JP6901445B2 - Curable composition - Google Patents

Description

The present invention relates to a curable composition suitable for in-situ foam foam formation. The curable composition of the present invention can form a foam having excellent aesthetics as well as excellent heat insulating properties and heat resistance.

Generally, in building structures, heat insulating materials are installed together with flame-retardant materials in order to improve heat insulating performance.
As such a heat insulating material, an organic heat insulating material such as urethane foam, phenol foam, or styrene foam is mainly used. For example, urethane foam is widely used because it has excellent heat insulating properties and can be installed at a relatively low cost.
In recent years, with the improvement of heat resistance of urethane foam, it has become possible to use urethane foam alone, and since it has become possible to use it as a surface material, further expansion of applications is expected. (For example, Patent Documents 1, 2, etc.)

WO2014 / 112394 JP 2015-151524

However, with the expansion of applications, such urethane foams have come to be used in conspicuous places, and the aesthetics of the surface have become a problem. There is an urgent need for improvement.

As a result of intensive research to solve the above problems, the present inventor contains a polyol compound, a foaming agent, a catalyst, a flame retardant, a dye, and a polyisocyanate compound, and contains a specific amount of a phosphinate compound and a dye as the flame retardant. The present invention has been completed by finding that the curable composition has excellent aesthetic properties as well as excellent heat insulating properties and heat resistance.

That is, the present invention has the following features.
1. 1. A curable composition for foam formation,
Contains polyol compounds, foaming agents, catalysts, flame retardants, dyes, and polyisocyanate compounds,
The flame retardant contains a phosphinate compound
The mixing amount of the phosphinate compound is 10 parts by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the polyol compound.
The mixing amount of the dye is 0.01 part by weight or more and 1 part by weight or less with respect to 100 parts by weight of the polyol compound.
A curable composition, wherein the mixing ratio (weight ratio) of the dye and the phosphinate compound is 0.01: 100 to 0.5: 100 .

According to the present invention, it is possible to form a foam having excellent heat insulation and heat resistance as well as excellent aesthetics without color unevenness and the like.

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

The curable composition of the present invention is applicable for foam formation and contains a polyol compound, a foaming agent, a catalyst, a flame retardant, a dye, and a polyisocyanate compound as essential components.

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 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, the aromatic polyester polyol is a polyol having an aromatic hydrocarbon in one molecule, and is, for example, an aromatic polybasic acid such as orthophthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride and a polyhydric alcohol. Examples thereof include a condensed polyester polyol obtained by reacting with and a phthalic acid-based polyester polyol obtained by decomposing a phthalic acid-based polyester molded product such as polyethylene terephthalate. Examples of the polyvalent alcohol include divalent or higher alcohols and derivatives thereof, divalent or higher phenols, polyols and the like.
The aliphatic polyester polyol is a polyol having an aliphatic hydrocarbon in one molecule, and is polyvalent with an aliphatic polybasic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, and fumaric acid. Examples thereof include condensed polyester polyol obtained by reacting with alcohol.
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. Examples thereof include condensed polyester polyols.
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, 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). 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 and N-bis (2-hydroxyethyl) aminomethylphosphonate, which are diols 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 equimolar to the hydroxyl group contained in 1 g of the sample. 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 polyol compound is a value measured with a mixture of all the polyol compounds.

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 hydrofluorocarbons (HFCs) 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-pentafluoroethane (HFC365mfc), 1,1,1,2,2 Examples thereof include 3,4,5,5,5-decafluoropentane (HFC4310mee).

Examples of the hydrofluoroolefin (HFO) include pentafluoropropenes 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 water are suitable, for example, hydrofluoroolefins and water, hydrochlorofluoroolefins and water, and hydrofluoroolefins. Each foaming 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, and 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. Is.

The catalyst is not particularly limited, and examples thereof include a nurateization catalyst, a resination catalyst, a foaming 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 (organic acids such as acetic acid, caproic acid (n-hexanoic acid), octyl acid (2-ethylhexanoic acid), myristic acid, lactic acid, etc.), trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium , Hydrooxides of trialkylhydroxyalkylammoniums such as triethylhydroxyethylammonium or organic acid salts thereof (as organic acids, for example, acetic acid, caproic acid (n-hexanoic acid), octyl acid (2-ethylhexanoic acid), myristic acid. , Lactic acid, etc.), metal salts of alkylcarboxylic acids (eg acetic acid, caproic acid (n-hexanoic acid), octyl acid (2-ethylhexanoic acid), myristic acid, lactic acid, etc.), β of aluminum acetylacetone, lithium acetylacetone, etc. − Examples include metal chelate compounds of diketone, Friedel-crafts catalysts such as aluminum chloride and boron trifluoride, organic metal compounds such as titanium tetrabutyrate and tributylantimon oxide, and aminosilyl group-containing compounds such as hexamethylsilazane. , 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, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine or the like. Organic acid salt, bismastris (2-ethylhexanoate), bismastris (neodecanoate), bismastris (palmitate), bismastetramethylheptandioate, bismuth octylate, bismuth naphthenate, dibutyltin dilaurate, dibutyltin zimalate, Organic metals such as dibutyltin diacetate, dioctyltindiacetate, tin octylate, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-isopropyl imidazole, 1- Imidazole such as isobutyl-2-methylimidazole, or N-methyl-N'-(2-dimethylaminoethyl) piperazine, N, N'-dimethylpiperazine, N-methylpiperazin, 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 two of these. More than seeds 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.

The mixing amount of the catalyst is preferably 0.1 parts by weight or more and 50 parts by weight or less, more preferably 5 parts by weight or more and 48 parts by weight or less, and further preferably 10 parts by weight or more and 45 parts by weight or less with respect to 100 parts by weight of the polyol compound. Most preferably, it is 20 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 resinification catalyst and / or a foaming catalyst together with the nurate-forming catalyst, which is advantageous in terms of workability and foam-forming property. 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.

The curable composition of the present invention is characterized by containing a phosphinate compound as a flame retardant. By containing the phosphinate compound, the heat resistance of the foam can be dramatically improved, and the dye has the effect of uniformly dispersing the dye, which suppresses the bias of the dye, suppresses the color unevenness, and has excellent aesthetics. Foam can be formed.

Examples of the phosphinate compound include sodium phosphinate, calcium phosphinate, aluminum phosphinate, zinc phosphinate, calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, and ethylmethylphosphinic acid. Aluminum, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, tris (diethylphosphinic acid) aluminum, tris (methylethylphosphinic acid) aluminum, tris (dibutylphosphinic acid) aluminum, tris ( Butylethylphosphinic acid) aluminum, tris (diphenylphosphinic acid) aluminum, bis (diethylphosphinic acid) zinc, bis (methylethylphosphinic acid) zinc, bis (diphenylphosphinic acid) zinc, bis (diphenylphosphinic acid) titanyl, tetrakis ( Examples thereof include diethylphosphinic acid) titanyl, bis (methylethylphosphinic acid) titanyl, tetrakis (methylethylphosphinic acid) titanyl, bis (diphenylphosphinic acid) titanyl, tetrakis (diphenylphosphinic acid) titanyl, and the like. More than seeds can be used.
In the present invention, in particular, tris (diethylphosphinic acid) aluminum, tris (methylethylphosphinic acid) aluminum, tris (dibutylphosphinic acid) aluminum, tris (butylethylphosphinic acid) aluminum, tris (diphenylphosphinic acid) aluminum, bis ( Diethylphosphinic acid) zinc, bis (methylethylphosphinic acid) zinc, bis (diphenylphosphinic acid) zinc, bis (diethylphosphinic acid) titanyl, tetrakis (diethylphosphinic acid) titanyl, bis (methylethylphosphinic acid) titanyl, tetrakis (diethylphosphinic acid) It is preferable to use alkylphosphinic acid metal salt compounds such as methyl ethylphosphinic acid) titanyl, bis (diphenylphosphinic acid) titanyl, and tetrakis (diphenylphosphinic acid) titanyl. Tris (alkylphosphinic acid) aluminum selected from methyl ethylphosphinic acid) aluminum, tris (butylethylphosphinic acid) aluminum, and tris (diphenylphosphinic acid) aluminum is preferable.

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 μm or more and 30 μm or less. 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 g / cm ³ or more and 1.8 g / cm ³ or less, and more preferably 1.2 g / cm ³ or more and 1.5 g / cm ³ or less. The density is a value at 20 ° C.

In the curable composition of the present invention, a flame retardant other than the above phosphinate compound can be included as the flame retardant. For example, halogen-based flame retardants, organic brominated flame retardants, nitrogen-based flame retardants, metal hydrate-based flame retardants, antimony-based flame retardants, boron-based flame retardants, silicon-based flame retardants, etc. Examples thereof include salt compounds, halogenated phosphazene, red phosphorus, phosphorus trichloride, phosphorus pentachloride and other phosphorus-based flame retardants, 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 cresylphenyl. Phosphate, cresildiphenyl phosphate, octyldiphenyl phosphate, trixylenyl phosphate, diisopropylphenyl phosphate, tris (2-ethylhexyl) phosphate, resorcinol bisdiphenyl phosphate, bisphenol A bis (diphenyl phosphate), resorcinol bisdixylenyl phosphate, tris (Chloroethyl) phosphate, Tris (chloropropyl) phosphate, Tris (dichloropropyl) phosphate, Bis (2,3-dibromopropyl) -2,3-dichloropropyl phosphate, Tris (2,3-dibromopropyl) phosphate, Bis ( Chloropropyl) monooctyl phosphate, hydroquinonyl diphenyl phosphate, phenylnonylphenyl hydroquinonyl phosphate, phenyldinonyl phenyl phosphate, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphate, dimethyl- Examples thereof include 4-hydroxy-3,5-dibromobenzylphosphonate and diphenyl-4-hydroxy-3,5-dibromobenzylphosphonate.

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

Examples of the halogenated phosphazene include hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene, dodecachlorocyclohexaphosphazene, hexabromocyclotriphosphazene, hexafluorocyclotriphosphazene, octafluorocyclotetraphosphazene, and deca. Fluorocyclopentaphosphazene, dodecafluorocyclohexaphosphazene, hexamethoxycyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, hexaphenoxycyclotriphosphazene, diethoxytetrafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, methoxypentafluorocyclotri Examples thereof include phosphazene, propoxypentafluorocyclotriphosphazene, butoxypentafluorocyclotriphosphazene and the like.

In the present invention, the mixing amount of the flame retardant is 10 parts by weight or more and 1000 parts by weight or less (preferably 30 parts by weight or more and 600 parts by weight or less, more preferably 50 parts by weight or more and 400 parts by weight or less) with respect to 100 parts by weight of the polyol compound. The following) is included. Of these, the phosphinate compound is 10 parts by weight or more and 200 parts by weight or less (more preferably 20 parts by weight or more and 120 parts by weight or less, still more preferably 25 parts by weight or more and 100 parts by weight or less) with respect to 100 parts by weight of the polyol compound. , Most preferably 30 parts by weight or more and 70 parts by weight or less).
In particular, in the present invention, it is preferable to use the phosphoric acid ester and the phosphinate compound in combination, and when the phosphoric acid ester and the phosphinate compound are used in combination, the mixing ratio (weight ratio) of the phosphoric acid ester and the phosphinate compound is determined. The ratio of the phosphoric acid ester to the phosphinate compound is preferably 90: 10 to 50:50, more preferably 85: 15 to 55:45, and further preferably 80:20 to 60:40. Within such a range, the workability is excellent and the heat resistance can be further improved.

Examples of the dye include acidic dyes, azo dyes, basic dyes, direct dyes, fluorescent dyes, yarn dyes, oxidation dyes, solvent dyes, sulfide dyes, architectural dyes, etc., and one or more of these. Can be used. Since such a dye has excellent miscibility with the above-mentioned phosphinate compound, it is easy to disperse uniformly even in the curable composition, and the dispersibility of the dye is not biased, and color unevenness is suppressed. It is possible to form a foam having excellent aesthetics.

In the present invention, it is particularly preferable to use an acid dye and a solvent dye, and it is particularly preferable to use a metal complex salt dye having a metal complex salt structure.
The metal complex salt dye has excellent miscibility with the above-mentioned phosphinate compound, and easily disperses uniformly even in the curable composition. Further, it is possible to suppress color unevenness and form a foam having excellent aesthetics without being affected by the reaction action and the foaming action at the time of spraying and showing a bias in the dispersibility of the dye.
Examples of such a metal complex salt dye include C.I. I. Solvent Yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, 161, 169, C.I. I. Solvent Orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99, C.I. I. Solvent Red 8, 35, 49, 83: 1, 84: 1, 90, 90: 1, 91, 92, 109, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 218, 225, 233, 234, 243, C.I. I. Solvent Violet 2, 21, 21: 1, 46, 49, 56, 58, 61, C.I. I. Solvent Blue 5, 70, 137, C.I. I. Solvent Brown 28, 42, 43, 44, 53, 62, 63, C.I. I. Solvent Black 27, 34, C.I. I. Acid Yellow 59, 121, C.I. I. Acid Orange 74, 162, C.I. I. Acid Red 211 and the like can be mentioned, and one or more of these can be used. Specific examples thereof include the Bali First series (manufactured by Orient Chemical Industries Co., Ltd.), the Eisenspiron series (manufactured by Hodogaya Chemical Co., Ltd.), and the Orazole series (manufactured by BASF Japan Ltd.).

In the present invention, the mixing amount of the dye is preferably 0.01 parts by weight or more and 1 part by weight or less, and more preferably 0.015 parts by weight or more and 0.5 parts by weight or less, based on 100 parts by weight of the polyol compound. More preferably, it is 0.02 part by weight or more and 0.3 part by weight or less.
The mixing ratio (weight ratio) of the dye and the phosphinate compound is 0.01: 100 to 0.5: 100 (preferably 0.02: 100 to 0.3: 100). To do. With such a mixing ratio, it is possible to further suppress color unevenness and form a foam having excellent aesthetics.

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, superiority in terms of cost, and the like. Examples of MDI include monomeric MDI and polypeptide MDI (polymethylene polyphenyl isocyanate).

The curable composition of the present invention preferably has an isocyanate index of 250 or more and 500 or less (further, 280 or more and 480 or less, further 300 or more and 450 or less).
Excellent heat resistance can be obtained by mixing the above-mentioned polyol compound and the above-mentioned polyisocyanate compound in such a range. 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.). is there.

The curable composition of the present invention may contain a defoaming agent in addition to the above-mentioned components. 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 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 defoaming agent is preferably 0.1 parts by weight or more and 40 parts by weight or less, and more preferably 0.5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the polyol compound.

Further, the curable composition of the present invention may 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, a propenyl group and the like. In the present invention, heat resistance, storage stability, workability and the like can be further improved by using such an ethylenically unsaturated double bond-containing compound.

The ethylenically unsaturated double bond-containing compound preferably has an ethylenically unsaturated double bond concentration of 0.5 mmol / g or more and 20 mmol / g or less in one molecule from the viewpoint of the above-mentioned effects and the like, and is preferably 5 mmol. More preferably, it is / g or more and 15 mmol / g or less. The concentration of ethylenically unsaturated double bonds in the molecule is represented by the number of moles of ethylenically unsaturated double bonds in the molecule, and the number of ethylenically unsaturated double bonds in the molecule is the molecular weight. It is 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 ((()). Reactants with (meth) acrylic acid, etc.), reactants with amines (eg, divalent or higher amines, alkanolamines, etc.) and unsaturated carboxylic acids, unsaturated carboxylic acid thioesters of thiols or unsaturated alkyl thioethers, Examples thereof include 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 alone or in combination of two or more.

Among these, examples of the reaction product of the polyhydric alcohol and the unsaturated carboxylic acid include pentaerythritol tetra (meth) acrylate, pentaerythritol trimethylolpropane (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) acryloxypoly) phenyl) propane. Propoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxipolybutoxy) 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. Oxide-modified urethane di (meth) acrylate and the like can be mentioned.

The mixing amount of the ethylenically unsaturated double bond-containing compound is preferably 1 part by weight or more and 100 parts by weight or less, more preferably 5 parts by weight or more and 80 parts by weight or less, and further preferably 10 parts by weight with respect to 100 parts by weight of the polyol compound. It is 50 parts by weight or more and 50 parts by weight or less. 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, a colorant such as a pigment, a surfactant, a polymerization inhibitor, a fiber, or the like can be mixed in the curable composition of the present invention.
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 two-component form described later, and also contributes to production stability when added in the polyol production process.
Examples of the fiber include organic fibers such as cellulose fiber, polyester fiber, polyethylene fiber, polypropylene fiber, wood fiber and polyamide fiber, and inorganic fiber such as glass fiber and ceramic fiber. Such fibers can impart workability, foam formability, dimensional stability and the like. In the present invention, 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 curable composition of the present invention is a composition for forming a foam suitable for in-situ foaming, preferably a composition for forming a rigid polyurethane foam, and more preferably a composition for forming a rigid polyisocyanurate foam.
Such a curable composition is used in the field of a building or the like, where it is applied to a base material and foamed, and the base material is coated with a foam. 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 preferable that the curable composition of 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 foam formation). In such a two-component type, for example, the first liquid may contain a polyol compound, a foaming agent, a catalyst, a flame retardant, and a dye, and the second liquid may contain a polyisocyanate compound. ..

The viscosity of the first liquid is preferably 20 mPa · s or more and 500 mPa · s or less, more preferably 30 mPa · s or more and 350 mPa · s, from the viewpoint of storage stability, handleability, workability at the time of foam formation, etc. of the first liquid. It is s or less, more preferably 50 mPa · s or more and 250 mPa · s or less. The viscosity is the viscosity at 20 rpm (guideline value at the fourth rotation) measured by a BH type viscometer at a temperature of 20 ° C. 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. As a result, stirring work and the like during construction are reduced, and advantageous effects can be obtained in terms of handleability, workability, miscibility with polyisocyanate compounds, and the like.
The viscosity of the second liquid is preferably 20 mPa · s or more and 500 mPa · s or less, more preferably 30 mPa · s or more and 350 mPa · s or less, and further preferably 50 mPa · s or more and 250 mPa · s or less.

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 mixing type spray coating machine or the like) is used to use the first liquid. The mixture of the second liquid and the second liquid may be sprayed. In this case, it is preferable that the temperatures of the first liquid and the second liquid are set to 20 ° C. or higher and 60 ° C. or lower, more preferably 30 ° C. or higher and 50 ° C. or lower, respectively. The first liquid and the second liquid thus set to a predetermined temperature are mixed at the tip of the spray gun and sprayed toward the base material to form a foam on the base material. The spraying environment is preferably 5 ° C. or higher and 45 ° C. or lower.
The mixing of the first liquid and the second liquid is preferably about 1: 1 in volume ratio. 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.

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

As the first liquid, a liquid prepared by uniformly mixing the following raw materials at the weight ratio shown in Table 1 was prepared. As the second liquid, a liquid made of polyvinyl MDI was prepared.
-Polyol compound 1: Aromatic polyester polyol (terephthalic acid-based polyester polyol, viscosity 1900 mPa · s, acid value: 0 mgKOH / g, hydroxyl value: 250 mgKOH / g)
-Polyol compound 2: Aromatic / aliphatic polyester polyol (phthalic acid / adipic acid-based polyester polyol, viscosity 900 mPa · s, acid value: 0 mgKOH / g, hydroxyl value: 350 mgKOH / g)
-Polyol compound 3: Aliphatic polyester polyol (fumaric acid-based polyester polyol, viscosity 6000 mPa · s, acid value: 0 mgKOH / g, hydroxyl value: 150 mgKOH / g)
・ Foaming agent 1: Hydrochlorofluoroolefin ・ Foaming agent 2: Water (hydroxyl value: 6233 mgKOH / g)
-Catalyst 1: Nurateization catalyst (glycol solution of tetraalkylammonium 2-ethylhexanoate)
-Catalyst 2: Nurateization catalyst (glycol solution of tetraalkylammonium lactate)
-Catalyst 3: Resinization catalyst (octylic acid solution of bismuth octylate)
-Flame retardant 1: Phosphinate compound (tris (diethylphosphinic acid) aluminum, average particle size 4 μm, density 1.35 g / cm ³ )
-Flame retardant 2: Phosphinate compound (tris (diethylphosphinic acid) aluminum, average particle size 10 μm, density 1.35 g / cm ³ )
-Flame retardant 3: Phosphate compound (sodium phosphinate, average particle size 5 μm, density 1.39 g / cm ³ )
-Flame retardant 4: Organic phosphate compound (tris (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)
・ Defoaming agent: Silicone-based defoaming agent ・ Dye 1: C.I. I. Solvent Red 8 (metal complex salt dye)
-Dye 2: C.I. I. Solvent blue 78 (luminescent dye)

(Examples 1 to 12, Comparative Example 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 1, and the obtained mixed liquid is used as a base material (slate plate) in an atmosphere of 5 ° C. It was sprayed with a spray gun and foamed to obtain a test piece (thickness 50 mm) in which one side of the base material was covered with foam. Each test was carried out on the obtained test piece by the following method. The results are shown in Table 1.

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

(2) Thermal conductivity A foam portion 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) Aesthetic appearance The surface of the formed foam was visually observed. The evaluation criteria are as follows.
⊚: There was no color unevenness and it was excellent in aesthetics.
◯: There was almost no color unevenness, and it was excellent in aesthetics.
Δ: Some color unevenness was conspicuous.
X: Color unevenness was conspicuous and the aesthetic appearance was inferior.

Claims (1)

A curable composition for foam formation,
Contains polyol compounds, foaming agents, catalysts, flame retardants, dyes, and polyisocyanate compounds,
The flame retardant contains a phosphinate compound
The mixing amount of the phosphinate compound is 10 parts by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the polyol compound.
The mixing amount of the dye is 0.01 part by weight or more and 1 part by weight or less with respect to 100 parts by weight of the polyol compound.
A curable composition, wherein the mixing ratio (weight ratio) of the dye and the phosphinate compound is 0.01: 100 to 0.5: 100 .