JP2010184974A - Fire-resistant heat-insulating covering material - Google Patents

Abstract

Disclosed is a fire-resistant and heat-insulating coating material that has sufficient resistance and fire resistance without impairing the excellent heat insulation properties of urethane foam, and can protect structures such as ceilings, walls, and steel frames from flames over a long period of time.
The present invention provides a polyurethane foam comprising at least an organic isocyanate, a polyol, water, a urethanization catalyst, a flame retardant, a foam stabilizer, and a foaming agent, and the urethane foam composition contains obsidian powder. And a fireproof thermal insulation covering material containing expansive graphite in a weight ratio of 40 PHR or more, preferably 60 PHR or more and 1500 PHR or less with respect to the active hydrogen-containing compound. Such a fireproof thermal insulation coating material is made of polyurethane foam, so it has ease of foaming on site and excellent thermal insulation, and is made flame retardant with flame retardants, obsidian powder and expansibility The graphite expands to form a refractory heat insulation shell and exhibits sufficient flame retardant fire resistance.
[Selection figure] None

Description

  The present invention relates to a fire-resistant and heat-insulating covering material made of a hard, soft polyurethane foam used for the purpose of heat insulation as a core material for a ceiling, wall, floor, furniture, joinery, vehicle or the like of a building.

  Modern buildings have become more air-tight due to improved performance of joinery, and various heat insulation and anti-condensation materials have been developed and used from the viewpoint of preventing condensation and energy saving caused by differences from the outside temperature. Among them, polyurethane foams are not only excellent in these performances, but are also widely used because they are excellent in light weight, adhesiveness, cost, etc. On the other hand, since they are fossil materials, their fire resistance is very poor, This measure has long been a concern in the construction industry because it often causes fire damage.

  In order to solve this problem, various heat insulating building materials have been researched and developed. As substitutes for polyurethane foam, materials such as asbestos, glass wool, rock wool, calcium silicate board, rock wool sound absorbing board or fireproof paint are available. Asbestos is known for its strong carcinogenicity, and its overall performance, including workability, does not surpass that of polyurethane foams. Therefore, research and development for improving the anti-fire and fire resistance of polyurethane foams It was done in various ways.

  In the past, as a countermeasure for this, a method has been proposed in which a polyurethane foam is mixed with a flame retardant or the like to make it flame retardant, or by using expansive graphite to provide fire resistance (Patent Document 1, Patent). Reference 2). However, since these methods have poor shape retention during combustion, a method using boric acid or ammonium phosphate has been disclosed as a method for improving this defect (Patent Document 3). In addition, in order to obtain a composition having higher fire resistance and less smoke generation, it is necessary to increase the amount of addition of inorganic additives and the like. However, these methods cannot provide a composition having sufficient fire resistance and low smoke generation.

Japanese Patent No. 2732435 JP 2001-348487 A Japanese Patent Laid-Open No. 2002-3713

  It is an object of the present invention to provide a fire-resistant and heat-insulating coating material that has sufficient anti-fire and fire resistance without impairing the excellent heat insulation properties of urethane foam, and can protect structures such as ceilings, walls, and steel frames from flames for a long time. .

  The fireproof thermal insulation coating material of the present invention is a polyurethane foam comprising at least an organic isocyanate, an active hydrogen-containing compound, water, a urethanization catalyst, a flame retardant and a foam stabilizer, and is not heated and foamed obsidian powder and expanded. The active graphite contains 40 PHR or more (preferably 60 PHR or more) and 1500 PHR or less in a weight ratio with respect to the active hydrogen-containing compound.

  The inventors of the present invention provide a polyurethane foam comprising an organic isocyanate, an active hydrogen-containing compound, a urethanization catalyst, a flame retardant, and a foam stabilizer. The obsidian powder and the expandable graphite are added to the active hydrogen-containing compound. By adding 40 PHR or more and 1500 PHR or less by weight, borax, boric acid, (poly) ammonium phosphate, sepiolite, kaolin, clay, ultrafine powdered anhydrous silica, white carbon, etc. may be added as necessary. Thus, it has been found that a fire-resistant and heat-insulating coating material capable of imparting sufficient anti-fire and fire-proof performance while maintaining the heat insulating property of a conventional polyurethane foam can be provided.

  That is, in the present invention, water, a first liquid containing an active hydrogen-containing compound component (polyol) having two or more active hydrogen-containing groups capable of reacting with a urethanization catalyst and an organic isocyanate, and a second liquid containing an organic isocyanate component It consists of a polyurethane foam-forming composition, and the first and / or second liquid contains obsidian powder that has not been heated and foamed, a certain amount of expandable graphite, flame retardant, foam stabilizer, foaming agent, etc. According to the above, a refractory heat insulating coating material characterized by blending one or more selected from borax, boric acid, ammonium (poly) phosphate, sepiolite, kaolin, clay, ultrafine particulate anhydrous silica, and white carbon ( A foamable refractory compound) is provided. Here, when the inorganic powder is applied by spraying or the like, a part or all of the inorganic powder can be sprayed at the same time as the powder at the time of spraying so that it can be blended at a higher concentration.

  Obsidian powder that imparts fireproofing and fire resistance is conventionally known as an additive for building materials due to its light weight and fire resistance as a heated foam (product name pearlite). In addition, there is a technique using an obsidian foam obtained by applying heat to obsidian (JP-A-10-266504) in order to improve the resistance and fire resistance of the polyurethane foam. In the present invention, obsidian powder is used. It is characterized by blending without heating and foaming.

  The reason for using obsidian powder without heating and foaming is that the volume is bulky, the particle size is greatly hindered when discharged from construction equipment, it is impossible to mix a large amount, and the specific gravity is large. It is to avoid the cause of non-uniformity due to differences.

  The obsidian powder used in the present invention is suitably an inorganic mineral fine powder from about 10 mesh to about 150 mesh. By setting the particle size to this level, it is possible to add a large amount and improve fire resistance. Can be made. If it is finer than this, the composition solution will thicken and a large amount of compounding will not be possible, and workability will be inferior. It becomes impossible.

  The expandable graphite used in the present invention is not particularly limited. Expandable graphite is a crystalline compound in which powders of natural graphite, pyrolytic graphite, etc. are treated with inorganic acids such as sulfuric acid and nitric acid and strong oxidizing agents such as concentrated nitric acid and permanganate, and maintain a graphite layered structure. And is thermally expanded when exposed to temperatures of about 200 ° C. or higher. In addition to the deoxidation treatment, there are various types of powders in addition to the neutralized type, and any powder can be used. The particle size is preferably about 40 to 800 μm. If the particle size is smaller than 40 μm, the composition solution will thicken, and a large amount of the composition cannot be blended, workability is inferior, and foaming does not occur sufficiently during combustion foaming. If it is larger than 800 μm, the foamed product at the time of combustion foaming becomes too large, the shell strength is lowered, and it becomes impossible to withstand the flame.

  The contents of obsidian powder and expandable graphite can be appropriately set according to the type of polyurethane resin, desired expansion ratio, etc., but usually 40 PHR or more, preferably 60 PHR in weight ratio with respect to 100 parts by mass of the active hydrogen-containing compound. Above, use at 1500 PHR or less. Even if polyurethane resin, flame retardant, etc. are thermally decomposed and lost, if it is 40 PHR or more, these obsidian powder and expansive graphite expand to form a refractory heat insulation combustion shell, and exhibit sufficient flame retardant fire resistance performance. This is because if the PHR exceeds 1500 PHR, the strength is remarkably lowered and the function as a fire-resistant and heat-insulating coating cannot be performed. Incidentally, when the content of obsidian powder and expandable graphite is 60 PHR or more by weight with respect to 100 parts by mass of the active hydrogen-containing compound, there is an advantage that a combustion shell having sufficient anti-fire and fire resistance is formed. For this reason, this 60 PHR or more is a desirable range of the contents of obsidian powder and expandable graphite.

  In the present invention, a flame retardant is added in order to realize sufficient flame resistance and fire resistance. Examples of the flame retardant include phosphoric acid compounds, halogen compounds, antimony compounds, metal hydroxide compounds, red phosphorus, and the like. Any of these can be used, but a liquid phosphate compound, a liquid halogen compound, or the like is desirable. This is because by using a liquid product, the viscosity of the composition can be kept low, workability can be improved, and obsidian powder and expandable graphite can be blended in a larger amount. The liquid phosphoric acid ester compound, the liquid halogen compound and the like vary depending on the materials used, but usually 5 PHR to 200 PHR, preferably about 10 PHR to 150 PHR is desirable with respect to the polyol component. If it is less than 5 PHR, sufficient flame retardancy cannot be exhibited, and if it is more than 200 PHR, the mechanical strength of the foam is lowered and cannot be used.

  In the present invention, one or more selected from borax, boric acid, ammonium (poly) phosphate, sepiolite, kaolin, clay, ultrafine particulate anhydrous silica, and white carbon can be added as necessary. This is because the fireproof and heat insulating combustion shell after the polyurethane resin is thermally decomposed can be further stabilized. Usually, the active hydrogen-containing compound (polyol component) is 100 PHR or less, preferably 60 PHR or less. If it exceeds 60 PHR, the viscosity of the solution will increase and workability will deteriorate.

  Since the fireproof thermal insulation coating material of the present invention uses polyurethane foam, it has ease of foaming on site and excellent heat insulation properties, and is made flame retardant with flame retardants, obsidian powder and The expandable graphite expands to form a fireproof insulation shell, which provides sufficient flameproof fireproof performance, and can provide sufficient fireproofing and fireproof performance while retaining the heat insulation properties of conventional polyurethane foams. Thus, an excellent fire-resistant and flame-retardant material can be provided. In addition, since obsidian powder is used without heating and foaming, the volume does not increase, the particle size is small when discharged from construction equipment, it can be blended in large quantities, and the specific gravity is small, It has the advantage of being uniform and easy to handle.

  When using a liquid phosphate ester compound or a liquid halogen compound as the flame retardant, since it is a liquid product, the viscosity of the composition can be kept low and workability can be improved. Obsidian powder and expandable graphite Can be added in a larger amount.

  After the polyurethane resin is thermally decomposed by adding one or more selected from borax, boric acid, ammonium (poly) ammonium phosphate, sepiolite, kaolin, clay, ultrafine powdered anhydrous silica, and white carbon. There is an advantage that the refractory heat insulation shell can be made more stable. Sepiolite, kaolin, clay, ultrafine powdered anhydrous silica, and white carbon reduce the fluidity of the mixed solution, and can improve workability by making it difficult to sag when the composition is applied to a wall surface using a spray or the like. .

Hereinafter, the best mode of the present invention will be described in detail.
In the present invention, various known polyfunctional aliphatic, alicyclic and aromatic isocyanates can be used as the isocyanate component. For example, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4-dicyclohexylmethane diisocyanate. (HMDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4-diphenylmethane diisocyanate (MDI), orthotoluidine diisocyanate (TODI) , Naphthylene diisocyanate (NDI), xylylene diisocyanate (XDI), lysine diisocyanate (LDI), and isocyanate-containing prepolymers using these isocyanates. As the polyisocyanate, it is preferable to use a polyisocyanate having an NCO content of 5 to 55%, preferably 20 to 50% and an average number of NCO groups per molecule of 2 to 5, preferably 2 to 4. . Particularly preferred polyisocyanates are those based on methylene diphenyl diisocyanate and / or their polymer homologs.

  The water used in the present invention generates carbon dioxide by reaction with the polyisocyanate compound and acts as a blowing agent. The amount of water used is determined by the density of the desired foam, and is suitably 1.5 to 20 parts by weight per 100 parts by weight of the active hydrogen-containing compound. When the ratio of the amount of water used is lower than 1.5 parts by weight, the density of the foam becomes too high. On the other hand, when the amount exceeds 20 parts by weight, the mechanical strength is lowered and cannot be used.

  Examples of the active hydrogen-containing compound include a compound having two or more active hydrogen-containing functional groups such as a hydroxyl group and an amino group, or a mixture of two or more of the compounds. In particular, a compound having two or more hydroxyl groups, a mixture thereof, or a mixture containing the same as a main component and further containing a polyamine or the like is preferable. Examples of the compound having two or more hydroxyl groups include polyols, and examples of the polyol include polyether polyols, polyester polyols, polyhydric alcohols, castor oil polyols, castor oil modified polyols, and hydroxyl group-containing diethylene polymers.

  Examples of polyether polyols include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol, 1,4-butanediol, bisphenol A, bisphenol F, etc., or alkylene oxide 1 Bifunctional polyol, trimethylolpropane, hexanetriol, glycerin, etc., which is addition-polymerized with one species or two or more species, or trifunctional polyol, pentaerythritol, sorbitol, sugar, etc., obtained by addition polymerization of these with alkylene oxide Examples are polyfunctional polyols obtained by addition polymerization of alkanolamine, and those obtained by addition polymerization of alkylene oxide to alkanolamine.

  Examples of the polyester polyol include a polyester polyol having a terminal hydroxyl group obtained by condensation of a polyhydric alcohol and a polybasic acid component. Examples of the polyhydric alcohol component include diols such as polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol, and 1,4-butanediol, triols such as trimethylolpropane, hexanetriol, and glycerin. Examples of polybasic components include succinic acid, adipic acid, maleic acid, fumaric acid, phthalic acid, siophthalic acid, het acid, succinic anhydride, maleic anhydride, and phthalic anhydride. It is done.

  The polyurethane foam is obtained by adding water in an amount sufficient to produce a polyurethane foam having a desired foam density to the isocyanate compound and an active hydrogen-containing compound having two or more active hydrogen-containing groups capable of reacting with the organic isocyanate. It is made using a catalyst and a foam stabilizer. The amount used is in the range of 0.7 to 5.0, preferably 0.8 to 3.0, equivalent ratio of isocyanate groups to active hydrogen in the polyol component mixture. If the equivalent ratio is less than 1.0, unreacted active hydrogen groups remain and flame retardancy and heat resistance deteriorate, and if it is greater than 5.0, the brittleness of the foam increases and the adhesion to the face material deteriorates. Become.

  In the present invention, foaming can be performed using a foaming agent together with water. Examples of the blowing agent include low-boiling solvents such as fluorinated hydrocarbons, methylene chloride, pentane, cyclopentane, acetone, methyl ethyl ketone, methyl acetate, and ethyl acetate.

  As the urethanization catalyst, those generally known as urethanization catalysts can be used. For example, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane-1,3-diamine, N, N, N ′, N′-tetramethylhexene— 1,6-diamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N-dicyclohexylmethylamine, bis (N, N-dimethylaminoethylpiperazyl) ethane, N, N ′, Tertiary amines such as N ″ -tris (diethylaminopropyl) hexahydrotriazine, dibutyltin dilaurate, dibutyltin diacetate and the like can be used alone or in combination.

  As the foam stabilizer, for example, a general foam stabilizer such as an oxyalkylene copolymer of polydimethylsiloxane or a fluorosurfactant can be used as necessary. As the foaming agent, an organic solvent having a low boiling point is generally used, and these may be added in combination with water. That is, they are a fluorocarbon foaming agent, methylene chloride, (cyclo) pentane, (cyclo) hexane, ethyl acetate, acetone and the like.

  Liquid phosphoric esters and liquid halogen compounds used as flame retardants are trisphenyl phosphate, cresyl diphenyl phosphate, tris-resyl phosphate, trixylenyl phosphate, tris (t-butylated phenyl) phosphate, tris (i Aromatic condensation such as -propylated phenyl) phosphate, 2-ethylhexyl diphenyl phosphate, 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl) phosphate, bisphenol A bis (diphenyl phosphate) Phosphate esters, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, tris (chloroethyl) phosphate, 2,2bis (chloromethyl) trimethylenebis (biphenyl) (2-chloroethyl) phosphate), polyoxyalkylene bisdichloroalkyl phosphate, halogen-containing condensed phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, Examples include trilauryl phosphate, orthophosphates such as lysyl phosphate, tristearyl phosphate, trioleyl phosphate, chlorinated paraffin, and the like.

  In order to assist the flame retardant with the flame retardant, decabromodiphenyl ether, tetrabromobisphenol A and its epoxy oligomer and carbonate oligomer, tetrabromobisphenol A bis (dibromopropyl ether), tetrabromobis (aryl ether) , Tetrabromobis (pentabromophenyl) ethane, 1,2bis (2,4,6-tribromophenoxy) ethane, 2,4,6-tris (2,4,6-tribromophenoxy) -1,3 , 5-triazine, brominated polystyrene, polybrominated styrene, ethylene bistetrabromophthalimide, hexabromocyclododecane, hexabromobenzene, pentabromobenzyl acrylate, pentabromobenzyl acrylate and the like brominated flame retardants, antimony trioxide, Antimony oxide, magnesium hydroxide, can be added to the inorganic flame retardant such as aluminum hydroxide.

  In the present invention, a crosslinking agent, a viscosity reducing agent, an inorganic filler, and a colorant can be used as necessary. As the crosslinking agent, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, triethanolamine, ethylenediamine, or the like can be used alone or in combination. As the thickening agent, nitrogen-containing, sulfur-containing, phosphorus-based, ether-based, hydrocarbon-based, ester-based, carbonate-based and the like room temperature liquid solvents and / or plasticizers, etc., or a wetting and dispersing agent having surface activity. Examples of inorganic fillers and colorants include calcium carbonate, calcium hydroxide, calcium oxide talc, silica stone powder, gypsum, glass powder, titanium oxide, and carbon black. These additives and other additives may be mixed in advance in the mixture containing the polyol component (B), or may be added during the reaction.

  As a foaming method of the polyurethane resin, a foaming method known in the technical field of polyurethane can be used without limitation. For example, a continuous production method, a discontinuous production method, a spray method, an injection method, or the like can be used. In particular, the spray method is a method in which a two-component undiluted solution is mixed and sprayed onto a construction object with a spray device, and when reaching the object, it is foamed and cured, and is an effective method because construction is easy. In addition, the continuous production method is a method in which a mixed stock solution is flowed on the lower surface material on the continuous conveyor, and the upper surface material is supplied and continuously foamed, and a sandwich panel can be produced by cutting to a predetermined length. it can. The foamable refractory compound obtained in this way should be sprayed or injected into the voids of a polyurethane foam coating machine where it is required to insulate, prevent condensation, prevent fire or fire, such as roofs, walls and partitions of structures. Thus, it can be used for new uses as a fireproofing and fireproofing material in addition to the characteristics of conventional polyurethane foams.

The density of the hard heat-insulating refractory coating material of the present invention ^is preferably ^{10kg / m 3 ~900kg / m 3} , more preferably from 20~800kg / ^{m 3.}

<Example 1>
The following materials b to l and water, a foaming agent, and a foam stabilizer were mixed in the formulation shown in Table 1. And this mixed composition and the material a (4, 4- diphenylmethane diisocyanate) are mixed by the mixing | blending of Table 1, and it inject | pours into the container which carried out the mold release process of the 200 mm square immediately after mixing, it was made to foam, and Example 1 A fireproof insulation coating was obtained.

a) 4,4-diphenylmethane diisocyanate: Sumidur 44V-20 (Suika Bayer Urethane), NCO% = 31.0%
b) Trifunctional polyol having a molecular weight of about 400 obtained by addition polymerization of trimethylolpropane and propylene oxide c) Trifunctional polyol having a molecular weight of about 3000 obtained by addition polymerization of glycerin and propylene oxide d) Hydroxyl equivalent weight obtained by condensation polymerization of adipic acid and neopentyl glycol 500 bifunctional polyols e) Quaternary ammonium salt catalyst (Dabco TMR) (Air Products)
f) 12% dibutyltin dilaurate solution: TN-12 (Sakai Chemical)
g) Tris (chloropropyl) phosphate h) Obsidian powder: Fuyoex No. 0 (Navy perlite)
i) Expandable graphite: SYZR1002 (Sanyo Trading)
j) Ammonium phosphate: Theien S (Taipei Chemical Industry)
k) Aluminum hydroxide: Heidilite H-310 (Showa Denko)
l) Sepiolite: Miracle LFC-2Z (Omi Mining)
Foam stabilizer: oxyalkylene copolymer of polydimethylsiloxane (SZ-580 Toray, Dow Corning Co., Ltd.)
Foaming agent: 1,1,1,2-tetrafluoroethane (HFC-134a)

<Examples 2 to 5>
Except for changing the material to the formulation shown in Table 1, the refractory insulation coating materials of Examples 2 to 5 were obtained in the same manner as in Example 1.

<Comparative Examples 1 and 2>
Except for changing the material to the formulation shown in Table 1, the fireproof and heat insulating covering materials of Comparative Examples 1 and 2 were obtained in the same manner as in Example 1.

<Example 6>
The materials of b to 1 except for the material h (obsidian powder), water, a foaming agent, and a foam stabilizer were mixed in the formulation shown in Table 1. Then, using a spray device (manufactured by Kawata Co., Ltd.), mixing the mixed composition and the material a (4,4-diphenylmethane diisocyanate) with the composition of Table 1, the material h (obsidian powder) The powder was sprayed at the same time so as to be blended and cured and foamed to obtain a fireproof and heat insulating coating material.

<Combustion test>
The fireproof thermal insulation coating materials of Examples 1 to 6 and Comparative Examples 1 and 2 were each cut into a plate shape of 50 mm × 200 mm × 200 mm to obtain test pieces. While heating the surface of each test piece with a 1300 degreeC burner, the time-dependent change of the back surface temperature was measured, and fireproof performance was evaluated. The results are shown in Table 2.

  As shown in the results of Table 2, the test pieces of Examples 1 to 6 exhibited sufficient fire resistance, but the test piece of the comparative example lost its fire resistance over time.

  Moreover, in the said combustion test, stability of the outer shell of each test piece heated with the burner was evaluated. As a result, the test piece of Comparative Example 1 had a weak outer shell after heating, and peeling of the outer shell was observed. Although the outer shell of the test piece of Comparative Example 2 had strength, the volume was reduced, and the outer shell was peeled off in some places, and it was recognized that the fire resistance was lost. On the other hand, in the test pieces of Examples 1 to 6, even after the burner was heated, the outer shell had sufficient strength, and peeling of the outer shell was not observed. It was found that the outer shell of the test piece 6 had excellent stability.

Claims (3)

  Made of polyurethane foam using at least organic isocyanate, active hydrogen-containing compound, water, urethanization catalyst, flame retardant and foam stabilizer, obsidian powder and expandable graphite not heated and foamed as active hydrogen-containing compounds, respectively On the other hand, a fireproof and heat insulating covering material containing 40 PHR or more and 1500 PHR or less in a weight ratio.   The fire-resistant and heat-insulating coating material according to claim 1, wherein the flame retardant contains a liquid phosphate ester and / or a liquid halogen compound.   3. The method according to claim 1 or 2, comprising one or more selected from borax, boric acid, ammonium (poly) phosphate, sepiolite, kaolin, clay, ultrafine particulate anhydrous silica, and white carbon. Fireproof insulation coating.