JP2020037681A - Curable composition - Google Patents

Abstract

To provide a curable composition that can form a foam having excellent performances such as low thermal conductivity, heat resistance.SOLUTION: A curable composition contains a polyol compound, a foaming agent, a foaming aid, a catalyst, a flame retardant, and a polyisocyanate compound, and contains, as the flame retardant, granules with an average particle size of 1 μm or less.SELECTED DRAWING: None

Description

  The present invention relates to a novel curable composition. The curable composition of the present invention can form a foam having low heat conductivity and excellent heat resistance.

  In general, in a building or the like, a foam is provided on a base material such as a wall surface, a ceiling surface, a floor surface, or the like, so that heat flowing between indoors and outdoors is suppressed. Such a foam is a material having low thermal conductivity, and as a typical example, an organic foam such as a urethane foam, a phenol foam, and a 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 applied at relatively low cost. Have been. However, since organic foams such as urethane foams are mainly composed of organic substances, there is a tendency that it is difficult to obtain high performance in resistance to flames and high heat, that is, heat resistance.

JP 2006-53966 A

  In Patent Literature 1 and the like, an attempt has been made to impart heat resistance and the like to a low heat conductive foam by using a composition containing a polyol compound, an isocyanate compound, and a flame retardant. As this flame retardant, a phosphorus flame retardant such as triphenyl phosphate, a halogen flame retardant such as decabromodiphenyl oxide, and a metal hydrate flame retardant such as aluminum hydroxide and magnesium hydroxide are described.

  However, the compositions described in the above patent documents have room for improvement in the heat resistance of the formed foam.

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

  The present inventors have conducted intensive studies in order to solve the above problems, and as a result, it has been found that the curable composition for forming a foam preferably contains a powder having an average particle diameter of 1 μm or less as a flame retardant. Upon completion, the present invention has been completed.

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 and a polyisocyanate compound,
The flame retardant contains a powder having an average particle diameter of 1 μm or less,
Curable composition characterized by the above-mentioned.
2. The flame retardant comprises a powder having an average particle diameter of 0.01 μm or more and 1 μm or less, and a powder having an average particle diameter of more than 1 μm and 100 μm or less. 3. The curable composition according to item 1.

  ADVANTAGE OF THE INVENTION According to this invention, the foam which has the outstanding performance in low heat conductivity, heat resistance, etc. 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 forming a foam, and is characterized by containing a polyol compound, a foaming agent, a catalyst, a flame retardant, 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 them, examples of the polyester polyol include an aromatic polyester polyol, an aliphatic polyester polyol, an aromatic / aliphatic polyester polyol, and one or more of these can be used.
Specifically, the aromatic polyester polyol is a polyol having an aromatic hydrocarbon in one molecule, for example, an aromatic polybasic acid such as orthophthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride, and a polyhydric alcohol. And a phthalic acid-based polyester polyol obtained by decomposing a phthalic acid-based polyester molded product such as polyethylene terephthalate. Examples of the polyhydric alcohol include dihydric or higher alcohols and derivatives thereof, dihydric or higher phenols, and polyols.
Aliphatic polyester polyols are polyols having an aliphatic hydrocarbon in one molecule, and include, for example, aliphatic polybasic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, and fumaric acid, and polyhydric acids. And condensed polyester polyols obtained by reacting with alcohol.
The aromatic / aliphatic polyester polyol is a polyol having an aliphatic hydrocarbon and an aromatic hydrocarbon in one molecule, and is obtained by reacting an aromatic polybasic acid or an aliphatic polybasic acid with a polyhydric alcohol. And the like.
In the present invention, it is preferable to include a polyester polyol as the polyol compound.

  Examples of the polyether polyol include an aromatic polyether polyol, a phosphorus-containing polyether polyol, a glycerin-based polyether polyol, and an amino group-containing polyether polyol. Specifically, as the aromatic polyether polyol, for example, bisphenol A type polyether polyol obtained by adding an alkylene oxide (eg, ethylene oxide, propylene oxide, etc.) using bisphenol A as an initiator, an aromatic amine ( For example, by adding an alkylene oxide using toluenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, triethanolamine, Mannich condensate or the like as an initiator, The resulting aromatic amine-based polyether polyol and the like can be mentioned. Examples of the phosphorus-containing polyether polyol include dialkyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, which is a diol having a phosphate ester structure. Examples of the glycerin-based polyether polyol include a polyether polyol obtained by adding an alkylene oxide using glycerin as an initiator. Examples of the amino group-containing polyether polyol include those obtained by adding an alkylene oxide using a low molecular weight amine (eg, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, etc.) as an initiator.

The hydroxyl value of the polyol compound in the present invention is not particularly limited, but is preferably from 50 mgKOH / g to 500 mgKOH / g.
The hydroxyl value is a value represented by the number of mg of potassium hydroxide in an equimolar amount to the hydroxyl group contained in 1 g of the sample, and is defined by JIS K1557-1: 2007 Plastics-Polyurethane raw material polyol test method-Part 1: Hydroxyl value Is a value measured based on how to obtain The hydroxyl value of the polyol compound is a value measured for a mixture of all polyol compounds.

  Examples of the foaming agent include hydrocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, hydrofluoroolefin, hydrochlorofluoroolefin, water, liquefied carbon dioxide, and the like, and one or more of these can be used.

  Among them, examples of the hydrocarbon include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like. Examples of the hydrochlorofluorocarbon (HCFC) include 1,1-dichloro-1-fluoroethane (HCFC-141B), 1-chloro-1,1-difluoroethane (HCFC-142B), and chlorodifluoromethane (HCFC-22). And the like. Examples of the hydrofluorocarbon (HFC) include difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,1-trifluoroethane (HFC143a), 1,1, 2,2-tetrafluoroethane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), 1,1,1,2,3,3,3-hepta Fluoropropane (HFC227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluorobutane (HFC365mfc), 1,1,1,2,2,2 3,4,5,5,5-decafluoropentane (HFC4310mee) and the like.

Examples of the hydrofluoroolefin (HFO) include pentafluoropropene such as 1,2,3,3,3-pentafluoropropene (HFO1225ye), 1,3,3,3-tetrafluoropropene (HFO1234ze), Tetrafluoropropene such as 3,3,3-tetrafluoropropene (HFO1234yf) and 1,2,3,3-tetrafluoropropene (HFO1234ye) and trifluoropropene such as 3,3,3-trifluoropropene (HFO1243zf) , Tetrafluorobutene (HFO1345), pentafluorobutene (HFO1354), hexafluorobutene (HFO1336), heptafluorobutene (HFO1327), heptafluoropentene (HFO1474), octafluoropentene (H O1438), nonafluorobutyl pentene (HFO1429), etc., or their isomers (cis isomer, and trans form) and the like. Examples of the hydrochlorofluoroolefin (HCFO) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), Examples thereof include dichlorotrifluoropropene (HCFO1223) and the like, and isomers thereof (cis-form and trans-form).
As the blowing agent in the present invention, one or more selected from hydrofluoroolefins, hydrochlorofluoroolefins, and water are preferable. For example, hydrofluoroolefins and water, hydrochlorofluoroolefins and water, and hydrofluoroolefins Each blowing agent such as hydrochlorofluoroolefin and water can be used in combination.

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

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

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

  Examples of the resination catalyst include triethylenediamine (TEDA), triethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N , N ', N'-tetramethylpropylenediamine, N, N, N', N ", N" -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ', N ", N' Tertiary amines such as '-pentamethyldipropylenetriamine, N, N, N', N'-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, and the like Organic acid salt, bismuth tris (2-ethylhexanoate), bismuth tris (neodecanoate), bismuth tris (palmitate), bis Organic metal such as tetramethylheptane diate, bismuth octylate, bismuth naphthenate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, dioctyltin diacetate, tin octylate, 1-methylimidazole, 2-methylimidazole, Imidazole such as 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 1-isobutyl-2-methylimidazole, or N-methyl-N '-(2-dimethylaminoethyl) piperazine , N, N'-dimethylpiperazine, N-methylpiperazine, N-methylmorpholine, N-ethylmorpholine, 1,8-diazabicyclo [5.4.0] undecene-7,1,1 '-(3- (dimethyl Amino) propyl Imino) bis (2-propanol) and the like, one or two or more of these can be used.

  Examples of the foaming catalyst include N, N, N ', N', N "-pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N', N"- Pentamethyldipropylenetriamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethoxyethanol, N, N, N ′, N ″, N ′ ″, N ′ ″-hexamethyl Triethylenetetramine, N, N, N ', N "-tetramethyl-N"-(2-hydroxylethyl) triethylenediamine, N, N, N', N "-tetramethyl- (2-hydroxylpropyl ) Tertiary amines such as triethylenediamine or organic acid salts thereof, and one or more of these can be used.

The mixing amount of the catalyst is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 48 parts by weight, and still more preferably 1 to 45 parts by weight, based on 100 parts by weight of the polyol compound. Parts by weight, most preferably 3 parts by weight or more and 40 parts by weight or less. When the catalyst contains an active hydrogen-containing component, the isocyanate index is calculated in consideration of the active hydrogen-containing component contained in the catalyst.
In the present invention, it is particularly preferable to include a resin conversion catalyst and / or a foaming catalyst together with the nullation catalyst, which is advantageous in terms of foamability and workability. When the catalyst contains an active hydrogen-containing component, the isocyanate index is calculated in consideration of the active hydrogen-containing component contained in the catalyst.

Examples of the flame retardant include halogen-based flame retardants, organic bromine-based flame retardants, nitrogen-based flame retardants, phosphorus-based flame retardants, metal hydrate-based flame retardants, antimony-based flame retardants, boron-based flame retardants, and silicon-based flame retardants. And the like. In the present invention, the flame retardant contains a powder having an average particle diameter of 1 μm or less (preferably 10 nm to 900 nm, more preferably 30 nm to 800 nm) (hereinafter also referred to as “particle A”). It is characterized by. By including such a granular material, heat resistance is improved, and a more excellent foam can be formed, and a foam having excellent low thermal conductivity and excellent strength can be obtained.
In the present invention, together with the powder A, the powder having an average particle diameter of more than 1 μm and 100 μm or less (preferably 2 μm or more and 60 μm or less, more preferably 3 μm or more and 40 μm or less) (hereinafter also referred to as “particle B”). ) Is preferable. By containing the powder B together with the powder A, more excellent heat resistance and lower thermal conductivity can be obtained.
The average particle size of the flame retardant is a value measured by a laser diffraction type particle size distribution analyzer.

Specifically, examples of the powder A and the powder B include polyphosphate compounds, phosphinate compounds, halogenated phosphazenes, phosphoramidates, cyclic phosphoramidates, cyclic phosphate esters, and red phosphorus. Phosphorus flame retardants, such as phosphorus, trichloride, and phosphorus pentachloride; metal hydrate flame retardants, such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, and scandium hydroxide; trioxide Antimony-based flame retardants such as antimony and antimony pentoxide; boron-based flame retardants such as boron nitride, borax, anhydrous borax, boric acid, boric anhydride, zinc borate; and silicon-based flame retardants such as silica. And one or more of these can be used.
In particular, in the present invention, the powder A is a silicon-based flame retardant such as silica, and the powder B is a polyphosphate compound, a phosphinate compound, a halogenated phosphazene, a phosphoramidate, a cyclic phosphoramidate, Use of phosphorus-based flame retardants such as cyclic phosphate, red phosphorus, phosphorus trichloride, phosphorus pentachloride, etc. (more preferably one or more phosphorus-based flame retardants selected from phosphinate compounds and cyclic phosphoramidates) It is preferable that such a combination can improve both heat resistance performances, and can exhibit more excellent heat resistance. Furthermore, it is possible to form a foam having better strength.

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

Examples of the phosphinate compound include sodium phosphinate, calcium phosphinate, aluminum phosphinate, zinc phosphinate, calcium dimethyl phosphinate, aluminum dimethyl phosphinate, zinc dimethyl phosphinate, calcium ethyl methyl phosphinate, and ethyl methyl phosphinate. Aluminum, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, aluminum tris (diethylphosphinate), aluminum tris (methylethylphosphinate), aluminum tris (dibutylphosphinate), tris ( Aluminum (butylethylphosphinate), aluminum tris (diphenylphosphinate), bis (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.

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

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

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

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

  Further, as the flame retardant, a liquid flame retardant may be included in addition to the powder A and the powder B. Examples of the liquid flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, trisnonyl phenyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, and cresyl phenyl phosphate. Zirdiphenyl phosphate, octyl diphenyl phosphate, trixylenyl phosphate, diisopropyl phenyl phosphate, tris (2-ethylhexyl) phosphate, resorcinol bisdiphenyl phosphate, bisphenol A bis (diphenyl phosphate), resorcinol bisdixylenyl phosphate, tris (chloroethyl) Phosphate, Tris (chloropropyl) phosphate, Tris (Dichloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropylphosphate, tris (2,3-dibromopropyl) phosphate, bis (chloropropyl) monooctylphosphate, hydroquinonyldiphenylphosphate, Phenylnonylphenylhydroquinonyl phosphate, phenyldinonylphenyl phosphate, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzylphosphonate, dimethyl-4-hydroxy-3,5-dibromobenzylphosphonate And organic phosphoric ester compounds such as diphenyl-4-hydroxy-3,5-dibromobenzylphosphonate. One or more of these can be used.

The mixing amount of the flame retardant is preferably 1 part by weight or more and 1000 parts by weight or less, more preferably 5 parts by weight or more and 600 parts by weight or less, more preferably 10 parts by weight or more and 400 parts by weight or less with respect to 100 parts by weight of the polyol compound. It is.
Of these, the powder A is preferably 0.01 to 3 parts by weight, more preferably 0.05 to 2 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the polyol compound. It is at least 08 parts by weight and at most 1 part by weight.
Powder B is preferably 1 part by weight or more and 1000 parts by weight or less (more preferably 3 parts by weight or more and 300 parts by weight or less, still more preferably 5 parts by weight or more and 100 parts by weight or less, based on 100 parts by weight of the polyol compound. Most preferably, it is 10 parts by weight or more and 70 parts by weight or less.
When the phosphinate compound is contained as the powder B, the mixing amount of the catalyst is preferably 20 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the polyol compound.
When the powder B contains a cyclic phosphoramidate, the amount of the catalyst is preferably 3 parts by weight or more and 20 parts by weight or less based on 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), 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 130 or more and 500 or less (more preferably 150 or more and 480 or less, more preferably 170 or more and 450 or less).
By mixing the polyol compound and the polyisocyanate compound in such a range, excellent heat resistance can be obtained.
In addition, when the phosphinate compound is contained as the powder B, the isocyanate index is preferably 250 or more and 500 or less (more preferably 280 or more and 480 or less, further preferably 300 or more and 450 or less).
The isocyanate index is represented by 100 times the value obtained by dividing the number of equivalents of isocyanate groups in the polyisocyanate compound by the total number of equivalents of active hydrogen in active hydrogen-containing components (polyol compound, water, etc.). is there.

  The 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. In particular, by including the ethylenically unsaturated double bond-containing compound and the above-described powder A, and further including the powder B, heat resistance, storage stability, workability, and the like can be further improved.

  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 them, as a reaction product of the polyhydric alcohol and the unsaturated carboxylic acid, for example, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolpropanetri (meth) acrylate, trimethylolpropanedi (meth) acrylate, ditri Methylolpropane tetra (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene / poly B propylene glycol di (meth) acrylate, alkylene oxide modified trimethylolpropane tri (meth) acrylate.

  Examples of the bisphenol A-based (meth) acrylate compound include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypoly) Propoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc. Is mentioned.

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

  The mixing amount of the ethylenically unsaturated double bond-containing compound is preferably 1 part by weight or more and 100 parts by weight or less, more preferably 5 parts by weight or more and 90 parts by weight or less, further preferably 10 parts by weight or less, based on 100 parts by weight of the polyol compound. Not less than 80 parts by weight. When the ethylenically unsaturated double bond-containing compound contains a plurality of hydroxyl groups, it is regarded as a polyol compound. The isocyanate index is calculated in consideration of the active hydrogen-containing component contained in the ethylenically unsaturated double bond-containing compound.

The curable composition of the present invention may contain, for example, a colorant, a surfactant, a polymerization inhibitor, and fibers in addition to the above components.
Examples of the colorant include a pigment and a dye.
Examples of the surfactant include a nonionic surfactant, an anionic surfactant, and a cationic surfactant. Such a surfactant can provide storage stability and dispersion stability.
Examples of the polymerization inhibitor include a hydroquinone-based polymerization inhibitor, a benzoquinone-based polymerization inhibitor, a catechol-based polymerization inhibitor, and a piperidine-based polymerization inhibitor. Such a polymerization inhibitor imparts long-term storage stability 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-liquid type, for example, the first liquid may be a form containing a polyol compound, a foaming agent, a catalyst, and a flame retardant, and the second liquid may be a form containing a polyisocyanate compound.

The viscosity of the first liquid is preferably 20 mPa · s or more and 500 mPa · s or less, more preferably 30 mPa · s or more and 350 mPa · s from the viewpoints of storage stability of the first liquid, handleability, workability at the time of foam formation, and the like. s or less, more preferably 50 mPa · s or more and 250 mPa · s or less. Note that the viscosity is a viscosity at 20 rpm measured at 20 ° C. by a BH type viscometer (a guideline value at the fourth rotation). With such a viscosity, the curable composition can be set to a relatively low viscosity while sufficiently ensuring the storage stability of the curable composition. Thereby, the stirring work or the like at the time of construction is reduced, and advantageous effects can be obtained also in handleability, workability, miscibility with the polyisocyanate compound, and the like.
The viscosity of the second liquid is preferably from 20 mPa · s to 500 mPa · s, more preferably from 30 mPa · s to 350 mPa · s, and still more preferably from 50 mPa · s to 250 mPa · s.

When applying 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.

  In addition, as a building material such as a building or a civil engineering structure, it can be used as a heat insulating sandwich panel in which a foam is laminated between face materials such as a metal plate. Such an insulated sandwich panel is manufactured by forming a foam in advance and bonding two face materials together, or by applying a curable composition to one face material and foaming to form a foam. A method of bonding two face materials, a method of injecting a curable composition between two face materials, and foaming to form a foam.

  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: Resinification catalyst (octylic acid solution of bismuth octylate)
Flame retardant 1: phosphinate compound (aluminum tris (diethylphosphinate), average particle size 4 μm, density 1.35 g / cm ³ )
Flame retardant 2: phosphinate compound (aluminum tris (diethylphosphinate), average particle size 10 μm, density 1.35 g / cm ³ )
Flame retardant 3: cyclic phosphoramidate (R1: all methylene groups, R2: all methyl groups, R3: all hydrogen atoms, R4: butylene group cyclic phosphoramidate in formula 4; average particle size 3 μm)
Flame retardant 4: cyclic phosphoramidate (R1: all methylene groups in formula 4, R2: all methyl groups, N (R3) -R4- (R3) N: nitrogen-containing 6-membered cyclic structure (piperidine structure) (Phosphoramidate, average particle size 3 μm)
Flame retardant 5: organic phosphate compound (tris (chloropropyl) phosphate, density 1.29 g / cm ³ )
Flame retardant 6: silica (average particle size 50 nm, density 2.65 g / cm ³ )
Flame retardant 7: silica (average particle size 850 nm, density 2.65 g / cm ³ )
Flame retardant 8: silica (average particle size 1.2 μm, density 2.65 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)
・ Foam stabilizer: Silicone foam stabilizer

(Examples 1 to 11, 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) Heat resistance The heat resistance was measured using a corn calorimeter specified in ISO5660. The heating intensity was 50 kW / m ² , and the heating time was 20 minutes. The following evaluation items were evaluated. The evaluation criteria are as follows.
(3-1) Heat resistance 1 (dimensional change)
A: Dimensional change in thickness direction after test is 12 mm or less B: Dimensional change in thickness direction after test is more than 12 mm and 16 mm or less C: Dimensional change in thickness direction after test is more than 16 mm and 20 mm or less D: Thickness direction after test Dimensional change of more than 20 mm (3-2) Heat resistance 2 (total heat generation)
A: The total calorific value 10 MJ / ^{m 2} or less B: the total calorific value 10 MJ / ^{m 2} Ultra 15 mJ / ^{m 2} or less C: the total calorific value 15 mJ / ^{m 2} Ultra 20 MJ / ^{m 2} or less D: the total calorific value 20 MJ / M ² more than (3-3) heat resistance 3 (maximum heat generation rate)
A: Maximum heating rate of 100 kW / ^{m 2} or less B: the maximum heating rate of 100 kW / ^{m 2} Ultra 150 kW / ^{m 2} or less C: the maximum heating rate of 150 kW / ^{m 2} ultra 200kW / ^{m 2} or less D: the maximum heat release rate is 200kW / ^{m 2} more than

Claims (2)

A curable composition for forming a foam,
Contains a polyol compound, a foaming agent, a catalyst, a flame retardant and a polyisocyanate compound,
The flame retardant contains a powder having an average particle diameter of 1 μm or less,
Curable composition characterized by the above-mentioned. 2. The curable composition according to claim 1, wherein the flame retardant includes a powder having an average particle diameter of 0.01 μm or more and 1 μm or less, and a powder having an average particle diameter of more than 1 μm and 100 μm or less.