JP7230103B2 - Curable composition - Google Patents

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 base materials such as wall surfaces, ceiling surfaces, floor surfaces, etc., heat transfer between indoors and outdoors is suppressed. Such foam is a material with low thermal conductivity, and typical examples thereof include organic foams such as urethane foam, phenol foam, and styrene foam. Among these, urethane foam is frequently used because it has excellent low thermal conductivity of about 0.025 W/(mK) and can be constructed at a relatively low cost. It is 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 uses an inorganic phosphorus compound as the flame retardant.

However, since the flame retardant of Patent Document 1 is mainly composed of an inorganic compound, 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 terms of low thermal conductivity and heat resistance.

The present inventors have made intensive studies to solve the above problems, and have found that a curable composition for foam formation uses an organic phosphorus compound as a flame retardant and has a specific phosphorus content relative to the polyol compound. The inventors have found that the 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. A curable composition for forming a foam comprising:
containing a polyol compound, a blowing agent, a catalyst, a flame retardant, and a polyisocyanate compound,
A two-part curable composition comprising a first liquid containing a polyol compound, a foaming agent, a catalyst, and a flame retardant, and a second liquid containing a polyisocyanate compound,
The flame retardant contains an organic phosphorus compound, and the organic phosphorus compound contains a phosphate ester and an alkylphosphinate compound, and the mixing ratio (weight ratio) of the phosphate ester and the alkylphosphinate compound is acid ester: alkylphosphinate compound ratio is 90:10 to 50:50,
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 mixing ratio of the polyol compound and the polyisocyanate compound has an isocyanate index of 130 or more and 500 or less,
A curable composition characterized by being
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, a foam having excellent properties such as low thermal conductivity and heat resistance can be formed.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated.

The curable composition of the present invention is applicable for foam formation, and contains a polyol compound, a foaming agent, a catalyst, a flame retardant, and a polyisocyanate compound, and is characterized by containing an organic phosphorus compound as a flame retardant. It is something to do.

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

Among these, polyester polyols include, for example, aromatic polyester polyols, aliphatic polyester polyols, aromatic/aliphatic polyester polyols, and the like, and one or more of these can be used.
Specifically, an aromatic polyester polyol is a polyol having an aromatic hydrocarbon in one molecule. Condensed polyester polyols obtained by reacting with , and phthalic acid-based polyester polyols obtained by decomposing phthalic acid-based polyester moldings such as polyethylene terephthalate. Examples of polyhydric alcohols include dihydric or higher alcohols and derivatives thereof, dihydric or higher phenols, and polyols.
Aliphatic polyester polyol is a polyol having an aliphatic hydrocarbon in one molecule, for example, aliphatic polybasic acids and polyvalent Examples thereof include condensed polyester polyols obtained by reacting with alcohol.
Aromatic/aliphatic polyester polyols are polyols containing aliphatic hydrocarbons and aromatic hydrocarbons in one molecule, and are obtained by reacting aromatic polybasic acids and aliphatic polybasic acids with polyhydric alcohols. and condensed polyester polyols.
In the present invention, it is preferred that polyester polyol is included as the polyol compound.

Examples of polyether polyols include aromatic polyether polyols, phosphorus-containing polyether polyols, glycerin-based polyether polyols, and amino group-containing polyether polyols. Specifically, aromatic polyether polyols include, for example, bisphenol A-type polyether polyols obtained by adding alkylene oxide (e.g., ethylene oxide, propylene oxide, etc.) using bisphenol A as an initiator, aromatic amines ( For example, toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, triethanolamine, Mannich condensate, etc.) by adding an alkylene oxide as an initiator. The resulting aromatic amine-based polyether polyol and the like can be mentioned. Phosphorus-containing polyether polyols include, for example, dialkyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonates, which are diols having a phosphate ester structure. Examples of glycerin-based polyether polyols include polyether polyols obtained by adding alkylene oxide using glycerin as an initiator. Examples of amino group-containing polyether polyols include those obtained by adding an alkylene oxide to 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 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 that is equimolar to the hydroxyl groups contained in 1 g of the sample, and is defined in JIS K 1557-1:2007 Plastics-Polyurethane raw material polyol test method-Part 1: Hydroxyl value. It is a value measured based on the method of obtaining. The hydroxyl value of a polyol compound is a value measured with a mixture of all polyol compounds.

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

Among these, examples of hydrocarbons include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane. Hydrochlorofluorocarbons (HCFC) include, for example, 1,1-dichloro-1-fluoroethane (HCFC-141B), 1-chloro-1,1-difluoroethane (HCFC-142B), chlorodifluoromethane (HCFC-22) etc. Hydrofluorocarbons (HFC) include, for example, 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, 3,4,5,5,5-decafluoropentane (HFC4310mee) and the like.

Hydrofluoroolefins (HFO) include, for example, pentafluoropropenes such as 1,2,3,3,3-pentafluoropropene (HFO1225ye), 1,3,3,3-tetrafluoropropene (HFO1234ze), 2, Tetrafluoropropenes such as 3,3,3-tetrafluoropropene (HFO1234yf), 1,2,3,3-tetrafluoropropene (HFO1234ye), trifluoropropenes such as 3,3,3-trifluoropropene (HFO1243zf) , tetrafluorobutene (HFO1345), pentafluorobutene (HFO1354), hexafluorobutene (HFO1336), heptafluorobutene (HFO1327), heptafluoropentene (HFO1447), octafluoropentene (HFO1438), nonafluoropentene (HFO1429), etc. , or isomers thereof (cis isomers, trans isomers), and the like. Examples of hydrochlorofluoroolefins (HCFO) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), Dichlorotrifluoropropene (HCFO1223) and the like, or isomers thereof (cis isomer, trans isomer) and the like can be mentioned.
As the foaming agent in the present invention, one or more selected from hydrofluoroolefins, hydrochlorofluoroolefins and water are suitable. 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, and 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. is. When the foaming agent contains hydrofluoroolefin and/or hydrochlorofluoroolefin and water, the mixing ratio (weight ratio) of the hydrofluoroolefin and/or hydrochlorofluoroolefin and water is from 100:0.5. 100:5 (more preferably 100:0.8 to 100:4). Within such a range, it is possible to obtain a foam having excellent low thermal conductivity, excellent heat resistance, and excellent strength.

The catalyst is not particularly limited, but includes, for example, nurate-forming catalysts, resin-forming catalysts, foaming catalysts, and the like, and one or more of these can be used.

Nurate-forming catalysts are not particularly limited as long as they are effective catalysts for isocyanurate-forming. Salts (organic acids such as acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, lactic acid, etc.), trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium , trialkylhydroxyalkylammonium hydroxides such as triethylhydroxyethylammonium or organic acid salts thereof (organic acids such as acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid , lactic acid, etc.), metal salts of alkylcarboxylic acids (e.g., acetic acid, caproic acid (n-hexanoic acid), octylic acid (2-ethylhexanoic acid), myristic acid, lactic acid, etc.), β of aluminum acetylacetone, lithium acetylacetone, etc. - Metal chelate compounds of diketones, Friedel-Crafts catalysts such as aluminum chloride and boron trifluoride, organometallic compounds such as titanium tetrabutylate and tributylantimony 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 Organic acid salts, bismuth tris (2-ethylhexanoate), bismuth tris (neodecanoate), bismuth tris (palmitate), bismuth tris (palmitate), bismuth tetramethylheptanedioate, bismuth octylate, bismuth naphthenate, dibutyltin dilaurate, dibutyltin dimaleate, Organic metals such as dibutyltin diacetate, dioctyltin diacetate, tin octylate, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 1- Imidazoles such as 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-(dimethylamino)propyl)imino)bis(2-propanol) and the like, one or two of these More than one species can be used.

Examples of foaming catalysts 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 and organic acid salts thereof, and the like, and one or more of these can be used.

The amount of the catalyst to be mixed 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 with respect to 100 parts by weight of the polyol compound. parts or less, most preferably 3 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 resinification catalyst and/or a foaming catalyst together with a nurate catalyst, which is advantageous in workability and foam formation. 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 organophosphorus compounds include
trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, trisnonylphenyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, cresylphenyl phosphate, cresyl xylenyl phosphate, cresyl diphenyl 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, phenyl nonylphenyl hydroquinonyl phosphate, phenyl dinonyl phenyl phosphate, diphenyl-4-hydroxy-2,3,5,6-tetrabromobenzyl phosphate , dimethyl-4-hydroxy-3,5-dibromobenzylphosphonate, diphenyl-4-hydroxy-3,5-dibromobenzylphosphonate and other phosphoric acid esters,
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- 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-di 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-anthryl)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-di 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-2,4,8,10-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-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-diphenyl Cyclic compounds such as methyl-9-((2,4-di-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane phosphate ester,
Calcium dimethylphosphinate, Aluminum dimethylphosphinate, Zinc dimethylphosphinate, Calcium ethylmethylphosphinate, Aluminum ethylmethylphosphinate, Zinc ethylmethylphosphinate, Calcium diethylphosphinate, Aluminum diethylphosphinate, Zinc diethylphosphinate, Tris ( diethylphosphinate) aluminum, tris(methylethylphosphinate) aluminum, tris(dibutylphosphinate) aluminum, tris(butylethylphosphinate) aluminum, tris(diphenylphosphinate) aluminum, bis(diethylphosphinate) zinc, bis( methylethylphosphinate)zinc, bis(diphenylphosphinate)zinc, bis(diethylphosphinate)titanyl, tetrakis(diethylphosphinate)titanyl, bis(methylethylphosphinate)titanyl, tetrakis(methylethylphosphinate)titanyl, bis alkylphosphinate compounds such as titanyl (diphenylphosphinate) and tetrakis(diphenylphosphinate) titanyl;
hexamethoxycyclotriphosphazene, ethoxypentafluorocyclotriphosphazene, hexaphenoxycyclotriphosphazene, diethoxytetrafluorocyclotriphosphazene, phenoxypentafluorocyclotriphosphazene, methoxypentafluorocyclotriphosphazene, propoxypentafluorocyclotriphosphazene, butoxypenta alkylhalogenated phosphazenes such as fluorocyclotriphosphazenes,
phosphoramidates represented by the following formulas 1 and 2,
(Formula 1)
OR1
│
O=PN(R2) ₂
│
OR1
(Formula 2)
OR1 OR1
│ │
O=P-N(R2)-R3-(R2)N-P=O
│ │
OR1 OR1
(R1 may be the same or different and an alkyl group having 1 to 12 carbon atoms, R2 may be the same or different, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R3 is 1 to 12 carbon atoms. and N(R2) ₂ , N(R2)-R3-(R2)N may be a nitrogen-containing heterocyclic structure.)
Cyclic phosphoramidates represented by the following formulas 3 and 4 (formula 3)
R2 R1-O
＼ ／ ＼
CP=O
／ ＼ ／ ＼
R2 R1-ON(R3) ₂
(Formula 4)
R2 R1-O O-R1 R2
\ / \ / \ /
C P=O O=P C
／ ＼ ／ ＼ ／ ＼ ／ ＼
R2 R1-O N(R3)-R4-(R3)N O-R1 R2
(R1 may be the same or different alkylene groups having 1 to 3 carbon atoms, R2 may be the same or different alkyl groups having 1 to 12 carbon atoms, R3 may be the same or different hydrogen atoms 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 and N(R3)-R4-(R3)N are nitrogen-containing heterocyclic structures may be.)
etc., and one or more of these can be used.

In the present invention, the organic phosphorus compound is one or more selected from phosphate esters, cyclic phosphate esters, alkylphosphinate compounds, phosphoramidates, and cyclic phosphoramidates, and alkylphosphinate compounds, cyclic It preferably contains one or more selected from phosphoramidates, which can improve workability and further improve heat resistance.
In the present invention, when an alkylphosphinate compound is included as the organic phosphorus compound, it is preferable to include a phosphoric acid ester and an alkylphosphinate compound, and workability and heat resistance can be improved. In particular, when the phosphate ester and the alkylphosphinate compound are included, the total amount of the phosphate 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. 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 phosphate ester and the alkylphosphinate compound is 90:10 to 50:50, further 85:15 to 55:45, in terms of the phosphate ester:alkylphosphinate compound ratio. Further, it is preferably 80:20 to 60:40. By being in such a range, it is possible to improve workability and further improve heat resistance.
In particular, when a cyclic phosphoramidate is included, the 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, still more preferably 10 parts by weight or more and 50 parts by weight or less). By being in such a range, it is possible to improve workability and further improve heat resistance.

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) relative to 100 parts by weight of the polyol compound. It is characterized by being If the phosphorus content is low, heat resistance may be poor, and if the phosphorus content is high, thermal conductivity, strength, and foam formation may be poor.

As flame retardants, in addition to the above organic phosphorus compounds, phosphorus-based flame retardants other than organic phosphorus compounds, halogen-based flame retardants, organic bromine-based flame retardants, nitrogen-based flame retardants, metal hydrate-based flame retardants, antimony-based flame retardants, Retardants, boron-based flame retardants, silicon-based flame retardants, and the like can also be used.
For example, phosphorus-based flame retardants other than organophosphorus compounds include:
polyphosphate compounds such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melem polyphosphate, melam polyphosphate, and melon polyphosphate;
phosphinate compounds such as sodium phosphinate, calcium phosphinate, aluminum phosphinate, zinc phosphinate;
Hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, decachlorocyclopentaphosphazene, dodecachlorocyclohexaphosphazene, hexabromocyclotriphosphazene, hexafluorocyclotriphosphazene, octafluorocyclotetraphosphazene, decafluorocyclopentaphosphazene, dodecafluorocyclohexane Halogenated phosphazenes such as saphosphazene,
red phosphorus, phosphorus trichloride, phosphorus pentachloride and the like. When phosphorus-based flame retardants other than these organic phosphorus compounds are included, 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, and still more preferably 95% by weight or more and 100% by weight, based on the total amount of the flame retardant. % or less, most preferably 100% by weight.
The amount of the flame retardant mixed 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 preferred.

As the polyisocyanate compound, various polyisocyanate compounds known in the technical field of polyurethane can be used. Examples of polyisocyanate compounds 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 preferred from the viewpoints of ease of handling, speed of reaction, physical properties of the resulting foam, superiority in terms of cost, and the like. Examples of MDI include monomeric MDI and polymeric MDI (polymethylene polyphenyl isocyanate).

The curable composition of the present invention preferably has an isocyanate index of 130 to 500 (more preferably 150 to 480, more preferably 170 to 450).
Excellent heat resistance can be obtained by mixing the polyol compound and the polyisocyanate compound in such a range.
When an alkylphosphinate compound is included as the organic phosphorus compound, the isocyanate index is preferably 250 or more and 500 or less (more preferably 280 or more and 480 or less, furthermore 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 number of active hydrogen equivalents of the active hydrogen-containing component (polyol compound, water, etc.). be.

The curable composition of the present invention can contain a foam stabilizer in addition to the components described above. Examples of foam stabilizers include silicone-based foam stabilizers such as polyether-modified silicone compounds, fluorine-containing compound-based foam stabilizers, and the like. These can be used singly or in combination of two or more. Examples of polyether-modified silicone compounds include graft copolymers of polydimethylsiloxane and polyoxyethylene glycol or polyoxyethylene-propylene glycol. The amount of the foam stabilizer mixed is preferably 0.1 parts by weight or more and 40 parts by weight or less, more preferably 0.5 parts by weight or more and 30 parts by weight or less, relative to 100 parts by weight of the polyol compound.

The curable composition of the present invention can also contain an ethylenically unsaturated double bond-containing compound in addition to the components described above. Examples of ethylenically unsaturated double bonds include (meth)acryloyl groups, allyl groups, propenyl groups and the like. In the present invention, heat resistance, storage stability, workability, etc. 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 included 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. Moreover, when a cyclic phosphoramidate is included as an 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 effects. /g or more and 15 mmol/g or less is more preferable. The concentration of ethylenically unsaturated double bonds in a molecule is expressed 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 by 1000 times (mmol/g) of the numerical value divided by .

Specific examples of ethylenically unsaturated double bond-containing compounds include, for example, polyhydric alcohols (e.g., dihydric or higher alcohols and derivatives thereof, dihydric or higher phenols, polyols, etc.) and unsaturated carboxylic acids (( meth)acrylic acid, etc.), reaction products of amines (e.g., divalent or higher amines, alkanolamines, etc.) and unsaturated carboxylic acids, unsaturated carboxylic acid thioesters or unsaturated alkylthioethers of thiols, Examples include bisphenol A-based (meth)acrylate compounds, reaction products of glycidyl group-containing compounds and unsaturated carboxylic acids, (meth)acrylate compounds having urethane bonds in the molecule, nonylphenoxypolyethyleneoxyacrylate, and the like. These can be used singly or in combination of two or more.

Among them, examples of reaction products of polyhydric alcohols and unsaturated carboxylic acids include pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta( meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, ditri Examples include methylolpropane tetra(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene/polypropylene glycol di(meth)acrylate, alkylene oxide-modified trimethylolpropane tri(meth)acrylate, and the like.

Examples of the bisphenol A-based (meth)acrylate compounds include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 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)acryloxytetraethyleneglycol isocyanate) hexamethylene isocyanurate, alkylene Examples thereof include oxide-modified urethane di(meth)acrylate.

The amount of the ethylenically unsaturated double bond-containing compound mixed 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, per 100 parts by weight of the polyol compound. It is more than 80 parts by weight and 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. Also, 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, the curable composition of the present invention may contain, for example, colorants, surfactants, polymerization inhibitors, fibers, and the like.
Examples of coloring agents include pigments and dyes.
Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and the like. Such surfactants can impart storage stability and dispersion stability.
Examples of polymerization inhibitors include hydroquinone-based polymerization inhibitors, benzoquinone-based polymerization inhibitors, catechol-based polymerization inhibitors, and piperidine-based polymerization inhibitors. Such a polymerization inhibitor imparts long-term storage stability in the later-described two-liquid type form, and also contributes to production stability when added during the polyol production process.
Examples of 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 forming properties, 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 foam-in-place, preferably a rigid polyurethane foam-forming composition, more preferably a rigid polyisocyanurate foam-forming composition.
Such a curable composition is applied to a substrate and foamed at a site such as a building, and the substrate is coated with a foam, or a substrate (surface material) is applied to one or both sides of the foam. It can be laminated and used for applications such as freezers/refrigerators, plants, tunnels, vehicles, ships, aircraft, electronic devices, and home appliances. Specific examples of target substrates include concrete, mortar, metal plates, inorganic boards, plywood, plastic plates, and wooden boards. 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 in the form of a two-liquid type at the time of circulation, and mixed at the time of use (during foam formation). In such a two-component form, 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·s or less, from the viewpoint of the storage stability of the first liquid, handling properties, workability during foam formation, and the like. s or less, more preferably 50 mPa·s or more and 250 mPa·s or less. The viscosity is the viscosity measured at 20 rpm with a BH type viscometer at a temperature of 20° C. (guideline value for 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. As a result, stirring work and the like during construction can be reduced, and advantageous effects can be obtained in terms of handleability, workability, miscibility with the polyisocyanate compound, 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 still more preferably 50 mPa·s or more and 250 mPa·s or less.

When applying the curable composition to a substrate, for example, using a spray foaming machine for spraying work (for example, a two-liquid tip mixing type spray coating machine), the first liquid and the second liquid can be sprayed. In this case, the temperatures of the first liquid and the second liquid are preferably set to 20° C. or higher and 60° C. or lower, more preferably 30° C. or higher and 50° C. or lower. The first liquid and the second liquid, which have been set to a predetermined temperature in this manner, are mixed at the tip of the spray gun and sprayed toward the substrate to form a foam on the substrate. As for the spraying environment, it is possible to carry out construction preferably at 5°C or higher and 45°C or lower.
It is preferable to mix the first liquid and the second liquid at a volume ratio of about 1:1. A foam formed by such a method can exhibit excellent performance in terms of 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 about 15 mm or more and 500 mm or less.

It can also be used as a heat insulating sandwich panel in which foam is laminated between face materials such as metal plates as a building material for buildings, civil engineering structures, and the like. Such heat-insulating sandwich panels are produced by a method in which a foam is produced in advance and two face materials are pasted together; Examples include a method of bonding two face materials together, a method of injecting a curable composition between two face materials and foaming them to form a foam, and the like.

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

As the first liquid, a uniform mixture of the following raw materials at the weight ratios shown in Table 1 was prepared. As the second liquid, one made 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 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)
・Blowing agent 1: hydrochlorofluoroolefin ・Blowing agent 2: hydrofluoroolefin ・Blowing agent 3: water (hydroxyl value: 6233 mgKOH/g)
Catalyst 1: nurate catalyst (glycol solution of tetraalkylammonium 2-ethylhexanoate)
- Catalyst 2: nurate catalyst (glycol solution of tetraalkylammonium lactate)
- Catalyst 3: Resin catalyst (octylic acid solution of bismuth octylate)
- Flame retardant 1: Alkylphosphinate compound (tris(diethylphosphinate) aluminum, phosphorus content 23.8% by weight)
- Flame retardant 2: Phosphate ester (trimethyl phosphate, 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: phosphinate compound (sodium phosphinate, phosphorus content 35.2% by weight)
・ Flame retardant 6: Cyclic phosphoramidate (R1 in formula 4: all methylene groups, R2: all methyl groups, R3: all hydrogen atoms, R4: butylene group cyclic phosphoramidate, phosphorus content 16.1 weight %)
・Flame retardant 7: Cyclic phosphoramidate (R1 in formula 4: all methylene groups, R2: all methyl groups, N(R3)-R4-(R3)N: cyclic nitrogen-containing six-membered ring structure (piperidine structure) phosphoramidate, phosphorus content 16.2% by weight)
・ Flame retardant 8: Phosphate ester (tris (chloropropyl) phosphate, phosphorus content 9.5% by weight)
· Double bond compound: 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 1-30, Comparative Examples 1-2)
The first liquid and the second liquid are each heated to 40 ° C., mixed so that the isocyanate index shown in Table 1, and the obtained mixed solution is applied to the substrate (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 the entire one side of the substrate was coated with foam. Each test was carried out on the obtained specimens by the following methods. Results are shown in Table 1.

(1) Formability The state of the formed foam was visually observed. Evaluation criteria are as follows.
A: A homogeneous foam was formed.
◯: Almost homogeneous foam was formed.
Δ: Some abnormalities (brittleness, uneven foaming, poor adhesion, etc.) were observed in the foam.
x: Abnormalities were observed in the foam.

(2) Thermal conductivity A foam portion of the specimen was cut out and thermal conductivity was measured using a thermal conductivity meter. Evaluation criteria are as follows.
○: Thermal conductivity is 0.03 W / (m K) or less ×: Thermal conductivity is greater than 0.03 W / (m K)

(3) Heat resistance A cone calorimeter specified in ISO 5660 was used. The heating intensity was 50 kW/m ² and the heating time was 20 minutes. The following evaluation items were evaluated. 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: Total calorific value is 10 MJ/m ² or less B: Total calorific value is more than 10 MJ/m ² or less and 15 MJ/m ² or less C: Total calorific value is more than 15 MJ/m ² or less than 20 MJ/m ² D: Total calorific value is 20 MJ / ^m2 greater than (3-3) heat resistance 3 (maximum heat release rate)
A: The maximum heat generation rate is 100 kW/m ² or less B: The maximum heat generation rate is more than 100 kW/m ² or less than 150 kW/m ² C: The maximum heat generation rate is more than 150 kW/m ² or less than 200 kW/m ² D: The maximum heat generation rate is 200 kW / ^m2 >

Claims (2)

A curable composition for forming a foam comprising:
containing a polyol compound, a blowing agent, a catalyst, a flame retardant, and a polyisocyanate compound,
A two-part curable composition comprising a first liquid containing a polyol compound, a foaming agent, a catalyst, and a flame retardant, and a second liquid containing a polyisocyanate compound,
The flame retardant contains an organic phosphorus compound, and the organic phosphorus compound contains a phosphate ester and an alkylphosphinate compound, and the mixing ratio (weight ratio) of the phosphate ester and the alkylphosphinate compound is acid ester: alkylphosphinate compound ratio is 90:10 to 50:50,
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 mixing ratio of the polyol compound and the polyisocyanate compound has an isocyanate index of 130 or more and 500 or less,
A curable composition characterized by being 2. The curable composition according to claim 1, wherein the content of the organic phosphorus compound is 80% by weight or more and 100% by weight or less in the total amount of the flame retardant.