、Ｒ^２は、同一であるかまたは異なるものであり、線状または分枝状の炭素数１～６のアルキルである。Ｒ^３は、線状または分枝状の炭素数１～１０のアルキレン、炭素数６～１０のアリーレン、炭素数７～２０のアルキルアリーレン、または炭素数７～２０のアリールアルキレンである。Ｍは、Ｍｇ、Ｃａ、Ａｌ、Ｓｂ、Ｓｎ、Ｇｅ、Ｔｉ、Ｚｎ、Ｆｅ、Ｚｒ、Ｃｅ、Ｂｉ、Ｓｒ、Ｍｎ、Ｌｉ、Ｎａ、Ｋ、またはプロトン化窒素塩基である。ｍは１～４、ｎは１～４、ｘは１～４である。） As the phosphinate compound, an alkylphosphinic acid metal salt compound represented by the following (formula 1) or the following (formula 2), and one or more selected from these polymers are suitable.
(Equation 1)

(Equation 2)

(R ¹ and R ² are the same or different, and are linear or branched alkyls having 1 to 6 carbon atoms. R ³ is linear or branched carbon atoms 1 to 6. It is an alkylene having 10 carbon atoms, an arylene having 6 to 10 carbon atoms, an alkyl arylene having 7 to 20 carbon atoms, or an arylalkylene having 7 to 20 carbon atoms. M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base. M is 1 to 4, n is 1 to 4, and x is 1 to 4.)

R ¹ and R ² are preferably the same or different, and are methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl, or phenyl. R3 is preferably methylene ^, ethylene, n-propylene, i-propylene, n-butylene, t-butylene, n-pentylene, n-octylene, n-dodecylene, phenylene, naphthylene, methylphenylene, ethylphenylene, and the like. It is t-butylphenylene, methylnaphthylene, ethylnaphthylene, t-butylnaphthylene, phenylmethylene, phenylethylene, phenylpropylene, or phenylbutylene. The M is preferably Mg, Ca, Al, Sn, Ti, Zn, Fe, or Zr.

Such an alkylphosphinic acid metal salt compound can be obtained by reacting, for example, an alkyl subsulfonic acid and / or a phosphinic acid and / or an alkali metal salt thereof with an olefin in the presence of a free radical initiator to obtain an alkylphosphinic acid and / or an alkylphosphinic acid and / or an alkali metal salt thereof. / Or it can be obtained by obtaining an alkali metal salt thereof and further reacting with a metal compound or the like. Specifically, examples of the alkylphosphinic acid metal salt compound include tris (diethylphosphinic acid) aluminum, tris (methylethylphosphinic acid) aluminum, tris (butylethylphosphinic acid) aluminum, tris (diphenylphosphinic acid) aluminum, and bis. (Diethylphosphinic acid) zinc, bis (methylethylphosphinic acid) zinc, bis (diphenylphosphinic acid) zinc, bis (diethylphosphinic acid) titanyl, tetrakis (diethylphosphinic acid) titanium, bis (methylethylphosphinic acid) titanyl, tetrakis (Methylethylphosphinic acid) titanium, bis (diphenylphosphinic acid) titanyl, tetrakis (diphenylphosphinic acid) titanium and the like can be mentioned, and one or more of these can be used. Of these, tris (alkylphosphinic acid) aluminum selected from tris (diethylphosphinic acid) aluminum, tris (methylethylphosphinic acid) aluminum, tris (butylethylphosphinic acid) aluminum, and tris (diphenylphosphinic acid) aluminum is particularly preferable. be.

The phosphinate compound is preferably powdery at room temperature (20 ° C.), and its average particle size is preferably 50 μm or less, more preferably 0.5 to 30 μm. The average particle size referred to here can be measured by a laser diffraction type particle size distribution meter. The density of the phosphinate compound is preferably 1.0 to 1.8 g / cm ³ , more preferably 1.2 to 1.5 g / cm ³ . The density is a value at 20 ° C.

The mixing amount of the phosphinate compound is preferably 1 to 300 parts by weight, more preferably 2 to 150 parts by weight, still more preferably 3 to 135 parts by weight, and most preferably 3 to 135 parts by weight, based on 100 parts by weight of the solid content of the polyol compound. It is 5 to 100 parts by weight. When the mixing amount of the phosphinate compound is within such a range, it is suitable in terms of heat resistance and the like.

In the curable composition of the present invention, as the phosphorus compound, a phosphorus compound other than the above phosphinate compound, for example, an organic phosphoric acid ester compound or the like can also be used. Examples of the organic phosphoric acid ester compound include halogenated alkyl esters of phosphoric acid, alkyl phosphoric acid esters, aryl phosphoric acid esters, phosphonic acid esters and the like, and one or more of these can be used. Specific examples of the organic phosphate ester compound include tris (chloroethyl) phosphate, tris (β-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tributoxyethyl phosphate, tributyl phosphate, triethyl phosphate, and cresylphenyl phosphate. , Dimethylmethylphosphonate and the like. In the present invention, by containing the phosphinate compound and the organic phosphate ester compound as the phosphorus compound, the viscosity of the curable composition is reduced, the storage stability is improved, the workability during construction is improved, and the heat resistance of the foam is improved. Can be improved.

The mixing amount of the organic phosphoric acid ester compound is preferably 10 to 800 parts by weight, more preferably 30 to 600 parts by weight, and further preferably 50 to 400 parts by weight with respect to 100 parts by weight of the polyol compound.

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), hexamethylene diisocyanate (HMDI) and the like. In the present invention, MDI is preferable from the viewpoints of ease of handling, speed of reaction, physical characteristics of the obtained foam, cost advantage, and the like. Examples of MDI include monomeric MDI and polypeptide MDI (polymethylene polyphenyl isocyanate).

In the curable composition of the present invention, the polyol compound and the polyisocyanate compound have an isocyanate index of preferably 150 or more, more preferably 180 to 800, still more preferably 200 to 500, and most preferably 250 to 400. Etc. are desirable to mix. When the isocyanate index is within such a range, it is suitable in terms of heat resistance and the like. The isocyanate index is expressed as 100 times the numerical value obtained by dividing the equivalent number of isocyanate groups of the polyisocyanate compound by the total equivalent number of active hydrogen of the active hydrogen-containing component (polyol compound, water, etc.). be.

The curable composition can contain an ethylenically unsaturated double bond-containing compound in addition to the above-mentioned components. In the present invention, by using such an ethylenically unsaturated double bond-containing compound, effects such as heat resistance due to the phosphinic acid salt compound can be obtained even more efficiently. Examples of the ethylenically unsaturated double bond include a (meth) acryloyl group, an allyl group, a propenyl group and the like.

The ethylenically unsaturated double bond-containing compound preferably has an ethylenically unsaturated double bond concentration in the molecule of 0.5 to 20 mmol / g from the viewpoint of the above-mentioned effects and the like, and is preferably 5 to 15 mmol / g. Is more preferable. The concentration of ethylenically unsaturated double bonds in the molecule is represented by the number of moles of the ethylenically unsaturated double bonds in the molecule, and the number of ethylenically unsaturated double bonds in the molecule is the molecular weight. It is expressed as 1000 times (mmol / g) the value divided by.

Specific examples of the ethylenically unsaturated double bond-containing compound include polyhydric alcohols (for example, dihydric or higher alcohols and derivatives thereof, divalent or higher phenols, polyols, etc.) and unsaturated carboxylic acids ((for example). Reactants with (meth) acrylic acids, etc.), reactants with amines (eg, divalent or higher amines, alkanolamines, etc.) and unsaturated carboxylic acids, unsaturated carboxylic acid thioesters of thiols or unsaturated alkylthioethers, Examples thereof include a bisphenol A-based (meth) acrylate compound, a reaction product of a glycidyl group-containing compound and an unsaturated carboxylic acid, a (meth) acrylate compound having a urethane bond in the molecule, and nonylphenoxypolyethyleneoxyacrylate. These can be used in one type or two or more types.

Among these, examples of the reaction product of the polyhydric alcohol and the unsaturated carboxylic acid include pentaerythritol tetra (meth) acrylate, pentaerythritol trimethyl (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (dipentaerythritol penta (meth) acrylate. Meta) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, ditri Examples thereof include styrene propanetetra (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-based (meth) acrylate compound include 2,2-bis (4-((meth) acryloxipolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxipoly). Propoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc. Can be mentioned.

Examples of the (meth) acrylate compound having a urethane bond in the molecule include 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. Examples thereof include oxide-modified urethane di (meth) acrylate.

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

In addition to the above components, for example, flame retardants, colorants, surfactants, polymerization inhibitors, fibers and the like can be mixed in the curable composition in the present invention.
Examples of the flame retardant include halogen-based flame retardants, organic bromine-based flame retardants, nitrogen-based flame retardants, metal hydrate-based flame retardants, and the like, among which nitrogen-based flame retardants having a relatively low density are preferable. Is.
Examples of the colorant include pigments and dyes.
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants and the like. Such a surfactant can impart storage stability and dispersion stability.
Examples of the polymerization inhibitor include hydroquinone-based polymerization inhibitors, benzoquinone-based polymerization inhibitors, catechol-based polymerization inhibitors, piperidine-based polymerization inhibitors, and the like. Such a polymerization inhibitor imparts long-term storage stability in the form of a two-component type described later, and also contributes to production stability when added in the polyol production process.
Examples of the fiber include organic fiber and inorganic fiber. Such fibers can impart construction workability, foam formability, dimensional stability and the like. In the present invention, since a specific phosphorus compound is used, it is not necessary to use fibers, but when the fibers are mixed, the effect can be exhibited with a small amount of fibers.

The foam layer formed by such a curable composition is preferably a rigid polyurethane foam layer, more preferably a rigid polyisocyanurate foam layer.

[Inorganic dressing]
The coating material layer in the present invention is formed by an inorganic coating material containing an inorganic binder. In the present invention, by covering the surface of the foam layer with such an inorganic coating material, heat resistance, aesthetics and the like can be improved.

Examples of the inorganic binder include hydraulic inorganic substances, reactive silicon compounds, silicon resins and the like. Examples of water-hard inorganic substances include Portoland cement, alumina cement, ultrafast-hardening cement, expansion cement, acidic phosphate cement, silica cement, lime mixed cement, blast furnace cement, fly ash cement, keence cement, magnesia cement, and dolomite. , Hydrohard lime, gypsum and the like. Examples of the reactive silicon compound include water glass, alkoxysilanes and the like. Examples of the silicon resin include silicones and the like. These can be used in one or more or two or more. When a hydraulic inorganic substance is used as the inorganic binder, a color based on the hydraulic inorganic substance can be imparted.

In the inorganic coating material of the present invention, a desired color tone can be imparted by mixing a coloring pigment. Examples of the coloring pigment include titanium oxide, zinc oxide, aluminum oxide, carbon black, graphite, black iron oxide, copper chrome black, iron chrome black, cobalt black, copper manganese iron black, red iron oxide, molybdate orange, and permanent red. Permanent Carmine, Anthracinone Red, Perylene Red, Kinacridon Red, Yellow Iron Oxide, Titanium Yellow, First Yellow, Benzimidazolone Yellow, Chrome Green, Cobalt Green, Phthalocyanine Green, Ultramarine, Navy Blue, Cobalt Blue, Phthalocyanine Blue, Kinacridon Violet, Ji Oxazine violet and the like can be mentioned. These can be used in one type or two or more types.

In addition to the above components, the inorganic coating material includes extender pigments such as heavy calcium carbonate, clay, kaolin, talc, settling barium sulfate, barium carbonate, white carbon, and diatomaceous earth; and inorganic aggregates such as silica sand and cold water stone. Inorganic lightweight aggregates such as pearlite and expanded vermiculite; heat-absorbing substances such as aluminum hydroxide, magnesium hydroxide, zeolite, halloysite, allophene, and ettringite; inorganic fiber substances such as glass fiber and steel fiber; etc. can be mixed. .. Organic binders such as chloroprene rubber, butadiene rubber, acrylic resin, vinyl acetate resin, and epoxy resin; styrene resin foam, ethylene vinyl acetate resin foam, vinyl chloride resin foam, as long as the effects of the present invention are not significantly impaired. Organic lightweight aggregate such as body;
Organic fiber substances such as vinylon fiber and pulp fiber; In addition, a thickener, a defoaming agent, a water reducing agent, a swelling agent, a coagulation accelerator, a surfactant and the like can be mixed.

[Laminate]
The laminate of the present invention can be obtained by applying the above-mentioned curable composition to a base material and foaming it to form a foam layer, and then forming a coating material layer with the above-mentioned inorganic coating material. can.

It is desirable that the laminate of the present invention is formed on a base material in a field such as a building. The target base material is, for example, a material constituting a wall surface, a ceiling surface, a floor surface, etc. in a building or the like, and specific examples thereof include concrete, mortar, metal plate, inorganic board, plywood, and the like. .. These base materials may be surface-treated with an undercoat material or the like before foam formation.

It is desirable that the curable composition in the present invention is kept in a two-component form at the time of distribution and mixed at the time of use (at the time of forming a foam layer). In such a two-component form, for example, the first solution contains a polyol compound, a foaming agent, a catalyst, a defoaming agent, and a phosphorus compound, and the second solution contains a polyisocyanate compound. Can be done.

When the curable composition is applied to the base material, for example, a spray foaming machine for spraying work (for example, a two-component tip mixture type spray coating machine or the like) is used to use the first liquid. It may be carried out by spraying a mixture of the second liquid and the second liquid. In this case, it is preferable to set the temperature of the first liquid and the second liquid to be preferably about 20 to 60 ° C, more preferably about 30 to 50 ° C, respectively. The first liquid and the second liquid thus set to a predetermined temperature are mixed at the tip of the spray and sprayed toward the base material to form a foam on the base material. It is desirable that the mixing of the first liquid and the second liquid is about 1: 1 in volume ratio. The foam layer formed by such a method can exhibit excellent performance in low thermal conductivity, heat resistance and the like. The thickness of the foam layer is not particularly limited and may be appropriately set according to the required performance and the like, but is preferably 10 mm or more, more preferably about 15 to 500 mm.

In the present invention, the coating material layer can be formed by applying the above-mentioned inorganic coating material on the foam layer (surface), drying and curing the above-mentioned inorganic coating material. At this time, water or the like can be mixed with the inorganic coating material, if necessary. The inorganic dressing is preferably applied directly onto the foam layer. When applying the inorganic coating material, a coating tool such as a trowel, a spray, a roller, or a brush can be appropriately used. The thickness of the coating material layer to be formed may be appropriately set according to the application site, application, required performance, etc., but is preferably 0.2 to 20 mm, more preferably about 0.5 to 15 mm.

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

[Cursable composition]
Regarding the curable composition forming the foam layer, a first liquid (1st liquid 1 to 35) in which the following raw materials were uniformly mixed at the weight ratio shown in Table 1 was prepared. As the second liquid, a liquid made of polyvinyl MDI (second liquid 1) was prepared. In Table 1, the amount of the active ingredient is shown for the catalyst.
-Polyol compound 1: Aromatic polyester polyol (terephthalic acid-based polyester polyol, acid value: 0 mgKOH / g, hydroxyl value: 250 mgKOH / g)
Polyol compound 2: Aliphatic polyester polyol (succinic acid-based polyester polyol, acid value: 0 mgKOH / g, hydroxyl value: 100 mgKOH / g)
Polyol compound 3: Aromatic polyether polyol (Mannig-modified polyether polyol, acid value: 0 mgKOH / g, hydroxyl value: 350 mgKOH / g)
Polyol compound 4: Aromatic / aliphatic polyester polyol (phthalic acid / adipic acid-based polyester polyol, acid value: 0 mgKOH / g, hydroxyl value: 350 mgKOH / g)
Polyol compound 5: Aromatic polyester polyol (phthalic acid polyester polyol, acid value: 160 mgKOH / g, hydroxyl value: 250 mgKOH / g)
・ Foaming agent 1: Hydrochlorofluoroolefin ・ Foaming agent 2: Hydrofluoroolefin ・ Foaming agent 3: Water (hydroxyl value: 6233 mgKOH / g)
-Catalyst 1: Nurateization catalyst (tetraalkylammonium organic acid salt)
-Catalyst 2: Resinification catalyst (1,2-dimethylimidazole)
-Catalyst 3: Foaming catalyst (bis (2-dimethylaminoethyl) ether)
-Phosphorus compound 1: Phosphorate compound (tris (diethylphosphinic acid) aluminum, average particle size 4 μm, density 1.35 g / cm ³ )
-Phosphorus compound 2: Phosphorate compound (tris (diethylphosphinic acid) aluminum, average particle size 10 μm, density 1.35 g / cm ³ )
Phosphorus compound 3: Phosphinate compound (tris (diethylphosphinic acid) aluminum, average particle size 20 μm, density 1.35 g / cm ³ )
-Phosphorus compound 4: Organophosphate ester compound (tris (β-chloropropyl) phosphate, density 1.29 g / cm ³ )
Double bond compound 1: Ethylene unsaturated double bond-containing compound (trimethylol propantriacrylate, ethylenically unsaturated double bond concentration 10 mmol / g, hydroxyl value: 0 mgKOH / g)
Double bond compound 2: Ethylene unsaturated double bond-containing compound (pentaerythritol tetraacrylate, ethylenically unsaturated double bond concentration 11 mmol / g, hydroxyl value: 0 mgKOH / g)
Double bond compound 3: Ethylene unsaturated double bond-containing compound (pentaerythritol triacrylate, ethylenically unsaturated double bond concentration: 10 mmol / g, hydroxyl value: 25 mgKOH / g)
・ Defoaming agent: Silicone-based defoaming agent

[Inorganic dressing]
100 parts by weight of inorganic binder (ordinary Portoland cement), 100 parts by weight of inorganic lightweight aggregate (pearlite, average particle size 0.1 mm), 5 parts by weight of organic binder (ethylene vinyl acetate resin emulsion, solid content 50% by weight), An inorganic coating material 1 was obtained by uniformly mixing 10 parts by weight of an inorganic fiber (glass fiber) and 400 parts by weight of water. The dressing layer formed by the inorganic dressing 1 is referred to as a dressing layer 1.

[Test 1]
As Test 1, the following tests were performed on the foam layer formed by the curable composition.

The first liquid and the second liquid are each heated to 40 ° C., these are mixed so as to have the isocyanate index shown in Table 2, and the obtained mixed liquid is applied to a base material (slate plate) and foamed. A test piece (thickness 50 mm) having a foam layer formed on one surface of the base material was obtained. Each test was carried out on the obtained test piece by the following method. Table 2 shows the combinations of the first liquid and the second liquid forming each foam layer, and the results thereof.

(1) Foam forming property The state of the formed foam was visually observed. The evaluation criteria are as follows.
⊚: A homogeneous foam was formed.
◯: An almost homogeneous foam was formed.
Δ: Some abnormalities (non-uniform foaming, poor adhesion, etc.) were observed in the foam.
X: An abnormality was found in the foam.

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

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

(Evaluation item)
(3-1) Dimensional change A: Dimensional change in the thickness direction after the test is 5 mm or less B: Dimensional change in the thickness direction after the test is 10 mm or less C: Dimensional change in the thickness direction after the test is more than 10 mm and 20 mm or less X: Dimensional change in thickness direction after test is over 20 mm (3-2) Total calorific value A: Total calorific value is 8 MJ / m ² or less X: Total calorific value is over 8 MJ / m ² (3-3) Maximum heat generation rate A : Maximum heat generation rate is 200 kW / m ² or less X: Maximum heat generation rate is over 200 kW / m ²

(Evaluation criteria)
│ │ Heating time │ 3-1 │ 3-2 │ 3-3 │
│ AA │ 20 minutes │ A │ A │ A │
│ A │ 20 minutes │ B │ A │ A │
│ A'│ 20 minutes │ C │ A │ A │
│ B │ 10 minutes │ B │ A │ A │
│ B'│ 10 minutes │ C │ A │ A │
│ C │ 5 minutes │ B │ A │ A │
│ C'│ 5 minutes │ C │ A │ A │
│ D │ 5 minutes │ X │ X │ X │
Regarding heat resistance, it is superior AA>A>A'>B>B'>C>C'> D inferior.

[Test 2]
As test 2, the following test was performed on the laminated body of the foam layer and the dressing layer.

In the same manner as in Test 1, the first liquid and the second liquid are each heated to 40 ° C., these are mixed so as to have the isocyanate index shown in Table 2, and the obtained mixed liquid is used as a base material (slate plate). Was coated and foamed to form a foam layer (thickness 46 mm) on the entire one side of the substrate. Next, a laminate (Examples 1 to 35, Comparative Examples 1 to 4) was obtained by spraying an inorganic coating material on the surface of the foam layer to form a coating material layer (thickness 4 mm). The combinations of the foam layer and the dressing layer in each laminated body are shown in Table 3.

Each of the laminated bodies of Examples 1 to 35 had a white appearance and was excellent in aesthetics. When the heat resistance test was performed on the laminated bodies of Examples 1 to 35 by the same method as in Test 1, all of them showed excellent heat resistance as shown in Table 3.

Claims (4)

A laminate having a dressing layer on top of the foam layer.
The foam layer contains a polyol compound, a foaming agent, a catalyst, a foam stabilizer, a phosphorus compound, and a polyisocyanate compound, and is formed of a curable composition containing the phosphinate compound as the phosphorus compound. can be,
The coating material layer is a laminate characterized in that it is formed of an inorganic coating material containing an inorganic binder. The laminate according to claim 1, wherein the phosphorus compound contains an alkylphosphinic acid metal salt compound represented by the following (formula 1) or the following (formula 2).
(Equation 1)

(Equation 2)

(R ¹ and R ² are the same or different, and are linear or branched alkyls having 1 to 6 carbon atoms. R ³ is linear or branched carbon atoms 1 to 6. It is an alkylene having 10 carbon atoms, an arylene having 6 to 10 carbon atoms, an alkyl arylene having 7 to 20 carbon atoms, or an arylalkylene having 7 to 20 carbon atoms. M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base. M is 1 to 4, n is 1 to 4, and x is 1 to 4.) The laminate according to claim 1 or 2, wherein the curable composition has an isocyanate index of 150 to 800. The laminate according to any one of claims 1 to 3, wherein the foam layer has a thickness of 10 mm to 500 mm.