JP6568250B2 - Curable composition and coating method - Google Patents

Description

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

  In general, in buildings and the like, heat is generated and removed between indoors and outdoors by providing foam on walls, ceilings, floors, and the like. Such a foam is a material having low thermal conductivity, and representative examples thereof include organic foams such as urethane foam, phenol foam, and styrene foam. Of these, urethane foam is frequently used because it has excellent low thermal conductivity of about 0.025 W / (m · K) and can be constructed at a relatively low cost. It has been. However, since organic foams such as urethane foam are mainly composed of organic substances, there is a tendency that high performance is difficult to obtain in terms of resistance to flames and high heat, that is, heat resistance.

JP-T-2006-531966

  In Patent Document 1 (Japanese Patent Publication No. 2006-53966) 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. About this solid flame retardant, phosphorus flame retardant such as triphenyl phosphate, halogen flame retardant such as decabromodiphenyl oxide, metal hydrate flame retardant such as aluminum hydroxide and magnesium hydroxide, etc. are described. Yes.

  However, the composition as described in the above patent document has room for improvement in the heat resistance of the foam to be formed.

  This invention is made | formed in view of such a subject, and the main objective of this invention is to form the foam which has the performance excellent in low thermal conductivity, heat resistance, etc.

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

（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。）
３．１．または２．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 characteristics.
1. A curable composition for forming rigid polyurethane foam,
Contains a polyol compound, a foaming agent, a catalyst, a foam stabilizer, a phosphorus compound, and a polyisocyanate compound, and has an isocyanate index of 150 or more,
A curable composition comprising a phosphinate compound and an organophosphate compound as the phosphorus compound.
2. 1. The phosphinate compound includes an alkylphosphinic acid metal salt compound represented by the following (formula 1) or the following (formula 2). The curable composition as described.
(Formula 1)

(Formula 2)

(R ¹ and R ² are the same or different and are linear or branched alkyl having 1 to 6 carbon atoms. R ³ is linear or branched carbon having 1 to 6 carbon atoms. 10 alkylene, C6-C10 arylene, C7-C20 alkylarylene, or C7-C20 arylalkylene, where M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or protonated nitrogen base, m is 1-4, n is 1-4, and x is 1-4.
3.1. Or 2. A coating method comprising applying the curable composition described above to a substrate and coating the substrate with foam.

  According to the present invention, a foam having excellent performance in low thermal conductivity, heat resistance and the like can be formed.

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

  The curable composition of the present invention can be applied for foam formation, and contains a polyol compound, a foaming agent, a catalyst, a foam stabilizer, a phosphorus compound, and a polyisocyanate compound as essential components.

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

Among these, examples of the polyester polyol include aromatic polyester polyols, aliphatic polyester polyols, and aromatic / aliphatic polyester polyols, and one or more of these can be used. Specifically, as the aromatic polyester polyol, for example, a condensed polyester polyol obtained by reacting an aromatic polybasic acid such as orthophthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride with a polyhydric alcohol, polyethylene terephthalate, etc. And phthalic acid polyester polyols obtained by decomposing the phthalic acid polyester moldings. Examples of the aliphatic polyester polyol include a condensed polyester polyol obtained by reacting a polyhydric alcohol with an aliphatic polybasic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, and fumaric acid. It is done. Examples of aromatic / aliphatic polyester polyols include condensed polyester polyols obtained by reacting aromatic polybasic acids and aliphatic polybasic acids with polyhydric alcohols.
In the present invention, it is desirable to include a polyester polyol as the polyol compound, an aromatic polyester polyol from the viewpoint of heat resistance, an aliphatic polyester polyol from the viewpoint of adhesion, or an aromatic from the viewpoint of heat resistance, adhesion, and the like. / Aliphatic polyester polyols etc. can be used alone or in combination. In the present invention, it is particularly preferable to include an aromatic / aliphatic polyester polyol.

  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 alkylene oxide (for example, ethylene oxide, propylene oxide, etc.) using bisphenol A as an initiator, an aromatic amine ( For example, toluene diamine, diethyl toluene diamine, 4,4′-diaminodiphenyl methane, p-phenylene diamine, o-phenylene diamine, naphthalenediamine, triethanolamine, Mannich condensation product, etc.) Examples include aromatic amine-based polyether polyols obtained. Examples of phosphorus-containing polyether polyols include dialkyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, which is a diol having a phosphate ester structure. Examples of the glycerin-based polyether polyol include polyether polyols obtained by adding alkylene oxide using glycerin as an initiator. Examples of the amino group-containing polyether polyol include those obtained by adding an alkylene oxide using a low molecular weight amine (for example, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, etc.) as an initiator.

The hydroxyl value of the polyol compound in the present invention is not particularly limited, but is preferably 50 mgKOH / g or more and 500 mgKOH / g or less.
The hydroxyl value is a value represented by the number of mg of potassium hydroxide equimolar to the hydroxyl group contained in 1 g of the sample. JIS K1557-1: 2007 Plastic-polyurethane raw material polyol test method-Part 1: hydroxyl value It is the value measured based on how to find The hydroxyl value of (A) component is the value measured with the mixture of all the (A) components.

Further, the polyol compound in the present invention preferably contains a polyol having an acid value, particularly a polyester polyol having an acid value, from the viewpoint of storage stability and the like. Although it does not specifically limit as an acid value, It is desirable that they are 10 mgKOH / g or more and 300 mgKOH / g or less (further 20 mgKOH / g or more and 250 mgKOH / g or less). The acid value is the number of mg of potassium hydroxide required to neutralize the acid component present in 1 g of the sample. JIS K 5601-2-1: 1999 Paint component test method “Acid value (titration method) Is a value measured based on
The ratio of the polyol having an acid value contained in the polyol compound is preferably 0.1% by weight to 20% by weight, and more preferably 0.5% by weight to 15% by weight.

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

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

Examples of the hydrofluoroolefin (HFO) include pentafluoropropene such as 1,2,3,3,3-pentafluoropropene (HFO1225ye), 1,3,3,3-tetrafluoropropene (HFO1234ze), 2, Tetrafluoropropenes such as 3,3,3-tetrafluoropropene (HFO1234yf) and 1,2,3,3-tetrafluoropropene (HFO1234ye), and trifluoropropenes such as 3,3,3-trifluoropropene (HFO1243zf) , Tetrafluorobutene (HFO1345), pentafluorobutene (HFO1354), hexafluorobutene (HFO1336), heptafluorobutene (HFO1327), heptafluoropentene (HFO1447), octafluoropentene (HFO1347) O1438), nonafluorobutyl pentene (HFO1429), etc., or their isomers (cis isomer, and trans form) and the like. Examples of the hydrochlorofluoroolefin (HCFO) include 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), Examples thereof include dichlorotrifluoropropene (HCFO1223) and the like, and isomers (cis isomer and trans isomer) thereof.
As the foaming agent in the present invention, one or more selected from hydrofluoroolefin, hydrochlorofluoroolefin, and water are suitable. For example, hydrofluoroolefin and water, hydrochlorofluoroolefin and water, hydrofluoroolefin, A combination of a foaming agent such as hydrochlorofluoroolefin and water can be used.

  The mixing amount of the foaming agent 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.

Although it does not specifically limit as a catalyst, For example, a nurating catalyst, a foaming catalyst, a resinification catalyst etc. are mentioned, These 1 type (s) or 2 or more types can be used.
The nurating catalyst is not particularly limited as long as it is an effective catalyst for isocyanuration. For example, tetraalkylammonium hydroxide such as tetramethylammonium, tetraethylammonium, tetrabutylammonium, and trimethylbenzylammonium, or an organic acid thereof. Salts (organic acids such as acetic acid, caproic acid, octylic acid, myristic acid, lactic acid, etc.), trialkylhydroxyalkylammonium such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, triethylhydroxyethylammonium Hydroxide or its organic acid salt, alkyl carboxylic acid (eg acetic acid, caproic acid, octylic acid, myristic acid, lactic acid ) Metal salts, metal chelate compounds of β-diketones such as aluminum acetylacetone and lithium acetylacetone, Friedel-Crafts catalysts such as aluminum chloride and boron trifluoride, organometallic compounds such as titanium tetrabutyrate and tributylantimony oxide, Examples include aminosilyl group-containing compounds such as hexamethylsilazane, and one or more of these can be used.
Examples of the foaming catalyst include N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ′, N ″ — Pentamethyldipropylenetriamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethoxyethanol, N, N, N ′, N ″, N ′ ″, N ′ ″-hexamethyl Triethylenetetramine, N, N, N ′, N ″ -tetramethyl-N ″-(2-hydroxylethyl) triethylenediamine, N, N, N ′, N ″ -tetramethyl- (2-hydroxylpropyl) ) Tertiary amines such as triethylenediamine or organic acid salts thereof can be used, and 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, 135-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine or organic acid salts thereof; Bismuth tris (2-ethylhexanoate), bismuth tris (neodecanoate), bismuth tris (palmitate), bismuth tetramethylheptanedio , Bismuth naphthenate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, dioctyltin diacetate, tin octylate, and other organic metals, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2 -Imidazole such as ethyl-4-methylimidazole, 2-isopropylimidazole, 1-isobutyl-2-methylimidazole, or N-methyl-N '-(2-dimethylaminoethyl) piperazine, N, N'-dimethylpiperazine N-methylpiperazine, N-methylmorpholine, N-ethylmorpholine, 1,8-diazabicyclo [5.4.0] undecene-7, 1,1 ′-(3- (dimethylamino) propyl) imino) bis ( 2-propanol) and the like. One or more of them can be used.

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 active hydrogen-containing component is contained in the catalyst, the isocyanate index is calculated in consideration of the active hydrogen-containing component contained in the catalyst.
In the present invention, it is desirable to include a foaming catalyst and / or a resinification catalyst together with a nurating catalyst as a catalyst, and it is particularly desirable to include a foaming catalyst and a resinating catalyst together with a nurating catalyst.

  Examples of the foam stabilizer include silicone foam stabilizers such as polyether-modified silicone compounds, fluorine-containing compound foam stabilizers, and the like. These can be used alone or in combination of two or more. Examples of the polyether-modified silicone compound include a graft copolymer of polydimethylsiloxane and polyoxyethylene glycol or polyoxyethylene-propylene glycol. The mixing amount of the 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 the curable composition of this invention, a phosphinic acid salt compound is included as a phosphorus compound. In the present invention, the heat resistance and the like of the foam can be drastically improved by including such a phosphinate compound.

  In a conventional general urethane foam or the like, the entire foam is burnt and contracted by a flame or high heat, and a healthy part (a part that is not carbonized) is lost, and the dimensions of the foam may change greatly. On the other hand, in the foam formed by the curable composition of the present invention, when exposed to a flame or high heat, the combustion, shrinkage, dimensional change, etc. of the foam are suppressed, and further, the thermal decomposition in the foam after extinguishing is suppressed. Progress is also suppressed. Thereby, even if a foam is exposed to a flame or high heat, a healthy part tends to remain in the foam. As described above, the foam of the curable composition of the present invention can have a remarkable effect in heat resistance (particularly when the foam is directly exposed to a flame or high heat), etc., compared with the foam of the prior art. it can.

（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 alkylphosphinic acid metal salt compounds represented by the following (Formula 1) or (Formula 2) and polymers thereof are preferable.
(Formula 1)

(Formula 2)

(R ¹ and R ² are the same or different and are linear or branched alkyl having 1 to 6 carbon atoms. R ³ is linear or branched carbon having 1 to 6 carbon atoms. 10 alkylene, C6-C10 arylene, C7-C20 alkylarylene, or C7-C20 arylalkylene, where M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or protonated nitrogen base, m is 1-4, n is 1-4, and x is 1-4.

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 M is preferably Mg, Ca, Al, Sn, Ti, Zn, Fe, or Zr.

  Such alkyl phosphinic acid metal salt compounds are obtained by reacting, for example, alkyl sulfonic acid and / or phosphinic acid and / or alkali metal salts thereof with an olefin in the presence of a free radical initiator. It can be obtained by obtaining an alkali metal salt thereof and / or 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 (diphenylphosphinic acid) aluminum, bis (Diethylphosphinic acid) zinc, bis (methylethylphosphinic acid) zinc, bis (diphenylphosphinic acid) zinc, bis (diethylphosphinic acid) titanyl, tetrakis (diethylphosphinic acid) titanium, bis (methylethylphosphinic acid) titanyl, tetrakis (Methylethylphosphinic acid) titanium, bis (diphenylphosphinic acid) titanyl, tetrakis (diphenylphosphinic acid) titanium, and the like can be used, and one or more of these can be used. Among them, tris (alkylphosphinic acid) aluminum selected from tris (diethylphosphinic acid) aluminum, tris (methylethylphosphinic acid) aluminum, tris (butylethylphosphinic acid) aluminum, tris (diphenylphosphinic acid) aluminum is particularly preferable. is there.

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

  The mixing amount of the phosphinate compound is preferably 1 to 300 parts by weight, more preferably 2 to 150 parts by weight, still more preferably 3 to 135 parts by weight, most preferably 100 parts by weight of the solid content of the polyol compound. 5 to 100 parts by weight. If the mixing 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 this invention, phosphorus compounds other than the said phosphinate compound, for example, an organic phosphate compound etc., can also be used as a phosphorus compound. Examples of the organic phosphate compound include halogenated alkyl esters, alkyl phosphate esters, aryl phosphate esters, and phosphonate esters of phosphoric acid, and one or more of these can be used. Specific examples of the organic phosphate compound include tris (chloroethyl) phosphate, tris (β-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tributoxyethyl phosphate, tributyl phosphate, triethyl phosphate, cresylphenyl phosphate. And dimethylmethylphosphonate. In the present invention, by including a phosphinate compound and an organic phosphate compound as the phosphorus compound, the viscosity of the curable composition is reduced, the storage stability is improved, the workability is improved during construction, and the heat resistance of the foam And the like can be improved.

  The mixing amount of the organic phosphate compound is preferably 10 to 800 parts by weight, more preferably 30 to 600 parts by weight, and still more preferably 50 to 400 parts by weight with respect to 100 parts by weight of the polyol compound.

  Various polyisocyanate compounds known in the technical field of polyurethane can be used as the polyisocyanate compound. 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 from the standpoints of ease of handling, reaction speed, physical properties of the resulting foam, cost advantages, and the like. Examples of MDI include monomeric MDI, polymeric MDI (polymethylene polyphenyl isocyanate), and the like.

  In the curable composition of the present invention, the polyol compound and the polyisocyanate compound have an isocyanate index of preferably 150 or more, more preferably 180 to 800, still more preferably 200 to 500, and most preferably 250 to 400. Etc. are desirable. If the isocyanate index is within such a range, it is preferable in terms of heat resistance and the like. The isocyanate index is represented by 100 times the numerical value obtained by dividing the number of equivalents of isocyanate groups of a polyisocyanate compound by the total number of equivalents of active hydrogens of active hydrogen-containing components (polyol compound, water, etc.). is there.

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

  As the ethylenically unsaturated double bond-containing compound, those having an ethylenically unsaturated double bond concentration in one molecule of 0.5 to 20 mmol / g are preferable from the viewpoint of the above-mentioned effects, and 5 to 15 mmol / What is g is more preferable. The concentration of ethylenically unsaturated double bonds in the molecule is represented by the number of moles of ethylenically unsaturated double bonds in the molecule, and the number of ethylenically unsaturated double bonds in the molecule is the molecular weight. It is expressed by 1000 times (mmol / g) of the numerical value divided by.

  Specific examples of the ethylenically unsaturated double bond-containing compound include, for example, polyhydric alcohols (eg, dihydric or higher alcohols and derivatives thereof, dihydric or higher phenols, polyols, etc.) and unsaturated carboxylic acids (( A reaction product with an amine (for example, divalent or higher valent amines, alkanolamines, etc.) and an unsaturated carboxylic acid, an unsaturated carboxylic acid thioester or an unsaturated alkyl thioether of a thiol, Examples include bisphenol A-based (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 nonylphenoxypolyethyleneoxyacrylate. 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 ( (Meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, ditri Methylolpropane tetra (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene poly B propylene glycol di (meth) acrylate, alkylene oxide modified trimethylolpropane tri (meth) acrylate.

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

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

  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, 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. In addition, the isocyanate index is calculated in consideration of the active hydrogen-containing component contained in the ethylenically unsaturated double bond-containing compound.

In addition to the above components, for example, a flame retardant, a colorant, a surfactant, a polymerization inhibitor, fibers, and the like can be mixed in the curable composition of the present invention.
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 a relatively low density are preferable. It is.
Examples of the colorant include pigments and dyes.
Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. Such a surfactant can impart storage stability and dispersion stability.
Examples of the polymerization inhibitor include hydroquinone polymerization inhibitors, benzoquinone polymerization inhibitors, catechol polymerization inhibitors, piperidine polymerization inhibitors, and the like. Such a polymerization inhibitor imparts long-term storage stability in a two-component form described later, and also contributes to production stability when added during the polyol production process.
Examples of the 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. However, 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, preferably a rigid polyurethane foam-forming composition, more preferably a rigid polyisocyanurate foam-forming composition. Moreover, the curable composition of this invention is suitable for the use which is apply | coated and foamed to a base material at the field | areas, such as a building, and coat | covers a base material with a foam. The target base material is, for example, a material constituting a wall surface, ceiling surface, floor surface, or the like in a building or the like, and concrete examples include concrete, mortar, metal plate, inorganic board, plywood, and the like. . These base materials may have been subjected to surface treatment with a primer before forming the foam.

  It is desirable that the curable composition of the present invention is in a two-part form at the time of distribution and is mixed and used at the time of use (form formation). In such a two-pack type, for example, the first liquid includes a polyol compound, a foaming agent, a catalyst, a foam stabilizer, and a phosphorus compound, and the second liquid includes a polyisocyanate compound. Can do.

  The viscosity of the first liquid is preferably 500 mPa · s or less, more preferably 20 to 350 mPa · s, more preferably from the viewpoint of storage stability of the first liquid, handling properties, workability during foam formation, and the like. 50 to 250 mPa · s. The viscosity is a viscosity at 20 rpm (guide value for the fourth rotation) measured with a BH viscometer at a temperature of 20 ° C.

  When applying the curable composition to the substrate, for example, using a spray foaming machine or the like for spraying work (for example, a two-liquid tip mixed spraying machine or the like), the first liquid What is necessary is just to spray and apply the mixture of a 2nd liquid. In this case, the temperature of the first liquid and the second liquid is preferably set to 20 to 60 ° C., more preferably about 30 to 50 ° C., respectively. The first liquid and the second liquid thus set at a predetermined temperature are mixed at the spray tip and sprayed toward the base material to form a foam on the base material. The mixing of the first liquid and the second liquid is desirably about 1: 1 in volume ratio. The foam formed by such a method can exhibit excellent performance in low thermal conductivity, heat resistance, and the like. The thickness of the foam is not particularly limited, and may be set as appropriate according to required performance, but is preferably 10 mm or more, and more preferably about 15 to 500 mm.

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

As the first liquid, those (first liquids 1 to 35) in which the following raw materials were uniformly mixed at the weight ratio shown in Table 1 were prepared. As the second liquid, a liquid made of polymeric MDI (second liquid 1) was prepared. In Table 1, the amount of active ingredient is described for the catalyst.
Polyol compound 1: aromatic polyester polyol (terephthalic acid-based polyester polyol, acid value: 0 mgKOH / g, hydroxyl value: 250 mgKOH / g)
Polyol compound 2: Aliphatic polyester polyol (succinic polyester polyol, acid value: 0 mgKOH / g, hydroxyl value: 100 mgKOH / g)
Polyol compound 3: Aromatic polyether polyol (Mannich modified polyether polyol, acid value: 0 mgKOH / g, hydroxyl value: 350 mgKOH / g)
Polyol compound 4: aromatic / aliphatic polyester polyol (phthalic acid / adipic acid-based polyester polyol, acid value: 0 mgKOH / g, hydroxyl value: 350 mgKOH / g)
Polyol compound 5: Aromatic polyester polyol (phthalic polyester polyol, acid value: 160 mgKOH / g, hydroxyl value: 250 mgKOH / g)
-Foaming agent 1: Hydrochlorofluoroolefin-Foaming agent 2: Hydrofluoroolefin-Foaming agent 3: Water (Hydroxyl value: 6233 mgKOH / g)
・ Catalyst 1: Nurate catalyst (Tetraalkyl ammonium organic acid salt)
・ Catalyst 2: Resinification catalyst (1,2-dimethylimidazole)
Catalyst 3: foaming catalyst (bis (2-dimethylaminoethyl) ether)
Phosphorus compound 1: phosphinic acid salt compound (tris (diethylphosphinic acid) aluminum, average particle diameter 4 μm, density 1.35 g / cm ³ )
Phosphorus compound 2: Phosphinate compound (tris (diethylphosphinic acid) aluminum, average particle size 10 μm, density 1.35 g / cm ³ )
Phosphorus compound 3: phosphinate compound (tris (diethylphosphinic acid) aluminum, average particle diameter 20 μm, density 1.35 g / cm ³ )
Phosphorus compound 4: Organophosphate compound (tris (β-chloropropyl) phosphate, density 1.29 g / cm ³ )
Double bond compound 1: ethylenically unsaturated double bond-containing compound (trimethylolpropane triacrylate, ethylenically unsaturated double bond concentration: 10 mmol / g, hydroxyl value: 0 mgKOH / g)
Double bond compound 2: ethylenically unsaturated double bond-containing compound (pentaerythritol tetraacrylate, ethylenically unsaturated double bond concentration: 11 mmol / g, hydroxyl value: 0 mgKOH / g)
Double bond compound 3: ethylenically unsaturated double bond-containing compound (pentaerythritol triacrylate, ethylenically unsaturated double bond concentration: 10 mmol / g, hydroxyl value: 25 mgKOH / g)
・ Foam stabilizer: Silicone foam stabilizer

  The first and second liquids are each heated to 40 ° C. and mixed so as to have the isocyanate index shown in Table 2, and the obtained mixed liquid is applied to a base material (slate plate) and foamed. Thus, a test body (thickness 50 mm) in which the entire surface of the base material was covered with foam was obtained. Each test was implemented by the following method about the obtained test body. Table 2 shows combinations of the first liquid and the second liquid and the results.

(1) Foam formability The state of the formed foam was visually observed. The evaluation criteria are as follows.
A: A homogeneous foam was formed.
○: An almost homogeneous foam was formed.
Δ: Some abnormality (non-uniform foaming, poor adhesion, etc.) was observed in the foam.
X: Abnormality was observed in the foam.

(2) Thermal conductivity The foam part of the test body was cut out, and the thermal conductivity was measured using a thermal conductivity meter. The evaluation criteria are as follows.
○: Thermal conductivity is 0.03 W / (m · K) or less ×: Thermal conductivity is more than 0.03 W / (m · K)

(3) Heat resistance test The heat resistance test was performed using a corn calorimeter defined in ISO 5660. The heating intensity was 50 kW / m ² , and the heating time was 5 minutes, 10 minutes, and 20 minutes, respectively. Evaluation items and evaluation criteria are as follows.

(Evaluation item)
(3-1) Dimensional change A: Dimensional change in the thickness direction after the test is 5 mm or less B: Dimensional change in the thickness direction after the test is 10 mm or less C: Dimensional change in the thickness direction after the test is more than 10 mm and 20 mm or less X: Dimensional change in thickness direction after test exceeds 20 mm (3-2) Total heat generation amount A: Total heat generation amount is 8 MJ / m ² or less X: Total heat generation amount exceeds 8 MJ / m ² (3-3) Maximum heat generation rate A : Maximum heat generation rate is 200 kW / m ² or less X: Maximum heat generation rate is over 200 kW / m ²

(Evaluation criteria)
│ │Heating time │ 3-1 │ 3-2 │ 3-3 │
│AA │ 20 minutes │ A │ A │ A │
│A │ 20 minutes │ B │ A │ A │
│A '│ 20 minutes │ C │ A │ A │
│B │ 10 minutes │ B │ A │ A │
│B '│ 10 minutes │ C │ A │ A │
│C │ 5 minutes │ B │ A │ A │
│C '│ 5 minutes │ C │ A │ A │
│D │ 5 minutes │ X │ X │ X │
About heat resistance, it becomes excellent AA>A> A '>B>B'>C> C '> D inferior.

As is clear from the results in Table 2, the foams of the curable compositions of the present invention (Examples 1 to 35) have low thermal conductivity, and in heat resistance tests, dimensional changes, total heat generation, maximum heat generation rate, etc. Can be sufficiently suppressed, and a healthy part can be left in the foam, which exhibits excellent heat resistance.

Claims (3)

A curable composition for forming rigid polyurethane foam,
Contains a polyol compound, a foaming agent, a catalyst, a foam stabilizer, a phosphorus compound, and a polyisocyanate compound, and has an isocyanate index of 150 or more,
A curable composition comprising a phosphinate compound and an organophosphate compound as the phosphorus compound. As the phosphinate compounds, the following (Equation 1) or the following curable composition according to claim 1, comprising an alkyl phosphinic acid metal salt compound represented by (Formula 2).
(Formula 1)

(Formula 2)

(R ¹ and R ² are the same or different and are linear or branched alkyl having 1 to 6 carbon atoms. R ³ is linear or branched carbon having 1 to 6 carbon atoms. 10 alkylene, C6-C10 arylene, C7-C20 alkylarylene, or C7-C20 arylalkylene, where M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or protonated nitrogen base, m is 1-4, n is 1-4, and x is 1-4. A coating method comprising applying the curable composition according to claim 1 or 2 to a substrate and coating the substrate with foam.