JP2019065227A - Curable composition and coating method - Google Patents

Abstract

To provide a curable composition capable of forming a foam having excellent performance in low thermal conductivity, heat resistance, and adhesion.SOLUTION: The curable composition of the present invention contains a polyol compound, a foaming agent, a catalyst, a foam stabilizer, a phosphorus compound, and a polyisocyanate compound. The curable composition contains an aliphatic polyester polyol as the polyol compound and contains a phosphinate compound as the phosphorus compound.SELECTED DRAWING: None

Description

  The present invention relates to novel curable compositions. The curable composition of the present invention is capable of forming a foam which has low thermal conductivity and heat resistance as well as excellent adhesion.

  In general, in buildings and the like, heat is generated between indoors and outdoors by providing foam on wall surfaces, ceiling surfaces, floor surfaces and the like. Such foam is a material of low thermal conductivity, and as a typical example, organic foams such as urethane foam, phenol foam, styrene foam and the like are used. Among these, urethane foam is frequently used because it has excellent low thermal conductivity of about 0.025 W / (m · K) and that it can be applied at a relatively low cost. It is done. However, organic foams such as urethane foams tend to be difficult to obtain high performance in resistance to flames and high heat, that is, heat resistance, because organic foams are the main components.

Japanese Patent Application Publication No. 2016-531966

  In Patent Document 1 (Japanese Patent Laid-Open No. 2016-531966) and the like, an attempt is made to impart heat resistance and the like to a low thermal conductive foam by a composition containing a polyol compound, an isocyanate compound and a solid flame retardant. ing. As this solid flame retardant, phosphorus based flame retardants such as triphenyl phosphate, halogen based flame retardants such as decabromodiphenyl oxide, and metal hydrate based flame retardants such as aluminum hydroxide and magnesium hydroxide are described. There is.

  However, in the composition as described in the above-mentioned patent documents, there is room for improvement in the heat resistance of the formed foam. Furthermore, there is room for improvement in adhesion as well.

  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 low thermal conductivity and heat resistance, as well as excellent performance in adhesion.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said problem, the present inventors considered that the thing containing a specific compound was useful about the curable composition for foam formation, and came to completion of this invention. .

（式２）

４．１．から３．のいずれかに記載の硬化性組成物を基材に塗付し、当該基材をフォームで被覆することを特徴とする被覆方法。 That is, the present invention has the following features.
1. A curable composition for forming foam,
Containing a polyol compound, a blowing agent, a catalyst, a foam stabilizer, a phosphorus compound, and a polyisocyanate compound,
The polyol compound includes an aliphatic polyester polyol,
A curable composition comprising a phosphinate compound as the phosphorus compound.
2. The polyol compound is characterized in that it contains an aliphatic polyester polyol in an amount of more than 10% by weight based on the total amount of the polyol compound. The curable composition as described in-.
3. As the above-mentioned phosphorus compound, an alkylphosphinic acid metal salt compound represented by the following (formula 1) or the following (formula 2) is included. Or 2. Curable composition as described.
(Formula 1)

(Formula 2)

4.1. To 3. A coating method comprising applying the curable composition according to any one of the above to a substrate and coating the substrate with a foam.

  ADVANTAGE OF THE INVENTION According to this invention, the foam | form which has the outstanding performance in low thermal conductivity, heat resistance, adhesiveness, etc. can be formed.

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

  The curable composition of the present invention is applicable to foam formation, and contains, as essential components, a polyol compound, a foaming agent, a catalyst, a foam stabilizer, a phosphorus compound, and a polyisocyanate compound.

  The present invention includes an aliphatic polyester polyol as a polyol compound and a phosphinate compound as a phosphorus compound to form a foam having excellent low thermal conductivity and to exhibit excellent heat resistance and adhesion. It is a feature.

The aliphatic polyester polyol can be obtained, for example, by reacting an aliphatic polybasic acid such as succinic acid, adipic acid, sebacic acid, maleic acid or fumaric acid with a polyhydric alcohol such as diethylene glycol.
The content of the aliphatic polyester polyol in the polyol compound is preferably more than 10% by weight, more preferably 40% by weight or more, still more preferably 70% by weight, and most preferably 90% by weight or more. With such a ratio, it is easy to form a foam having more excellent adhesion and excellent low thermal conductivity.
In the present invention, in particular, among the aliphatic polyester polyols, (A) aliphatic polyester polyols obtained by reacting one or more aliphatic polybasic acids selected from maleic acid and fumaric acid with polyhydric alcohols (hereinafter referred to as It is preferable to include "aliphatic polyester polyol (A)". By including such an aliphatic polyester polyol (A), heat resistance and adhesion can be improved in addition to the above effects. The content of the aliphatic polyester polyol (A) contained in the aliphatic polyester polyol is preferably 50% by weight or more, more preferably 70% by weight or more, and most preferably 90% by weight or more.

  Examples of polyols other than aliphatic polyester polyols include aromatic polyester polyols, polyether polyols, polycarbonate polyols, polylactone polyols, polybutadiene polyols, polypentadiene polyols, castor oil polyols and the like.

Examples of aromatic polyester polyols include condensed polyester polyols obtained by reacting an aromatic polybasic acid such as orthophthalic acid, isophthalic acid, terephthalic acid and phthalic anhydride with polyhydric alcohol, and phthalic acid such as polyethylene terephthalate A phthalic acid type polyester polyol etc. which are obtained by decomposing a polyester molding etc. are mentioned.
Examples of polyether polyols include aromatic polyether polyols, phosphorus-containing polyether polyols, glycerin-based polyether polyols, amino group-containing polyether polyols and the like. 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, by adding an alkylene oxide using toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, triethanolamine, Mannich condensation product, etc. as an initiator) The aromatic amine-type polyether polyol etc. which are obtained are mentioned. Examples of the phosphorus-containing polyether polyol include dialkyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphonate which is a diol having a phosphoric acid ester structure. Examples of glycerin-based polyether polyols include polyether polyols obtained by adding alkylene oxide using glycerin as an initiator. Examples of the amino group-containing polyether polyol include those to which an alkylene oxide is added with a low molecular weight amine (eg, ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, neopentyl diamine, etc.) as an initiator.

（式２）

（Ｒ^１、Ｒ^２は、同一であるかまたは異なるものであり、線状または分枝状の炭素数１〜６のアルキルである。Ｒ^３は、線状または分枝状の炭素数１〜１０のアルキレン、炭素数６〜１０のアリーレン、炭素数７〜２０のアルキルアリーレン、または炭素数７〜２０のアリールアルキレンである。Ｍは、Ｍｇ、Ｃａ、Ａｌ、Ｓｂ、Ｓｎ、Ｇｅ、Ｔｉ、Ｚｎ、Ｆｅ、Ｚｒ、Ｃｅ、Ｂｉ、Ｓｒ、Ｍｎ、Ｌｉ、Ｎａ、Ｋ、またはプロトン化窒素塩基である。ｍは１〜４、ｎは１〜４、ｘは１〜４である。） As the phosphinate compound, one or more selected from an alkylphosphinic acid metal salt compound represented by the following (formula 1) or the following (formula 2), and a polymer thereof are preferable.
(Formula 1)

(Formula 2)

(R ¹ and R ² are the same or different and are linear or branched C ¹ to C 6 alkyl. R ³ is linear or branched C ¹ to C 6 10 alkylene, arylene having 6 to 10 carbons, alkylarylene having 7 to 20 carbons, or aryl alkylene having 7 to 20 carbons M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base, wherein m is 1 to 4, n is 1 to 4, and x is 1 to 4.)

The above R ¹ and R ² are preferably the same or different and are methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl or phenyl. R ³ is preferably methylene, ethylene, n-propylene, i-propylene, n-butylene, t-butylene, n-pentylene, n-octylene, n-dodecylene, phenylene, naphthylene, methylphenylene, ethylphenylene, t-butylphenylene, methylnaphthylene, ethylnaphthylene, t-butylnaphthylene, phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene. The above M is preferably Mg, Ca, Al, Sn, Ti, Zn, Fe or Zr.

  Such alkylphosphinic acid metal salt compounds are obtained, for example, by reacting an alkylsulfonic acid and / or phosphinic acid and / or an alkali metal salt thereof with an olefin in the presence of a free radical initiator to obtain an alkylphosphinic acid It can be obtained by / or obtaining an alkali metal salt thereof and further reacting with a metal compound. Specifically, as the alkylphosphinic acid metal salt compound, for example, tris (diethylphosphinic acid) aluminum, tris (methylethylphosphinic acid) aluminum, tris (butylethylphosphinic acid) aluminum, tris (diphenylphosphinate) aluminum, bis (Diethyl phosphinic acid) zinc, bis (methyl ethyl phosphinic acid) zinc, bis (diphenyl phosphinic acid) zinc, bis (diethyl phosphinic acid) titanyl, tetrakis (diethyl phosphinic acid) titanium, bis (methyl ethyl phosphinate) titanyl, tetrakis Examples thereof include (methylethylphosphinic acid) titanium, bis (diphenylphosphinic acid) titanyl, tetrakis (diphenylphosphinic acid) titanium and the like, and one or more of these can be used. Among these, tris (diethylphosphinic acid) aluminum, tris (methylethylphosphinic acid) aluminum, tris (butylethylphosphinic acid) aluminum, tris (diphenylphosphinic acid) aluminum are particularly preferable. is there.

The phosphinate compound is preferably powdery at normal temperature (20 ° C.), and the average particle size thereof is preferably 50 μm or less, more preferably 0.5 μm to 30 μm. In addition, the average particle diameter said here can be measured by a laser diffraction type particle size distribution analyzer. The density of the phosphinate compound is preferably 1.0 g / cm ³ or more and 1.8 g / cm ³ or less, more preferably 1.2 g / cm ³ or more and 1.5 g / cm ³ or less. The density is a value at 20 ° C.

  The mixing amount of the phosphinate compound is preferably 1 to 150 parts by weight, more preferably 10 to 135 parts by weight, still more preferably 20 to 115 parts by weight, and most preferably 35 to 100 parts by weight with respect to 100 parts by weight of the polyol compound. It is a weight part. If the mixing amount of the phosphinate compound is in such a range, it is preferable in terms of heat resistance and the like.

  In the curable composition of the present invention, phosphorus compounds other than the above phosphinate compounds, such as organic phosphoric acid ester compounds, can also be used as the phosphorus compound. Examples of organic phosphoric acid ester compounds include halogenated alkyl esters of phosphoric acid, alkyl phosphoric acid esters, aryl phosphoric acid esters, phosphonic acid esters and the like, and one or more of these can be used. Specific examples of organic phosphoric acid ester compounds include tris (chloroethyl) phosphate, tris (β-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tributoxyethyl phosphate, tributyl phosphate, triethyl phosphate, cresyl phenyl phosphate And dimethyl methyl phosphonate. In the present invention, by containing a phosphinate salt compound and an organic phosphoric acid ester compound as a phosphorus compound, the viscosity of the curable composition can be reduced, the storage stability can be improved, the workability during construction can be improved, and the heat resistance of the foam can be improved. Can be improved.

  The mixing amount of the organic phosphoric acid ester compound is preferably 50 to 800 parts by weight, more preferably 100 to 600 parts by weight, and still more preferably 150 to 400 parts by weight with respect to 100 parts by weight of the polyol compound.

  Examples of the blowing 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 them, examples of the hydrocarbon include propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and the like. As the hydrochlorofluorocarbon (HCFC), for example, 1,1-dichloro-1-fluoroethane (HCFC-141B), 1-chloro-1,1-difluoroethane (HCFC-142B), chlorodifluoromethane (HCFC-22) Etc. As the hydrofluorocarbon (HFC), 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 (HFC 227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluorobutane (HFC 365mfc), 1,1,1,2,2,2, 3,4,5,5,5-decafluoropentane (HFC 4310 mee) and the like.

  As hydrofluoroolefin (HFO), for example, pentafluoropropene such as 1,2,3,3,3-pentafluoropropene (HFO 1225ye), 1,3,3,3-tetrafluoropropene (HFO1234ze), 2,2,3 Tetrafluoropropenes such as 3,3,3-tetrafluoropropene (HFO 1234yf), 1,2,3,3-tetrafluoropropene (HFO 1234ye), trifluoropropenes such as 3,3,3-trifluoropropene (HFO 1243zf) , Tetrafluorobutene (HFO 1345), pentafluorobutene (HFO 1354), hexafluorobutene (HFO 1336), heptafluorobutene (HFO 1327), heptafluoropentene (HFO 1447), 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), Dichlorotrifluoropropene (HCFO 1223) and the like, or isomers thereof (cis form, trans form) and the like can be mentioned. As a foaming agent in this invention, 1 type, or 2 or more types chosen from a hydrofluoro olefin, a hydrochloro fluoro olefin, and water are suitable.

  The amount of the foaming agent mixed is preferably 10 to 200 parts by weight, more preferably 20 to 180 parts by weight, and still more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the polyol compound.

  As a catalyst, it is desirable to include a nuration catalyst. The nuration catalyst is not particularly limited as long as it is a catalyst effective for isocyanuration, and, for example, a hydroxide of tetraalkylammonium such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, trimethylbenzylammonium or the like, or an organic weak acid thereof Hydroxides of trialkylhydroxyalkyl ammonium such as salts, trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, triethylhydroxyethylammonium etc. or organic weak acid salts thereof, alkyl carboxylic acids (eg acetic acid, caproic acid, octylic acid) , Myristic acid etc.), aluminum acetylacetone, lithium acetylacetone etc Such as metal chelate compounds of tonnes, Friedel-Crafts catalysts such as aluminum chloride and boron trifluoride, organic metal compounds such as titanium tetrabutylate and tributylantimony oxide, and aminosilyl group-containing compounds such as hexamethyl silazane etc. One or more of these can be used. As the catalyst, in addition to the above-mentioned nuration catalyst, for example, known catalysts such as a tertiary amine catalyst, an imidazole catalyst and an organometallic catalyst can be used, and these may be used in combination with the above-mentioned nuration catalyst .

  The mixing amount of the catalyst (in terms of active ingredient) is preferably 0.1 to 40 parts by weight, more preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of the polyol compound. 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 foam stabilizer include silicone foam stabilizers such as polyether-modified silicone compounds, and fluorine-containing compound foam stabilizers. These can be used alone or in combination of two or more. Examples of polyether-modified silicone compounds include graft copolymers of polydimethylsiloxane with polyoxyethylene glycol or polyoxyethylene-propylene glycol, and the like. The mixing amount of the foam stabilizer is preferably 0.1 to 40 parts by weight, more preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of the polyol compound.

  In conventional general urethane foams and the like, the entire foam burns and shrinks due to flames and high heat, the sound part (non-carbonized part) is lost, and the dimensions of the foam may also be greatly changed. On the other hand, in the foam formed by the curable composition of the present invention, when exposed to a flame or high heat, combustion, shrinkage, dimensional change, etc. of the foam are suppressed, and further thermal decomposition in the foam after extinguishing. Progress is also suppressed. Thus, even if the foam is exposed to flames or high heat, a healthy part tends to remain in the foam. As described above, the foam by the curable composition of the present invention can obtain a remarkable effect in heat resistance (in particular, when the foam is directly exposed to a flame or high heat) as compared with foams according to the prior art. it can.

  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 preferred in terms of ease of handling, reaction speed, physical properties of the resulting foam, cost advantage and the like. As MDI, for example, monomeric MDI, polymeric MDI (polymethylene polyphenyl isocyanate) and the like can be mentioned.

  In the curable composition of the present invention, the above-mentioned polyol compound and the above-mentioned polyisocyanate compound such that the isocyanate index is preferably 150 or more, more preferably 200 to 800, still more preferably 250 to 500, most preferably 300 to 400. It is desirable to mix etc. If the isocyanate index is in such a range, it is preferable in terms of heat resistance and the like. The isocyanate index is represented by 100 times the value obtained by dividing the number of equivalents of the isocyanate group of the polyisocyanate compound by the total number of equivalents of active hydrogen of the active hydrogen-containing component (polyol compound, water, etc.). is there.

  The curable composition of the present invention can contain, in addition to the components described above, an ethylenically unsaturated double bond-containing compound other than the aliphatic polyester polyol (A). In the present invention, by the use of such an ethylenically unsaturated double bond-containing compound, effects such as heat resistance and the like by the phosphinate compound can be obtained more efficiently. Examples of the ethylenically unsaturated double bond include (meth) acryloyl group, allyl group, propenyl group and the like.

  The ethylenically unsaturated double bond-containing compound is preferably one having an ethylenic unsaturated double bond concentration in one molecule of 0.5 to 20 mmol / g, and more preferably 5 to 15 mmol / g, in view of the above-mentioned effects and the like. It is more preferable that it is g. 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 represented by 1000 times (mmol / g) of the value divided by.

  Specific examples of the ethylenically unsaturated double bond-containing compound include, for example, polyhydric alcohols (for example, alcohols having a valence of 2 or more and derivatives thereof, phenols having a valence of 2 or more, 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 bisphenol A (meth) acrylate compounds, reaction products of glycidyl group-containing compounds and unsaturated carboxylic acids, (meth) acrylate compounds having a urethane bond in the molecule, and nonylphenoxypolyethylene oxyacrylate. These can be used alone or in combination of two or more.

  Among these, as a reaction product of polyhydric alcohol and unsaturated carboxylic acid, for example, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta ( Meta) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, ditritriol 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 above-mentioned bisphenol A (meth) acrylate compounds 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 and the like Can be mentioned.

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

  The mixing amount of the ethylenically unsaturated double bond-containing compound is preferably 1 to 100 parts by weight, more preferably 5 to 90 parts by weight, still more preferably 10 to 80 parts by weight with respect to 100 parts by weight of the polyol compound. . When a plurality of hydroxyl groups are contained in the ethylenically unsaturated double bond-containing compound, 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.

  When the above ethylenically unsaturated double bond-containing compound is used, the mixing amount of the phosphinate compound is preferably 3 to 200 parts by weight, more preferably 5 to 150 parts by weight with respect to 100 parts by weight of the polyol compound. More preferably, it can be 10 to 100 parts by weight.

In the curable composition of the present invention, in addition to the above components, for example, a flame retardant, a colorant, a surfactant, a fiber, a radical scavenger, and the like can be mixed.
Examples of the flame retardant include halogen flame retardants, organic bromine flame retardants, nitrogen flame retardants, metal hydrate flame retardants, etc. Among them, nitrogen flame retardants having relatively low density are preferable. It is.
As a coloring agent, a pigment, a dye, etc. are mentioned, for example.
As surfactant, nonionic surfactant, anionic surfactant, cationic surfactant etc. are mentioned, for example. Such surfactants can impart storage stability and dispersion stability.
As a fiber, an organic fiber, an inorganic fiber, etc. are mentioned, for example. Such fibers can provide construction workability, foam formation, dimensional stability, and the like. In the present invention, since a specific phosphorus compound is used, a fiber may not be used, but the effect can be exhibited with a small amount of fiber.

Examples of radical scavengers include hydroquinone radical scavengers such as hydroquinone, methylhydroquinone, t-butylhydroquinone, dibutylhydroquinone, hydroquinone monomethyl ether, 4-methoxyphenol, 2,6-di-tert-butylphenol, 2,6. -Phenolic radical scavengers such as di-tert-butyl-p-cresol, benzoquinone radical scavengers such as benzoquinone, methylbenzoquinone, 2-hydroxybenzoquinone and t-butylbenzoquinone, catechol such as catechol and t-butyl catechol Phenothiazine-based radicals such as radical scavengers, phenothiazine, bis (α-methylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, bis (α, α-dimethylbenzyl) phenothiazine捉剤, naphthoquinone, naphthohydroquinone, pyrogallol, N- nitrosophenylhydroxylamine, benzothiazole, dimethyl aniline, vinylpyrene, butylated hydroxy anisole, butylated hydroxy toluene and the like.
Such a radical scavenger imparts long-term storage stability and contributes to improvement in heat resistance in the form of a two-pack type described later. Furthermore, when it is added in the polyol production process, it can also contribute to production stability. It is particularly effective when an aliphatic polyester polyol (A) is used as the polyol.
The mixing amount of the radical scavenger is not particularly limited, but is preferably 0.01 parts by weight or more and 3 parts by weight or less, more preferably 0.02 parts by weight or more and 1 part by weight or less, with respect to 100 parts by weight of the polyol compound. Is 0.03 parts by weight or more and 0.5 parts by weight or less.

  The curable composition of the present invention is a composition for forming a foam, preferably a composition for forming a rigid polyurethane foam, more preferably a composition for forming a rigid polyisocyanurate foam. In addition, the curable composition of the present invention is suitable for use in coating and foaming on a substrate at a site such as a building and covering the substrate with foam. The target substrates are, for example, materials constituting wall surfaces, ceiling surfaces, floor surfaces, etc. in buildings etc. Specifically, for example, concrete, mortar, metal plate, inorganic board, plywood, heat insulating plate etc. Can be mentioned. These substrates may be subjected to surface treatment with a primer or the like prior to foam formation.

  The curable composition of the present invention is preferably in the form of a two-pack type at the time of distribution, and is preferably used by mixing at the time of use (form formation). In such a two-component form, for example, the first liquid is a polyol composition containing a polyol compound, a foaming agent, a catalyst, a foam stabilizer, and a phosphorus compound, and the second liquid is a polyisocyanate compound. can do.

  The viscosity of the first liquid is preferably 500 mPa · s or less, more preferably 20 to 300 mPa · s, and still more preferably, from the viewpoint of storage stability of the first liquid, handling property, construction workability at the time of foam formation, etc. It is 50-250 mPa * s. The viscosity is the viscosity at 20 rpm measured at a temperature of 20 ° C. with a BH-type viscometer (the indicator value at the fourth rotation).

  When the curable composition is applied to a substrate, for example, a spray foamer for spraying work (for example, a two-component tip mixed type spray coater or the like) is used to form the first liquid. It is sufficient to spray and apply a mixture of water and the second liquid. In this case, it is preferable to set the temperature of the first liquid and the second liquid to be preferably 20 to 60 ° C., more preferably 30 to 50 ° C., respectively. The first and second liquids thus set at a predetermined temperature are mixed at the spray tip and sprayed toward the substrate to form a foam on the substrate. It is desirable that the mixing of the first liquid and the second liquid be about 1: 1 in volume ratio. The foam formed by such a method can exhibit excellent performance in low thermal conductivity, heat resistance, adhesion and the like. The thickness of the foam is not particularly limited and may be appropriately set according to the required performance etc., but is preferably 10 mm or more, more preferably about 15 to 500 mm. In addition, such construction can be performed without particular limitation, such as new construction and repair.

  The following examples are provided to further clarify the features of the present invention.

What prepared the following raw material uniformly mixed with the weight ratio shown in Table 1 as a 1st liquid (1st liquid ao) was prepared. As the second liquid, a liquid (second liquid a) consisting of polymeric MDI was prepared. In Table 1, the amount of the active ingredient is described for the catalyst.
Polyol compound 1: Aromatic polyester polyol (terephthalic acid polyester polyol, hydroxyl value: 250 mg KOH / g)
Polyol compound 2: Aliphatic polyester polyol (succinic acid polyester polyol, hydroxyl value: 100 mg KOH / g)
Polyol compound 3: aromatic polyether polyol (Mannich modified polyether polyol, hydroxyl value: 350 mg KOH / g)
Polyol compound 4: Aliphatic polyester polyol (fumaric acid polyester polyol, hydroxyl value: 150 mg KOH / g)
-Blowing agent 1: Hydrochlorofluoroolefin-Blowing agent 2: Hydrofluoroolefin-Blowing agent 3: Water (hydroxyl value: 6233 mg KOH / g)
Catalyst 1: Nuration catalyst (ethylene glycol solution of tetraalkyl ammonium organic acid salt, 50% by weight of active ingredient, hydroxyl value: 900 mg KOH / g)
・ Catalyst 2: imidazole based catalyst (100% by weight of active ingredient)
Phosphorus compound 1: Phosphinate salt compound (tris (diethylphosphinic acid) aluminum, average particle size 4 μm, density 1.35 g / cm 3)
· Phosphorus compound 2: Organic phosphoric acid ester compound (tris (β-chloropropyl) phosphate, density 1.29 g / cm 3)
· Double bond compound 1: compound having ethylenic unsaturated double bond (trimethylolpropane triacrylate, concentration of ethylenic unsaturated double bond: 10 mmol / g, hydroxyl value: 0 mg KOH / g)
· Radical scavenger 1: Hydroquinone · Radical scavenger 2: Hydroquinone monomethyl ether · Foam stabilizer: Silicone foam stabilizer

  The first liquid and the second liquid are heated to 40 ° C. respectively, mixed to obtain an isocyanate index as shown in Table 2, and the obtained mixed liquid is coated on a substrate (slate plate) and foamed. Thus, a test piece (thickness 50 mm) in which the entire one side of the substrate was coated with foam was obtained. Each test was implemented by the following method about the obtained test body. The combinations of the first solution and the second solution and the results are shown in Table 2.

(1) Adhesion The evaluation sample which cut | judged to 100 mm x 100 mm x 20 mm from the formed foam is produced, About this evaluation sample, JIS A 9526: 2006 "spray hard urethane foam for building heat insulation", adhesion strength test Adhesion was evaluated according to the same. The results are shown in Table 2. Evaluation is as follows.
:: adhesion strength is 100 kPa or more ○: adhesion strength is 80 kPa or more and less than 100 kPa Δ: adhesion strength is 60 kPa or more and less than 80 kPa ×: adhesion strength is less than 60 kPa

(2) Foam Forming Property The state of the formed foam was visually observed. Evaluation criteria are as follows.
:: A homogeneous foam was formed.
○: Almost homogeneous foam was formed.
Δ: Some abnormalities (nonuniform foaming etc.) were observed in the foam.
X: An abnormality was found in the form.

(3) Thermal conductivity The foam part of the test body was cut out, and the 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 0.03 W / (m · K)

(4) Heat resistance test It implemented using the corn calorie meter prescribed to ISO5660. The heating strength was 50 kW / m ² , and the heating time was 5 minutes, 10 minutes, and 20 minutes, respectively. The evaluation items and evaluation criteria are as follows.

(Evaluation item)
(4-1) Dimensional change ◎: The dimensional change in the thickness direction after the test is 10 mm or less ○: The dimensional change in the thickness direction after the test is more than 10 mm and 20 mm or less ×: The dimensional change in the thickness direction after the test is more than 20 mm (4 2) Total calorific value ○: Total calorific value is 8 MJ / m ² or less ×: Total calorific value is more than 8 MJ / m ² (4-3) Maximum calorific rate ○: Maximum calorific speed is 200 kW / m ² or less x: Maximum Heat generation rate is over 200 kW / m ²

(Evaluation criteria)
│ │ │ Heating time │ 4 │ 4 │ 4 3 │
│ A │ 20 minutes │ │ ○ │ ○ │
│A'│ 20 minutes│ ○ │ ○ │ ○ │
│ B │ 10 minutes │ │ ○ │ ○ │
│B'│ 10 minutes│ ○ │ ○ │ ○ │
│ C │ 5 minutes │ │ ○ │ ○ │
│C ││ 5 minutes│ ○ │ ○ │ ○ │
│ D │ 5 minutes │ x │ x │ x │
With regard to heat resistance, excellent A> A ′>B> B ′>C> C ′> D is inferior.

Claims (4)

A curable composition for forming foam,
Containing a polyol compound, a blowing agent, a catalyst, a foam stabilizer, a phosphorus compound, and a polyisocyanate compound,
The polyol compound includes an aliphatic polyester polyol,
A curable composition comprising a phosphinate compound as the phosphorus compound.   The curable composition according to claim 1, wherein the polyol compound contains an aliphatic polyester polyol in an amount of more than 10% by weight based on the total amount of the polyol compound. The curable composition according to claim 1 or 2, wherein the phosphorus compound contains an alkylphosphinic acid metal salt compound represented by the following (formula 1) or the following (formula 2).
(Formula 1)

(Formula 2)

A coating method comprising applying the curable composition according to any one of claims 1 to 3 to a substrate and coating the substrate with a foam.