JP2020033504A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition capable of forming a foam having excellent heat insulation and heat resistance as well as excellent aesthetics without color unevenness. The curable composition of the present invention is characterized by containing a polyol compound, a foaming agent, a catalyst, a flame retardant, a dye, and a polyisocyanate compound, and further containing a phosphinate compound as a flame retardant and a specific amount of the dye. To do. [Selection diagram] None

Description

  The present invention relates to curable compositions suitable for foamed-in-place foam formation. The curable composition of the present invention is capable of forming a foam having excellent aesthetics as well as excellent heat insulating properties 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, with the expansion of applications, such urethane foams are also being used in places that are visible to the public, and the aesthetics of the surface are becoming problematic. Improvement is urgently needed.

  The present inventor has conducted intensive studies to solve the above problems, and as a result, contains a polyol compound, a foaming agent, a catalyst, a flame retardant, a dye, a polyisocyanate compound, and contains a phosphinate compound and a dye as a flame retardant in a specific amount. The present inventors have found that the curable composition has excellent aesthetics as well as excellent heat insulating properties and heat resistance, and have completed the present invention.

That is, the present invention has the following features.
1. A curable composition for forming a foam,
Contains a polyol compound, a foaming agent, a catalyst, a flame retardant, a dye, and a polyisocyanate compound,
The flame retardant comprises a phosphinate 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.

  ADVANTAGE OF THE INVENTION According to this invention, the foam which has the outstanding heat insulation property, the color appearance, etc. and the outstanding aesthetics can be formed.

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

  The curable composition of the present invention can be applied 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 a polyester polyol, a polyether polyol, a polycarbonate polyol, a polylactone polyol, a polybutadiene polyol, a polypentadiene polyol, and a castor oil-based polyol. 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 (for example, ethylene oxide, propylene oxide, or the like) 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 with 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, for example, 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, still more 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.

  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.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 (for example, 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 metals such as tetramethylheptanedioate, 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 5 to 48 parts by weight, further preferably 10 to 45 parts by weight, based on 100 parts by weight of the polyol compound. And most preferably 20 to 40 parts by weight. 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.

  The curable composition of the present invention is characterized by containing a phosphinate compound as a flame retardant. By containing a phosphinate compound, the heat resistance of the foam can be dramatically improved, and the effect of uniformly dispersing the dye is suppressed. Can be formed.

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 (diethylphosphinate) 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.
In the present invention, in particular, aluminum tris (diethylphosphinate), aluminum tris (methylethylphosphinate), aluminum tris (dibutylphosphinate), aluminum tris (butylethylphosphinate), aluminum tris (diphenylphosphinate), bis ( Zinc (diethylphosphinic acid), zinc bis (methylethylphosphinic acid), zinc bis (diphenylphosphinic acid), titanyl bis (diethylphosphinic acid), titanyl tetrakis (diethylphosphinic acid), titanyl bis (methylethylphosphinic acid), tetrakis ( It is preferable to use metal salt compounds of alkyl phosphinic acid such as methyl ethyl phosphinic acid titanyl, bis (diphenyl phosphinic acid) titanyl, and tetrakis (diphenyl phosphinic acid) titanyl. In particular, among these, aluminum tris (alkylphosphinate) selected from aluminum tris (diethylphosphinate), aluminum tris (methylethylphosphinate), aluminum tris (butylethylphosphinate), and aluminum tris (diphenylphosphinate) It is suitable.

The phosphinate compound is preferably in a powder form at normal temperature (20 ° C.), and has an average particle size of preferably 50 μm or less, more preferably 0.5 μm or more and 30 μm or less. In addition, the average particle size mentioned here can be measured by a laser diffraction type particle size distribution meter. The density of the phosphinate compound is preferably from 1.0 g / cm ^{3 to} 1.8 g / cm ³ , more preferably from 1.2 g / cm ^{3 to} 1.5 g / cm ³ . The density is a value at 20 ° C.

  In the curable composition of the present invention, a flame retardant other than the above-mentioned phosphinate compound may be contained as the flame retardant. For example, halogen-based flame retardants, organic bromine-based flame retardants, nitrogen-based flame retardants, metal hydrate-based flame retardants, antimony-based flame retardants, boron-based flame retardants, silicon-based flame retardants, etc., and phosphate esters and polyphosphoric acids Salt compounds, phosphorus-based flame retardants such as halogenated phosphazenes, red phosphorus, phosphorus trichloride, phosphorus pentachloride and the like, 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 bisdixylenyl 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 Nonyldiphenylphosphate, phenylnonylphenylhydroquinonylphosphate, phenyldinonylphenylphosphate, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzylphosphonate, dimethyl-4-hydroxy-3,5-dibromo Benzylphosphonate, diphenyl-4-hydroxy-3,5-dibromobenzylphosphonate and the like.

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

  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.

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 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) based on 100 parts by weight of the polyol compound. , And 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 a phosphate ester and a phosphinate compound in combination. When a phosphate ester and a phosphinate compound are used in combination, the mixing ratio (weight ratio) of the phosphate ester and the phosphinate compound is: It is preferable that the ratio of the phosphoric acid ester to the phosphinate compound is 90:10 to 50:50, more preferably 85:15 to 55:45, and further preferably 80:20 to 60:40. By being in such a range, the workability is excellent and the heat resistance can be further improved.

  Examples of the dye include, for example, an acid dye, an azo dye, a basic dye, a direct dye, a fluorescent dye, a pre-dye dye, an oxidation dye, a solvent dye, a sulfur dye, and a building dye. Can be used. Such a dye is excellent in miscibility with the phosphinate compound described above, so that it is easily dispersed even in the curable composition, without dispersibility of the dye being observed, suppressing color unevenness, A foam having excellent aesthetics can be formed.

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 dye is excellent in miscibility with the above-mentioned phosphinate compound, and is easily dispersed uniformly in the curable composition. Furthermore, it is possible to form a foam having suppressed color unevenness and excellent aesthetics, without being affected by the reaction action and foaming action at the time of spraying work, and without dispersing the dispersibility of the dye.
Examples of such metal complex salt dyes 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, and one or more of these can be used. Specifically, for example, a Bali Fast series (manufactured by Orient Chemical Industry Co., Ltd.), an Eizen Spiron series (manufactured by Hodogaya Chemical Industry Co., Ltd.), an Orazole series (manufactured by BASF Japan Co., Ltd.) and the like can be mentioned.

In the present invention, the mixing amount of the dye is preferably 0.01 to 1 part by weight, more preferably 0.015 to 0.5 part by weight, based on 100 parts by weight of the polyol compound. More preferably, the content is 0.02 parts by weight or more and 0.3 parts 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). I 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), 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.

The curable composition of the present invention preferably has an isocyanate index of 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).
By mixing the polyol compound and the polyisocyanate compound in such a range, excellent heat resistance can be obtained. 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 curable composition of the present invention can contain a foam stabilizer in addition to the above-mentioned components. 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 curable composition 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.

  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 or less in one molecule are preferable from the viewpoint of the above-mentioned effects and the like. More preferably, it is not less 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 these, 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 80 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the polyol compound. Not less than 50 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.

The curable composition of the present invention may contain, for example, a colorant such as a pigment, a surfactant, a polymerization inhibitor, a fiber, and the like, in addition to the above components.
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 in a two-pack type described below, and also contributes to production stability when added during the polyol production process.
Examples of the fibers include organic fibers such as cellulose fibers, polyester fibers, polyethylene fibers, polypropylene fibers, wood fibers, and polyamide fibers, and inorganic fibers such as glass fibers and ceramic fibers. Such fibers can impart workability, foam formability, dimensional stability, and the like. In the present invention, fibers may not be used, but when fibers are mixed, the effect can be exhibited with a small amount of fibers.

The curable composition of the present invention is a foam-forming composition suitable for in-situ foaming, preferably a rigid polyurethane foam-forming composition, more preferably a rigid polyisocyanurate foam-forming composition.
Such a curable composition is applied to a base material at a site such as a building, foamed, and used for covering the base material with a foam. The target substrate is, for example, a material constituting a wall surface, a ceiling surface, a floor surface, and the like in a building or the like, and specifically, for example, concrete, mortar, a metal plate, an inorganic board, a plywood, or the like can be given. . These substrates may be subjected to a surface treatment or the like with an undercoat material before forming the foam.

  It is preferable that the curable composition of the present invention is formed into a two-pack form at the time of distribution, and is mixed and used at the time of use (at the time of foam formation). In such a two-pack form, for example, the first liquid can be a form containing a polyol compound, a foaming agent, a catalyst, a flame retardant, and a dye, and the second liquid can 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 the curable composition to a substrate, for example, the first liquid is sprayed using a spray foaming machine or the like for spraying work (for example, a two-liquid tip mixed type spray coating machine or the like). And a mixture of the second liquid and the second liquid. 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.

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

The first liquid was prepared by uniformly mixing the following raw materials at the weight ratios shown in Table 1. As the second liquid, a liquid composed of polymeric MDI was prepared.
Polyol compound 1: aromatic polyester polyol (terephthalic acid-based polyester polyol, viscosity 1900 mPa · s, acid value: 0 mgKOH / g, hydroxyl value: 250 mgKOH / g)
-Polyol compound 2: aromatic / aliphatic polyester polyol (phthalic acid / adipic acid-based polyester polyol, viscosity 900 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: Nullation catalyst (tetraalkylammonium lactate in glycol solution)
・ Catalyst 3: Resin catalyst (bismuth octylate solution in octylic acid)
Flame retardant 1: phosphinate compound (aluminum tris (diethylphosphinate), average particle size 4 μm, density 1.35 g / cm ³ )
Flame retardant 2: phosphinate compound (aluminum tris (diethylphosphinate), average particle size 10 μm, density 1.35 g / cm ³ )
Flame retardant 3: phosphinate 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: Ethylenically unsaturated double bond-containing compound (trimethylolpropane triacrylate, ethylenically unsaturated double bond concentration 10 mmol / g, hydroxyl value: 0 mgKOH / g)
Double bond compound 2: Ethylenically unsaturated double bond-containing compound (pentaerythritol tetraacrylate, ethylenically unsaturated double bond concentration 11 mmol / g, hydroxyl value: 0 mgKOH / g)
-Foam stabilizer: silicone-based foam stabilizer-Dye 1: C.I. I. Solvent Red 8 (metal complex 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., 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. The specimen was sprayed with a spray gun and foamed to obtain a test body (thickness: 50 mm) in which one side of the substrate was entirely covered with a foam. Each test was performed on the obtained test body by the following method. The results are shown in Table 1.

(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 The surface of the formed foam was visually observed. The evaluation criteria are as follows.
A: There was no color unevenness and the appearance was excellent.
：: Almost no color unevenness and excellent aesthetics.
Δ: Some color unevenness was conspicuous.
X: The color unevenness was conspicuous, and the appearance was poor.

Claims (1)

A curable composition for forming a foam,
Contains a polyol compound, a foaming agent, a catalyst, a flame retardant, a dye, and a polyisocyanate compound,
The flame retardant comprises a phosphinate 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.