JP7127974B2 - Curable composition and coating method - 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, heat resistance, and excellent adhesion.

Generally, in a building or the like, foam is provided on a wall surface, a ceiling surface, a floor surface, or the like to suppress heat transfer between indoors and outdoors. 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.

Japanese Patent Publication No. 2016-531966

In Patent Document 1 (Japanese National Publication of International Patent Application No. 2016-531966), etc., attempts have been made to impart heat resistance and the like to a low thermal conductive foam by using a composition containing a polyol-based compound, an isocyanate-based compound, and a solid flame retardant. ing. As for the solid flame retardants, phosphorus flame retardants such as triphenyl phosphate, halogen flame retardants such as decabromodiphenyl oxide, and metal hydrate flame retardants such as aluminum hydroxide and magnesium hydroxide are described. there is

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

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, heat resistance, and excellent adhesion.

As a result of intensive studies to solve the above problems, the present inventors conceived that a curable composition for foam formation containing a specific compound is beneficial, and have completed the present invention. .

（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。）
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 a foam comprising:
Containing a polyol compound, a blowing agent, a catalyst, a foam stabilizer, a phosphorus compound, and a polyisocyanate compound,
The polyol compound contains an aliphatic polyester polyol,
The phosphorus compound includes a phosphinate compound and an organic phosphoric acid ester compound ,
an isocyanate index of 250 to 800;
A curable composition characterized by:
2. 1. The polyol compound is characterized in that it contains more than 10% by weight of aliphatic polyester polyol relative to the total amount of the polyol compound. The curable composition according to .
3. 1. An alkylphosphinate metal salt compound represented by the following (formula 1) or (formula 2) below is included as the phosphinate compound. or 2. A curable composition as described.
(Formula 1)

(Formula 2)

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

According to the present invention, a foam having excellent properties such as low thermal conductivity, heat resistance and adhesion 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, as essential components, a polyol compound, a blowing agent, a catalyst, a foam stabilizer, a phosphorus compound and a polyisocyanate compound.

The present invention contains an aliphatic polyester polyol as a polyol compound and a phosphinate compound as a phosphorus compound, thereby forming a foam having excellent low thermal conductivity and exhibiting excellent heat resistance and adhesion. It is characterized.

Aliphatic polyester polyols can be obtained, for example, by reacting aliphatic polybasic acids such as succinic acid, adipic acid, sebacic acid, maleic acid and fumaric acid with polyhydric alcohols such as diethylene glycol.
The content of the aliphatic polyester polyol in the polyol compound is preferably over 10% by weight, more preferably 40% by weight or more, even more preferably 70% by weight, and most preferably 90% by weight or more. Such a ratio facilitates formation of a foam having better adhesion and excellent low thermal conductivity.
In the present invention, among aliphatic polyester polyols, (A) an aliphatic polyester polyol obtained by reacting one or more aliphatic polybasic acids selected from maleic acid and fumaric acid with a polyhydric alcohol (hereinafter referred to as Also referred to as "aliphatic polyester polyol (A)"). By containing 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, and castor oil-based polyols.

Examples of aromatic polyester polyols include condensed polyester polyols obtained by reacting aromatic polybasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride with polyhydric alcohols, and phthalic acid-based polyols such as polyethylene terephthalate. Examples thereof include phthalic acid-based polyester polyols obtained by decomposing polyester moldings.
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 to 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.

（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 alkylphosphinate metal salt compounds represented by the following (Formula 1) or the following (Formula 2) and polymers thereof are suitable.
(Formula 1)

(Formula 2)

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

R ¹ and R ² above are preferably the same or different and are methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, n-pentyl or phenyl. R ³ above 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 prepared, for example, by reacting alkylphosphinic acid and/or phosphinic acid and/or their alkali metal salts with an olefin in the presence of a free radical initiator to obtain alkylphosphinic acid and / Or it can be obtained by obtaining an alkali metal salt thereof and further reacting it with a metal compound. Specifically, the alkylphosphinate metal salt compounds include, for example, tris(diethylphosphinate)aluminum, tris(methylethylphosphinate)aluminum, tris(butylethylphosphinate)aluminum, tris(diphenylphosphinate)aluminum, bis (diethylphosphinate)zinc, bis(methylethylphosphinate)zinc, bis(diphenylphosphinate)zinc, bis(diethylphosphinate)titanyl, tetrakis(diethylphosphinate)titanium, bis(methylethylphosphinate)titanyl, tetrakis Titanium (methylethylphosphinate), bis(diphenylphosphinate)titanyl, tetrakis(diphenylphosphinate)titanium and the like can be mentioned, and one or more of these can be used. Among these, aluminum tris(alkylphosphinate) selected from aluminum tris(diethylphosphinate), aluminum tris(methylethylphosphinate), aluminum tris(butylethylphosphinate), and aluminum tris(diphenylphosphinate) is preferable. be.

The phosphinate compound is preferably powdery at room temperature (20° C.) and has an average particle size of preferably 50 μm or less, more preferably 0.5 μm or more and 30 μm or less. The average particle size referred to here can be measured with a laser diffraction particle size distribution meter. 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 amount of the phosphinate compound mixed 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. weight part. If the mixed amount of the phosphinate compound is within 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 ester compounds include tris(chloroethyl) phosphate, tris(β-chloropropyl) phosphate, tris(dichloropropyl) phosphate, tributoxyethyl phosphate, tributyl phosphate, triethyl phosphate, and cresylphenyl phosphate. , dimethylmethylphosphonate and the like. In the present invention, by including a phosphinate compound and an organic phosphoric acid ester compound as the phosphorus compound, the viscosity of the curable composition is reduced, the storage stability is improved, the workability during construction is improved, and the heat resistance of the foam can be improved.

The amount of the organic phosphoric acid ester compound mixed 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 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.

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.

Desirably, the catalyst contains a nurating catalyst. Nurate-forming catalysts are not particularly limited as long as they are effective catalysts for isocyanurate-forming. salts, trialkylhydroxyalkylammonium hydroxides such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium and triethylhydroxyethylammonium or their organic weak acid salts, alkylcarboxylic acids (e.g., acetic acid, caproic acid, octylic acid , myristic acid, etc.), metal chelate compounds of β-diketones such as aluminum acetylacetone and lithium acetylacetone, Friedel-Crafts catalysts such as aluminum chloride and boron trifluoride, titanium tetrabutylate, tributyl antimony oxide, etc. Organometallic compounds, aminosilyl group-containing compounds such as hexamethylsilazane, and the like can be mentioned, and one or more of these can be used. As the catalyst, in addition to the above-mentioned nurate-forming catalysts, for example, known catalysts such as tertiary amine catalysts, imidazole-based catalysts, organometallic catalysts, etc. may be used, and these may be used in combination with the above-mentioned nulate-forming catalysts. .

The amount of the catalyst to be mixed (converted to active ingredient) is preferably 0.1 to 40 parts by weight, more preferably 0.5 to 30 parts by weight, per 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 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 to 40 parts by weight, more preferably 0.5 to 30 parts by weight, per 100 parts by weight of the polyol compound.

In general conventional urethane foam, etc., the entire foam may burn and shrink due to flames or high heat, resulting in the loss of healthy portions (non-carbonized portions) and large changes in the dimensions of the foam. On the other hand, when the foam formed from the curable composition of the present invention is exposed to flames or high heat, the combustion, shrinkage, dimensional change, etc. of the foam are suppressed. progress is also inhibited. As a result, even if the foam is exposed to flames or high heat, healthy portions tend to remain in the foam. As described above, the foam made of the curable composition of the present invention can obtain a remarkable effect in terms of heat resistance (especially when the foam is directly exposed to flames or high heat), etc., as compared with the foam made by the prior art. can.

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).

In the curable composition of the present invention, the isocyanate index is preferably 150 or more, more preferably 200 to 800, still more preferably 250 to 500, most preferably 300 to 400, so that the above polyol compound and the above polyisocyanate compound It is desirable to mix etc. If the isocyanate index is within such a range, it is preferable in terms of heat resistance and the like. 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 an ethylenically unsaturated double bond-containing compound other than the aliphatic polyester polyol (A) in addition to the components described above. In the present invention, the use of such an ethylenically unsaturated double bond-containing compound makes it possible to more efficiently obtain the effects of the phosphinate compound, such as heat resistance. Examples of ethylenically unsaturated double bonds include (meth)acryloyl groups, allyl groups, propenyl groups and the like.

The ethylenically unsaturated double bond-containing compound preferably has an ethylenically unsaturated double bond concentration of 0.5 to 20 mmol/g, more preferably 5 to 15 mmol/g, in view of the effects described above. g is more preferred. 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 to be mixed is preferably 1 to 100 parts by weight, more preferably 5 to 90 parts by weight, and still more preferably 10 to 80 parts by weight with respect to 100 parts by weight of the polyol compound. . 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.

When the ethylenically unsaturated double bond-containing compound is used, the amount of the phosphinate compound mixed 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 10 to 100 parts by weight.

In addition to the above components, the curable composition of the present invention can be mixed with, for example, flame retardants, colorants, surfactants, fibers, radical scavengers, and the like.
Examples of flame retardants include halogen-based flame retardants, organic brominated flame retardants, nitrogen-based flame retardants, metal hydrate-based flame retardants, etc. Among these, nitrogen-based flame retardants with relatively low density are preferred. is.
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 fibers include organic fibers and inorganic fibers. Such fibers can impart workability, foam formability, dimensional stability, and the like. In the present invention, since a specific phosphorus compound is used, it is not necessary to use fibers, but the effect can be exhibited with a small amount of fibers.

Examples of radical scavengers include hydroquinone radical scavengers such as hydroquinone, methylhydroquinone, t-butylhydroquinone and 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, t-butylbenzoquinone, catechol, catechols such as t-butylcatechol Radical scavengers, phenothiazine-based radical scavengers such as phenothiazine, bis(α-methylbenzyl)phenothiazine, 3,7-dioctylphenothiazine, bis(α,α-dimethylbenzyl)phenothiazine, naphthoquinone, naphthohydroquinone, pyrogallol, N-nitroso phenylhydroxylamine, benzothiazole, dimethylaniline, vinylpyrene, butylated hydroxyanisole, butylated hydroxytoluene and the like.
Such a radical scavenger imparts long-term storage stability and contributes to an improvement in heat resistance in the form of a two-liquid type described below. Furthermore, when added during 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 amount of the radical scavenger to be mixed is not particularly limited. 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 foam-forming composition, preferably a rigid polyurethane foam-forming composition, more preferably a rigid polyisocyanurate foam-forming composition. Moreover, the curable composition of the present invention is suitable for applications in which the substrate is coated with the foam by applying it to a substrate and foaming it at the site of a building or the like. The target base material is, for example, a material that constitutes the wall surface, ceiling surface, floor surface, etc. in buildings, etc. Specifically, for example, concrete, mortar, metal plate, inorganic board, plywood, heat insulating board is mentioned. These substrates may be subjected to a surface treatment or the like with an undercoat material before forming the foam.

It is desirable that the curable composition of the present invention is in a two-component form at the time of distribution, and mixed at the time of use (during foam formation). In such a two-component form, for example, the first component is a polyol composition containing a polyol compound, a foaming agent, a catalyst, a foam stabilizer, and a phosphorus compound, and the second component 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, still more preferably 20 to 300 mPa s, more preferably It is 50 to 250 mPa·s. 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).

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 preferably 20 to 60.degree. C., more preferably about 30 to 50.degree. The first liquid and the second liquid, which have been set to a predetermined temperature in this manner, are mixed at the spray tip and sprayed toward the substrate to form a foam on the substrate. It is desirable 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, adhesion, and the like. The thickness of the foam is not particularly limited, and may be appropriately set according to the required performance, etc., 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 renovation.

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

As the first liquid, the following raw materials were uniformly mixed at the weight ratios shown in Table 1 (first liquids a to o). As the second liquid, one made of polymeric MDI (second liquid a) was prepared. In addition, in Table 1, the amount of the active ingredient is described for the catalyst.
- Polyol compound 1: aromatic polyester polyol (terephthalic acid-based polyester polyol, hydroxyl value: 250 mgKOH/g)
- Polyol compound 2: Aliphatic polyester polyol (succinic acid-based polyester polyol, hydroxyl value: 100 mgKOH/g)
- Polyol compound 3: aromatic polyether polyol (Mannich-modified polyether polyol, hydroxyl value: 350 mgKOH/g)
· Polyol compound 4: Aliphatic polyester polyol (fumaric acid-based polyester polyol, 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 (ethylene glycol solution of tetraalkylammonium organic acid salt, active ingredient 50% by weight, hydroxyl value: 900 mgKOH/g)
- Catalyst 2: imidazole-based catalyst (active ingredient 100% by weight)
Phosphorus compound 1: phosphinate compound (tris(diethylphosphinate) aluminum, average particle size 4 μm, density 1.35 g/cm3)
Phosphorus compound 2: organic phosphate compound (tris (β-chloropropyl) phosphate, density 1.29 g / cm3)
· Double bond compound 1: ethylenically unsaturated double bond-containing compound (trimethylolpropane triacrylate, ethylenically unsaturated double bond concentration: 10 mmol / g, hydroxyl value: 0 mgKOH / g)
・Radical scavenger 1: hydroquinone ・Radical scavenger 2: hydroquinone monomethyl ether ・Foam stabilizer: Silicone foam stabilizer

The 1st liquid and the 2nd liquid were each heated to 40 ° C., mixed so that the isocyanate index shown in Table 2, and the obtained mixed liquid was applied to the base material (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 carried out on the obtained specimens by the following methods. Table 2 shows the combinations of the first liquid and the second liquid and the results thereof.

(1) Adhesion An evaluation sample was cut to 100 mm × 100 mm × 20 mm from the formed foam, and the evaluation sample was subjected to JIS A 9526: 2006 "Blowing hard urethane foam for building insulation", in an adhesion strength test. Adhesion was evaluated according to the following. 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 △: Adhesion strength is 60 kPa or more and less than 80 kPa ×: Adhesion strength is less than 60 kPa

(2) 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 (uneven foaming, etc.) were observed in the foam.
x: Abnormalities were observed in the foam.

(3) Thermal conductivity A foam portion of the test sample 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)

(4) Heat resistance test A cone calorimeter specified in ISO 5660 was used. The heating intensity was 50 kW/m ² and the heating time was 5 minutes, 10 minutes and 20 minutes. Evaluation items and evaluation criteria are as follows.

(Evaluation item)
(4-1) Dimensional change ◎: Dimensional change in the thickness direction after the test is 10 mm or less ○: Dimensional change in the thickness direction after the test is more than 10 mm and 20 mm or less ×: 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 over 8 MJ / m ² (4-3) Maximum heat generation rate ○: Maximum heat generation rate is 200 kW / m ² or less ×: Maximum Exothermic rate exceeding 200 kW/m ²

(Evaluation criteria)
│ │heating time │ 4-1 │ 4-2 │ 4-3 │
│Ａ │ 20 minutes│ ◎ │ ○ │ ○ │
│Ａ´│ 20 minutes│ ○ │ ○ │ ○ │
│Ｂ │ 10 minutes│ ◎ │ ○ │ ○ │
│Ｂ´│ 10 minutes│ ○ │ ○ │ ○ │
│Ｃ │ 5 minutes│ ◎ │ ○ │ ○ │
│Ｃ´│ 5 minutes│ ○ │ ○ │ ○ │
│D │ 5 minutes│ × │ × │ × │
As for the heat resistance, it is superior A>A'>B>B'>C>C'>D inferior.

Claims (4)

A curable composition for forming a foam comprising:
Containing a polyol compound, a blowing agent, a catalyst, a foam stabilizer, a phosphorus compound, and a polyisocyanate compound,
The polyol compound contains an aliphatic polyester polyol,
The phosphorus compound includes a phosphinate compound and an organic phosphoric acid ester compound ,
an isocyanate index of 250 to 800;
A curable composition characterized by: 2. The curable composition according to claim 1, wherein the polyol compound contains more than 10% by weight of the aliphatic polyester polyol based on the total amount of the polyol compound. 3. The curable composition according to claim 1, wherein the phosphinate compound comprises an alkylphosphinate metal salt compound represented by the following (formula 1) or (formula 2) below.
(Formula 1)

(Formula 2)

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