JP6568252B2 - Liquid composition and coating method - Google Patents

Description

  The present invention relates to a novel liquid composition. The liquid composition of the present invention can form a foam by mixing with a polyisocyanate compound.

  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 and a solid flame retardant. 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, in the composition as described in the above patent document, when the storage period is long, the solid flame retardant may be settled or aggregated. In such a case, the composition must be sufficiently agitated as a pre-stage at the time of foam formation by spraying construction or the like, handling properties are difficult, and construction work becomes complicated. Further, due to poor dispersion of the solid flame retardant or poor mixing with the polyisocyanate compound, a homogeneous foam may not be formed, and sufficient performance in heat resistance and the like may be difficult to obtain.

  The present invention has been made in view of such problems, and the main object of the present invention is to improve the storage stability, workability, etc. of a liquid composition that forms a foam by mixing with a polyisocyanate compound. And to form a homogeneous foam having excellent performance in low thermal conductivity, heat resistance and the like.

  As a result of intensive studies to solve the above problems, the present inventors have found that it is beneficial that a liquid composition that forms a foam by mixing with a polyisocyanate compound is composed of a specific phosphorus compound. As a result, the present invention has been completed.

That is, the present invention has the following characteristics.
1. A liquid composition that forms a foam by mixing with a polyisocyanate compound,
Containing a polyol compound, a foaming agent, a catalyst, a foam stabilizer, and a phosphorus compound;
The mixing amount of the phosphorus compound is 10 to 1000 parts by weight with respect to 100 parts by weight of the polyol compound,
The phosphorus compounds, powdered phosphorus compound, and a liquid phosphorus compound, powdery phosphorus compounds: a liquid phosphorus compound = 1: 99 to 70: see containing 30 weight ratio,
Including a phosphinate compound as the powdered phosphorus compound,
Containing an organic phosphate compound as the liquid phosphorus compound,
A liquid composition characterized by the above.
2.1. A coating method comprising mixing the liquid composition described in 1 and a polyisocyanate compound, applying the mixture to a substrate, and coating the substrate with a foam.

  According to the present invention, storage stability, construction workability, and the like of a liquid composition that forms a foam by mixing with a polyisocyanate compound can be improved. Furthermore, a homogeneous 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 liquid composition of the present invention forms a foam by mixing with a polyisocyanate compound, and contains a polyol compound, a foaming agent, a catalyst, a foam stabilizer, and a phosphorus 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 liquid composition of this invention, a powdery phosphorus compound and a liquid phosphorus compound are included as a phosphorus compound in a specific ratio. In this invention, storage stability, handling property, construction workability | operativity, etc. can be improved by including such 2 types of phosphorus compounds. In addition, the miscibility with the polyisocyanate compound is increased (mixed quickly and uniformly), stable construction can be performed, and a homogeneous foam can be formed. Furthermore, advantageous effects are also obtained in terms of foam adhesion, strength, heat resistance, and the like. The state of powder, liquid, etc. represents the state of each component alone at 20 ° C.

  Such an effect has good compatibility between the powdered phosphorus compound and the liquid phosphorus compound, and the presence of the liquid phosphorus compound increases the dispersibility of the powdered phosphorus compound (at least part of the powdered phosphorus compound is dissolved). Furthermore, in the foam to be formed, it is considered that the powdered phosphorus compound is produced by being uniformly dispersed throughout the foam.

The powdery phosphorus compound has a density of 1.8 g / cm ³ or less (more preferably 1.0 to 1.6 g / cm ³ , and still more preferably 1.2 to 1.5 g / cm ³ ). Is preferred. In addition, the density said here is a value in 20 degreeC.

  The average particle size of the powdered phosphorus compound 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.

（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。） In the present invention, a phosphinate compound is preferable as the powdered phosphorus compound. By using such a phosphinate compound, it becomes possible to obtain more excellent performance in heat resistance and the like. 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. Of these, tris (diethylphosphinic acid) aluminum is particularly preferable.
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.

  As the liquid phosphorus compound, for example, an organic phosphate compound can be used. 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, it is particularly preferable to use the phosphinate compound as the powdery phosphorus compound and the organic phosphate compound as the liquid phosphorus compound.

  In the present invention, the mixing amount of the phosphorus compound (total mixing amount of the powdered phosphorus compound and the liquid phosphorus compound) is 10 to 1000 parts by weight, preferably 30 to 600 parts by weight, based on 100 parts by weight of the polyol compound. More preferably, it is 50-400 weight part. When the mixing amount of the phosphorus compound is within such a range, sufficient effects can be obtained in terms of handling properties, construction workability, foam formability, heat resistance, and the like.

  When there is too little phosphorus compound than the said mixing amount, it will become difficult to obtain sufficient performance in heat resistance. In addition, the viscosity of the liquid composition tends to increase, and when mixed with a polyisocyanate compound, it becomes difficult to rapidly perform uniform mixing. Therefore, foaming starts in an insufficiently mixed state, a homogeneous foam cannot be obtained, and abnormalities such as poor adhesion tend to occur. In spray construction, pressure abnormalities, clogging, etc. may occur. When there is too much phosphorus compound than the said mixing amount, there exists a possibility that the adhesiveness of a foam, intensity | strength, etc. may become inadequate.

  In the present invention, the weight ratio of the powdered phosphorus compound to the liquid phosphorus compound is powdered phosphorus compound: liquid phosphorus compound = 1: 99 to 70:30, preferably 2:98 to 60:40, more preferably 3. : 97-50: 50, more preferably 5: 95-40: 60. If the two phosphorus compounds are in such a weight ratio, sufficient effects can be obtained in terms of storage stability, handling properties, construction workability, foam formability, adhesion, strength, heat resistance, and the like. .

  If the weight ratio of the powdered phosphorus compound is too smaller than the above range, it is difficult to obtain sufficient performance in heat resistance. If the weight ratio of the powdered phosphorus compound is too larger than the above range, storage stability, handling properties, construction workability, foam adhesion and strength may be insufficient, and the foam may be flame or high heat. There is also a risk of cracking and the like when exposed to.

  The liquid composition of the present invention can contain an ethylenically unsaturated double bond-containing compound in addition to the components described above. Examples of the ethylenically unsaturated double bond include a (meth) acryloyl group, an allyl group, and a propenyl group. In the present invention, the use of such an ethylenically unsaturated double bond-containing compound makes it possible to obtain the above effect more efficiently. That is, even if the mixing amount of the phosphorus compound is set to be relatively small, excellent heat resistance and the like can be exhibited, and storage stability, workability and the like can be further improved.

  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 liquid 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 liquid composition of the present invention can be obtained by uniformly mixing the above components by a conventional method.

  The viscosity of the liquid composition of the present invention is preferably 500 mPa · s or less, more preferably 20 to 350 mPa · s, and still more preferably 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. In the present invention, the use of the phosphorus compound makes it possible to set the liquid composition to a relatively low viscosity while sufficiently securing the storage stability of the liquid composition. Thereby, the stirring operation | work at the time of construction, etc. is reduced, and an advantageous effect is acquired also in handling property, construction workability | operativity, miscibility with a polyisocyanate compound, etc.

  The liquid composition of the present invention forms a foam by mixing with a polyisocyanate compound, and is desirably used as a first liquid of a two-component material. That is, at the time of distribution, the first liquid made of the liquid composition of the present invention and the second liquid containing the polyisocyanate compound are combined to form a two-liquid type, and the first liquid and the second liquid are formed at the time of foam formation. It is desirable to mix and use.

  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.

  The viscosity of the polyisocyanate compound is preferably 500 mPa · s or less, more preferably 20 to 350 mPa · s, and still more preferably 50 to 200 mPa · s.

  When the liquid composition of the present invention is mixed with the polyisocyanate compound, the isocyanate index is preferably 150 or more, more preferably 180 to 800, still more preferably 200 to 500, and most preferably 250 to 400. It is desirable to do. 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 liquid 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. In addition, the liquid composition of the present invention is suitable for applications in which it is mixed with a polyisocyanate compound at a site such as a building, applied to a base material and foamed, and the base material is coated with 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.

  In order to coat the substrate with foam, for example, the above-mentioned liquid composition (first liquid) is used by using a spray foaming machine for spraying construction (for example, a two-liquid tip mixed spraying machine). What is necessary is just to spray and apply the mixture of a polyisocyanate compound (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.

  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 liquid composition of the present invention, when exposed to flame or high heat, foam combustion, shrinkage, dimensional change, etc. are suppressed, and further, the thermal decomposition in the foam after fire extinguishing 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 liquid composition of the present invention can obtain a remarkable effect in heat resistance (particularly when the foam is directly exposed to a flame or high heat) and the like as compared with the foam of the prior art. .

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

As a 1st liquid, the liquid composition (1st liquid 1-39) which mixed the following raw material uniformly in the weight ratio shown in Table 1 was prepared. In Table 1, the amount of active ingredient is described for the catalyst.
Polyol compound 1: aromatic polyester polyol (terephthalic acid polyester polyol, viscosity 1900 mPa · s, acid value: 0 mgKOH / g, hydroxyl value: 250 mgKOH / g)
Polyol compound 2: aromatic polyester polyol (terephthalic acid polyester polyol, viscosity 17000 mPa · s, acid value: 0 mgKOH / g, hydroxyl value: 250 mgKOH / g)
Polyol compound 3: aliphatic polyester polyol (succinic polyester polyol, viscosity 9000 mPa · s, acid value: 0 mgKOH / g, hydroxyl value: 100 mgKOH / g)
Polyol compound 4: aromatic polyether polyol (Mannich-modified polyether polyol, viscosity 4000 mPa · s, acid value: 0 mgKOH / g, hydroxyl value: 350 mgKOH / g)
Polyol compound 5: aromatic / aliphatic polyester polyol (phthalic acid / adipic acid-based polyester polyol, viscosity 900 mPa · s, acid value: 0 mgKOH / g, hydroxyl value: 350 mgKOH / g)
Polyol compound 6: aromatic polyester polyol (phthalic polyester polyol, viscosity 3000 mPa · s, 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)
Powdered phosphorus compound 1: Phosphinate compound (tris (diethylphosphinic acid) aluminum, average particle size 4 μm, density 1.35 g / cm ³ )
Powdered phosphorus compound 2: Phosphinate compound (tris (diethylphosphinic acid) aluminum, average particle size 10 μm, density 1.35 g / cm ³ )
Liquid phosphorus compound 1: Organophosphate compound (Tris (β-chloropropyl) phosphate, density 1.29 g / cm ³ )
・ Powder flame retardant: Aluminum hydroxide (average particle size 2μm)
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

(1) Storage stability About the 1st liquid, the external appearance change when it left to stand under 20 degreeC after manufacture for 14 days was observed visually. The evaluation criteria are as follows. The results are shown in Table 1.
○: No abnormality △: Mild sedimentation, aggregation, etc. occurred ×: Significant sedimentation, aggregation, etc. occurred

  Next, what consists of polymeric MDI (2nd liquid 1) was prepared as a 2nd liquid, and the following tests were done.

  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.

(2) 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.

(3) 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)

(4) Heat resistance test It was carried out 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)
(4-1) 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 more than 5 mm and 10 mm or less C: Dimensional change in the thickness direction after the test is more than 10 mm and less than 20 mm X: Dimensional change in thickness direction after test exceeds 20 mm (4-2) Total calorific value A: Total calorific value is 8 MJ / m ² or less X: Total calorific value exceeds 8 MJ / m ² (4-3) Maximum heat generation Speed A: Maximum heat generation rate is 200 kW / m ² or less X: Maximum heat generation rate exceeds 200 kW / m ²

(Evaluation criteria)
│ │Heating time │ 4-1 │ 4-2 │ 4-3 │
│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 Tables 1 and 2, the liquid compositions of the present invention (Examples 1 to 36) are free from sedimentation or aggregation over time, have excellent storage stability, and are easy to work. It was excellent. In addition, the foam formed using the liquid composition of the present invention is homogeneous, has low thermal conductivity, and sufficiently suppresses dimensional change, total heat generation, maximum heat generation rate, etc. in heat resistance tests. In addition, the sound part could remain in the foam and exhibited excellent heat resistance.

Claims (2)

A liquid composition that forms a foam by mixing with a polyisocyanate compound,
Containing a polyol compound, a foaming agent, a catalyst, a foam stabilizer, and a phosphorus compound;
The mixing amount of the phosphorus compound is 10 to 1000 parts by weight with respect to 100 parts by weight of the polyol compound,
The phosphorus compounds, powdered phosphorus compound, and a liquid phosphorus compound, powdery phosphorus compounds: a liquid phosphorus compound = 1: 99 to 70: see containing 30 weight ratio,
Including a phosphinate compound as the powdered phosphorus compound,
Containing an organic phosphate compound as the liquid phosphorus compound,
A liquid composition characterized by the above. A coating method comprising mixing the liquid composition according to claim 1 and a polyisocyanate compound, applying the mixture to a substrate, and coating the substrate with foam.