JP2021119255A - Curable composition - Google Patents

Abstract

To provide a curable composition capable of forming a foam having performance excellent in low thermal conductivity and heat resistance.SOLUTION: The curable composition contains a polyol compound, a foaming agent, a catalyst, a flame retardant and a polyisocyanate compound in which the flame retardant includes an organic phosphorous compound, includes as the organic phosphorous compound a phosphate and an alkyl phosphinate compound and has a mixture ratio (weight ratio) of the phosphate and the alkyl phosphinate compound being a ratio of the phosphate:the alkyl phosphinate compound of 90:10 to 50:50; and the phosphorus content in the flame retardant is not less than 1 pt.wt. to not more than 60 pts.wt. based on 100 pts.wt. of the polyol compound.SELECTED DRAWING: None

Description

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

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

WO2015 / 129850

For example, Patent Document 1 describes a polyurethane foam containing an isocyanate, a polyol, a catalyst, a foaming agent, a foam stabilizer, and a flame retardant, and an inorganic phosphorus compound is used as the flame retardant.

However, since the flame retardant of Patent Document 1 contains an inorganic compound as a main component, it is difficult to stably mix with an organic compound such as isocyanate or polyol, and the thermal conductivity and heat resistance of the formed foam are improved. There is room for.

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 thermal conductivity and heat resistance.

As a result of diligent studies to solve the above problems, the present inventors have used an organic phosphorus compound as a flame retardant and cured the curable composition for foam formation with a specific phosphorus content with respect to the polyol compound. We have found that the sex composition can form a foam having low thermal conductivity and excellent heat resistance, and have completed the present invention.

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, and polyisocyanate compounds,
The flame retardant contains an organic phosphorus compound, and the organic phosphorus compound contains a phosphoric acid ester and an alkylphosphinate compound, and the mixing ratio (weight ratio) of the phosphoric acid ester and the alkylphosphinate compound is phosphorus. The ratio of the acid ester: alkylphosphinate compound is 90: 10 to 50:50.
A curable composition characterized in that the phosphorus content in the flame retardant is 1 part by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the polyol compound.
2. 1. The content of the organic phosphorus compound in the total amount of the flame retardant is 80% by weight or more and 100% by weight or less. The curable composition according to.

According to the present invention, it is possible to form a foam having excellent performance in low thermal conductivity, heat resistance 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 is characterized by containing a polyol compound, a foaming agent, a catalyst, a flame retardant, and a polyisocyanate compound, and containing an organic phosphorus compound as the flame retardant. It is something to do.

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 polyhydric 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. Examples thereof include dichlorotrifluoropropene (HCFO1223) and the like, or isomers thereof (cis form, trans form) and the like.
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. When hydrofluoroolefin and / or hydrochlorofluoroolefin and water are contained as the foaming agent, the mixing ratio (weight ratio) of hydrofluoroolefin and / or hydrochlorofluoroolefin and water is 100: 0.5 to It is preferably 100: 5 (further, 100: 0.8 to 100: 4). Within such a range, a foam having excellent low thermal conductivity, heat resistance, and excellent strength can be obtained.

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-isopropylimidazole, 1- Imidazole such as isobutyl-2-methylimidazole, or N-methyl-N'-(2-dimethylaminoethyl) piperazine, N, N'-dimethylpiperazine, N-methylpiperazine, N-methylmorpholin, N-ethylmorpholin , 1,8-diazabicyclo [5.4.0] undecene-7, 1,1'-(3- (dimethylamino) propyl) imino) bis (2-propanol) and the like, and one or 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 0.5 parts by weight or more and 48 parts by weight or less, and further preferably 1 part by weight or more and 45 parts by weight with respect to 100 parts by weight of the polyol compound. Parts or less, 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 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 flame retardant is characterized by containing an organic phosphorus compound as an essential component. As such an organic phosphorus compound, for example, a phosphorus compound containing at least a hydrocarbon group is preferable.
Examples of such an organic phosphorus compound include
Trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, trisnonylphenyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresilphenyl phosphate, cresilxylenyl 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, tris (tribromoneopentyl) phosphate , Bis (chloropropyl) monooctyl phosphate, hydroquinonyl diphenyl phosphate, phenylnonylphenyl hydroquinonyl phosphate, phenyldinonylphenyl phosphate, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphate , Phenylic acid esters such as dimethyl-4-hydroxy-3,5-dibromobenzylphosphonate, diphenyl-4-hydroxy-3,5-dibromobenzylphosphonate,
3,9-bis (phenylmethyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ((2-methylphenyl)) Methyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ((3-methylphenyl) 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] undecane, 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-butylphenyl) methyl) 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-bis ((2-tert-butyl) Phenyl) methyl) -3,9-geo Xo-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) -3,9-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-anthril) methyl)- 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-bis (triphenyl) Methyl) -3,9-geo Xo-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-2,4,5,10-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-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3-diphenyl Methyl-9-((2,4-di-tert-butylphenyl) methyl) -3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] Cyclic such as undecane Methyl ester,
Calcium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, 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 (diethylphosphinic acid) titanyl, tetrakis (diethylphosphinic acid) titanyl, bis (methylethylphosphinic acid) titanyl, tetrakis (methylethylphosphinic acid) titanyl, bis Alkylphosphinate compounds such as (diphenylphosphinic acid) titanyl and tetrakis (diphenylphosphinic acid) titanyl,
Hexamethoxycyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, hexaphenoxycyclotriphosphazene, diethoxytetrafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, methoxypentafluorocyclotriphosphazene, propoxypentafluorocyclotriphosphazene, butoxypenta Alkyl halide phosphazenes such as fluorocyclotriphosphazene,
Phosphoramidate represented by the following formulas 1 and 2
(Equation 1)
OR1
│
O = PN (R2) ₂
│
OR1
(Equation 2)
O-R1 O-R1
│ │
O = PN (R2) -R3- (R2) NP = O
│ │
O-R1 O-R1
(R1 may be the same or different, an alkyl group having 1 or more and 12 or less carbon atoms, R2 may be the same or different and may be a hydrogen atom or an alkyl group having 1 or more and 12 or less carbon atoms, and R3 has 1 or more and 12 or less carbon atoms. In addition, N (R2) ₂ and N (R2) -R3- (R2) N may have a nitrogen-containing heterocyclic structure.
Cyclic phosphoramidate represented by the following formulas 3 and 4 (formula 3)
R2 R1-O
\ / \
CP = O
/ \ / \
R2 R1-ON (R3) ₂
(Equation 4)
R2 R1-O O-R1 R2
\ / \ / \ /
CP = OO = PC
/ \ / \ / \ / \
R2 R1-ON (R3) -R4- (R3) NO-R1 R2
(R1 may be the same or different and may be an alkylene group having 1 or more and 3 or less carbon atoms, R2 may be the same or different and may be an alkyl group having 1 or more and 12 or less carbon atoms, and R3 may be the same or different as a hydrogen atom. Alternatively, an alkyl group having 1 or more and 12 or less carbon atoms, R4 indicating an alkylene group having 1 or more and 12 or less carbon atoms, and N (R3) ₂ , N (R3) -R4- (R3) N have a nitrogen-containing heterocyclic structure. May be.)
Etc., and one or more of these can be used.

In the present invention, as the organic phosphorus compound, one or more selected from a phosphoric acid ester, a cyclic phosphoric acid ester, an alkylphosphinate compound, a phosphoramidate, and a cyclic phosphoramidate, and further, an alkylphosphinate compound and a cyclic compound. It is preferable to contain one or more selected from phosphoramidate, which is excellent in workability and can further improve heat resistance.
In the present invention, when the organophosphorus compound contains an alkylphosphinate compound, it is preferable to contain a phosphoric acid ester and an alkylphosphinate compound, and workability and heat resistance can be improved. In particular, when the phosphoric acid ester and the alkylphosphinate compound are contained, the total amount of the phosphoric acid ester and the alkylphosphinate compound is 10 parts by weight or more and 1000 parts by weight or less (preferably 30 parts by weight) with respect to 100 parts by weight of the polyol compound. It is preferably 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). The mixing ratio (weight ratio) of the phosphoric acid ester and the alkylphosphinate compound is the ratio of the phosphoric acid ester: alkylphosphinate compound, 90: 10 to 50:50, and further 85: 15 to 55:45. Further, it is preferably 80:20 to 60:40. Within such a range, the workability is excellent and the heat resistance can be further improved.
In particular, when cyclic phosphoramidate is contained, the amount of cyclic phosphoramidate is 1 part by weight or more and 100 parts by weight or less (more preferably 5 parts by weight or more and 70 parts by weight or less, more preferably more preferably) with respect to 100 parts by weight of the polyol compound. It is preferably 10 parts by weight or more and 50 parts by weight or less). Within such a range, the workability is excellent and the heat resistance can be further improved.

The phosphorus content is calculated based on the phosphorus content (% by weight) in one molecule, and can be calculated from the content of the organic phosphorus compound in the composition and the phosphorus content of the organic phosphorus compound. can.
In the present invention, the phosphorus content is 1 part by weight or more and 60 parts by weight or less (preferably 2 parts by weight or more and 55 parts by weight or less, more preferably 3 parts by weight or more and 50 parts by weight or less) with respect to 100 parts by weight of the polyol compound. It is characterized by being. When the phosphorus content is low, the heat resistance may be inferior, and when the phosphorus content is high, the heat conductivity, strength, and foam forming property may be poor.

In addition to the above organic phosphorus compounds, the flame retardants include phosphorus-based flame retardants other than organic phosphorus compounds, halogen-based flame retardants, organic brominated flame retardants, nitrogen-based flame retardants, metal hydrate-based flame retardants, and antimony-based flame retardants. A flame retardant, a boron-based flame retardant, a silicon-based flame retardant, or the like can also be used.
For example, as a phosphorus-based flame retardant other than an organic phosphorus compound, for example,
Polyphosphate compounds such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melem polyphosphate, melam polyphosphate, and melon polyphosphate,
Phosphinate compounds such as sodium phosphite, calcium phosphinate, aluminum phosphinate, zinc phosphinate,
Hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene, dodecachlorocyclohexaphosphazene, hexabromocyclotriphosphazene, hexafluorocyclotriphosphazene, octafluorocyclotetraphosphazene, decafluorocyclopentaphosphazene, dodecafluorocyclohexazene Halogenized phosphazene such as saphosphazene,
Examples include red phosphorus, phosphorus trichloride, phosphorus pentachloride and the like. When a phosphorus-based flame retardant other than these organic phosphorus compounds is contained, the phosphorus content may be calculated in the same manner as described above.

The content of the organic phosphorus compound in the flame retardant is preferably 80% by weight or more and 100% by weight or less, more preferably 90% by weight or more and 100% by weight or less, still more preferably 95% by weight or more and 100% by weight or less, based on the total amount of the flame retardant. % Or less, most preferably 100% by weight.
The mixing amount of the flame retardant is 1 part by weight or more and 1000 parts by weight or less (preferably 2 parts by weight or more and 600 parts by weight or less, more preferably 3 parts by weight or more and 400 parts by weight or less) with respect to 100 parts by weight of the polyol compound. Is preferable.

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 properties 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 130 or more and 500 or less (further, 150 or more and 480 or less, further 170 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.
When the organophosphorus compound contains an alkylphosphinate compound, the isocyanate index is preferably 250 or more and 500 or less (further, 280 or more and 480 or less, further 300 or more and 450 or less).
The isocyanate index is expressed as 100 times the numerical value obtained by dividing the equivalent number of isocyanate groups of the polyisocyanate compound by the total equivalent number of active hydrogen of the active hydrogen-containing component (polyol compound, water, etc.). be.

The curable composition 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.
In particular, in the present invention, when an alkylphosphinate compound is contained as an organic phosphorus compound together with an ethylenically unsaturated double bond-containing compound, the flame retardant effect is enhanced and more excellent heat resistance can be imparted. Further, when the cyclic phosphoramidate is contained as the organic phosphorus compound together with the ethylenically unsaturated double bond-containing compound, the flame retardant effect is enhanced and more excellent heat resistance can be imparted.

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 90 parts by weight or less, still more preferably 10 parts by weight, based on 100 parts by weight of the polyol compound. It is 50 parts by weight or more and 80 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, a surfactant, a polymerization inhibitor, a fiber, or the like can be mixed in the curable composition of the present invention.
Examples of the colorant include pigments and dyes.
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants and the like. Such a surfactant can impart storage stability and dispersion stability.
Examples of the polymerization inhibitor include hydroquinone-based polymerization inhibitors, benzoquinone-based polymerization inhibitors, catechol-based polymerization inhibitors, piperidine-based polymerization inhibitors, and the like. Such a polymerization inhibitor imparts long-term storage stability in the 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 can be applied to a base material and foamed at a site such as a building to cover the base material with a foam, or a base material (surface material) can be applied to one or both sides of the foam. It can be laminated and used in applications such as freezers / refrigerators, plants, tunnels, vehicles, ships, aircraft, electronic devices, and home appliances. Specific examples of the target base material include concrete, mortar, metal plate, inorganic board, plywood, plastic plate, wood plate 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 contains a polyol compound, a foaming agent, a foaming aid, a catalyst, and a flame retardant, and the second liquid contains a polyisocyanate compound. Can be done.

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 ·. 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 set at a predetermined temperature in this way 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.

Further, as a building material for buildings, civil engineering structures, etc., it can also be used as a heat insulating sandwich panel in which foam is laminated between face materials such as metal plates. Such a heat-insulating sandwich panel is a method in which foam is manufactured in advance and two face materials are bonded together. One face material is coated with a curable composition and foamed to form a foam, and then another method is used. Examples thereof include a method of laminating two face materials, a method of injecting a curable composition between the two face materials and foaming the two face materials to form a foam.

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

As the first liquid, a mixture of the following raw materials uniformly mixed 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: Hydrofluoroolefin ・ Foaming agent 3: 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: Alkylphosphinate compound (tris (diethylphosphinic acid) aluminum, phosphorus content 23.8% by weight)
-Flame retardant 2: Phosphate ester (trimethylphosphate, phosphorus content 22.1% by weight)
-Flame retardant 3: Phosphate ester (triethyl phosphate, phosphorus content 17.0% by weight)
-Flame retardant 4: Phosphate ester (triphenyl phosphate, phosphorus content 9.5% by weight)
-Flame retardant 5: Phosphate compound (sodium phosphite, phosphorus content 35.2% by weight)
Flame Retardant 6: Cyclic Phosphoramidate (R1: All Methylene Group, R2: All Methyl Group, R3: All Hydrogen Atom, R4: Butylene Group Cyclic Phosphoramidate, Phosphorus Content 16.1 Weight %)
-Flame retardant 7: Cyclic phosphoramidate (R1: all methylene group, R2: all methyl group, N (R3) -R4- (R3) N: nitrogen-containing 6-membered ring structure (piperidine structure) in formula 4) Phosphoramidate, phosphorus content 16.2% by weight)
-Flame retardant 8: Phosphate ester (tris (chloropropyl) phosphate, phosphorus content 9.5% by weight)
-Double bond compound: Ethylene unsaturated double bond-containing compound (trimethylol propantriacrylate, ethylenically unsaturated double bond concentration 10 mmol / g, hydroxyl value: 0 mgKOH / g)
・ Defoaming agent: Silicone-based defoaming agent

(Examples 1 to 30, Comparative Examples 1 to 2)
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 entirely 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) Heat resistance This was carried out using a corn calorimeter specified in ISO 5660. 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 the thickness direction after the test is 12 mm or less B: Dimensional change in the thickness direction after the test is more than 12 mm and 16 mm or less C: Dimensional change in the thickness direction after the test is more than 16 mm and 20 mm or less D: Thickness direction after the test Dimensional change is over 20 mm (3-2) Heat resistance 2 (total calorific value)
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 or} more (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 or} more

Claims (2)

A curable composition for foam formation,
Contains polyol compounds, foaming agents, catalysts, flame retardants, and polyisocyanate compounds,
The flame retardant contains an organic phosphorus compound, and the organic phosphorus compound contains a phosphoric acid ester and an alkylphosphinate compound, and the mixing ratio (weight ratio) of the phosphoric acid ester and the alkylphosphinate compound is phosphorus. The ratio of the acid ester: alkylphosphinate compound is 90: 10 to 50:50.
A curable composition characterized in that the phosphorus content in the flame retardant is 1 part by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the polyol compound. The curable composition according to claim 1, wherein the content of the organic phosphorus compound in the total amount of the flame retardant is 80% by weight or more and 100% by weight or less.