Polyurethane resin composition and method for insulating a building

Abstract

[Problem] To provide a polyurethane resin composition which has at least quasi-nonflammability and has characteristics suitable for forming an insulating layer of a building even without adding a foam stabilizer. [Solution] A polyurethane resin composition, which is characterized in that it is a polyurethane resin composition for forming a foam of an insulating material constituting a building, the foam has at least quasi-nonflammability in a heat release test according to ISO-5660, the polyurethane resin composition contains at least a polyisocyanate compound, an ester-based polyol compound, a trimerization catalyst, an additive, and a non-silicon-based surface conditioner, and does not contain a foam stabilizer, and the additive contains red phosphorus as an essential component and is combined with at least any one of a phosphate flame retardant and a chlorine-containing flame retardant.

Description

Technical Field

[0001] The present invention relates to a polyurethane resin composition used as a heat insulating material for buildings, etc. More specifically, the present invention relates to a polyurethane resin composition, etc. that can form a foam having at least quasi-incombustibility in the heat release test according to ISO-5660. Background Art

[0002] In RC and S houses, spray rigid polyurethane foam heat insulating materials are mostly used to prevent condensation, achieve heat insulation, and save energy.

[0003] In recent years, rarely, fires caused by ignition of heat insulating materials have occurred due to inadequate construction management, etc. In addition, even when a general fire occurs, there is a possibility that the fire spreads to the heat insulating material and causes a fire spread.

[0004] To prevent the combustion of such polyurethane foam, a refractory coating (inorganic spraying materials such as cement-based materials, etc.) is sometimes applied, but there are problems such as time-consuming for residual construction and insufficient adhesion to the polyurethane foam after construction and peeling off, etc.

[0005] Therefore, in order to impart flame retardancy to polyurethane foam, a polyurethane resin composition containing a flame retardant having red phosphorus as an essential component is disclosed in Patent Document 1 below.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent No. 6200435 Gazette Summary of the Invention

[0009] Problems to be Solved by the Invention

[0010] The polyurethane resin composition described in Patent Document 1 has at least any one of the following problems.

[0011] (1) Due to the foam stabilizer required for compounding, the self-adhesion of polyurethane is weakened, and therefore there is a possibility that the foam easily peels off from the sprayed surface. In particular, when forming a heat insulating layer of a building, repeated spraying is performed, so the possibility of the foam peeling off further increases.

[0012] (2) There is a possibility that cyclic siloxanes, etc. in the silicone-based foam stabilizer diffuse in the air and cause malfunctions such as incorrect operations due to poor contact of electrical and electronic devices, etc. It should be noted that these cyclic siloxanes are restricted substances that have an adverse effect on water quality in Canada and Europe, and cannot be said to be environmentally friendly.

[0013] (3) Since the stock solution has poor storage stability, raw materials settle during on-site construction, which has an adverse effect on productivity and the durability of construction machinery.

[0014] (4) When using HFO-1233zd as a foaming agent, if the polyol component is manufactured and stored for a long time, the foaming agent decomposes due to the influence of an amine catalyst or the like, generating HF, decomposing a silicone-based foam stabilizer, etc., and there is a high possibility of not foaming.

[0015] Accordingly, at least one object of the present invention is to provide a polyurethane resin composition having flame retardancy and, in order to avoid problems caused by the addition of a foam stabilizer, having characteristics suitable for forming an insulating layer of a building even without adding a foam stabilizer.

[0016] Solutions for Solving the Problems

[0017] The invention of the present application proposed to solve the above problems is characterized in that it is a polyurethane resin composition for forming a foam of an insulating material constituting a building, the foam has at least quasi-nonflammability in a heat release test according to ISO-5660, the polyurethane resin composition contains at least a polyisocyanate compound, an ester-based polyol compound, a trimerization catalyst, an additive, and a non-silicon-based surface conditioner, and does not contain a foam stabilizer, and the additive contains red phosphorus as an essential component and is combined with at least any one of a phosphate flame retardant and a chlorine-containing flame retardant.

[0018] In addition, in the above invention, as the phosphate flame retardant, at least any one of ammonium phosphate and aluminum phosphite can be selected.

[0019] In addition, in the above invention, as the chlorine-containing flame retardant, a chlorine-based phosphate ester can be used.

[0020] In addition, in the above invention, as the non-silicon-based surface conditioner, an acrylic-based surface conditioner can be used.

[0021] In addition, in the above invention, a foaming agent having HFO (hydrofluoroolefin) can also be contained.

[0022] In addition, in the above invention, an ether-based polyol compound can also be contained.

[0023] In addition, in the above invention, a bonding promoter can also be contained.

[0024] In addition, in the above invention, at least any one of a polyurethane foaming catalyst and a polyurethane metal catalyst can also be contained.

[0025] In addition, in the above invention, a dispersant can also be contained.

[0026] In addition, the present invention also provides a method for insulating a building, which uses the aforementioned polyurethane resin composition as a sprayable insulating material for on-site foaming.

[0027] Effects of the Invention

[0028] According to the present invention, it has at least any one of the following effects.

[0029] (1) In the present invention, by not containing a foam stabilizer in the compounding of the polyurethane resin composition, the adhesiveness of the foam becomes good. More specifically, it is possible to avoid the possibility of poor adhesion during repeated spraying accompanied by the improvement of the sliding property of the surface layer due to the use of a silicone-based foam stabilizer as a raw material for polyurethane foam. On the other hand, in the present invention, by not containing a foam stabilizer, it is particularly suitable for use in forming an insulating layer of a building by on-site spraying.

[0030] (2) In the present invention, especially by not containing a silicone-based foam stabilizer, there is no diffusion of cyclic siloxanes, and there are no adverse effects such as malfunction due to poor contact of electrical / electronic devices, etc., and water pollution.

[0031] (3) In the present invention, in addition to red phosphorus, it also contains a phosphate-based flame retardant and a chlorine-based flame retardant. Thus, through dehydration condensation, hydrolysis, dehydration carbonization (expansion effect), and the formation of a foaming layer during combustion, a further high flame retardancy can be obtained.

[0032] (4) In the present invention, since no foam stabilizer is contained in the compounding of the polyurethane resin composition, in particular, there is no problem that HFO blowing agents such as HFO1233zd decompose to generate hydrogen fluoride due to amine catalysts, etc., and there is no decomposition of silicone foam stabilizers, etc., due to this hydrogen fluoride, and there is no problem of non-foaming due to such decomposition; there is no problem of slow chemical reaction. As a result, there is no obstacle in the use of HFO blowing agents, and the effects achieved by using HFO blowing agents (improvement of long-term storage stability of raw materials, improvement of on-site workability) can be obtained. Description of the Drawings

[0033] Figure 1 It is a comparison table of test results based on the presence or absence of a foam stabilizer.

[0034] Figure 2 It is a comparison table of test results based on different types of surface modifiers.

[0035] Figure 3 It is a comparison table of test results based on the presence or absence of an ether-based polyol compound.

[0036] Figure 4 It is a comparison table of test results based on the presence or absence of an adhesion promoter.

[0037] Figure 5 It is a comparison table of test results based on the presence or absence of a polyurethane-forming catalyst or a metal-resinifying catalyst.

[0038] Figure 6 It is a comparison table of test results based on the presence or absence of a dispersant.

[0039] Figure 7 It is a comparison table of test results based on the presence or absence of a phosphate-based flame retardant or a chlorine-based flame retardant. Detailed implementation mode

[0040] <1>Overall configuration

[0041] The polyurethane resin composition of the present invention is used to form a foam of a heat insulating material constituting a building, and contains at least a polyisocyanate compound, an ester-based polyol compound, a trimerization catalyst, an additive, and a non-silicon-based surface conditioner, and does not contain a foam stabilizer.

[0042] Furthermore, it is characterized in that the foam obtained from the above composition has at least quasi-incombustibility in the heat release test according to ISO-5660.

[0043] By dividing the above composition into a polyisocyanate compound (Component 1) and the components other than that (Component 2), methods such as spraying while mixing the two by spraying or spraying while mixing the two can form a heat insulating layer on a building.

[0044] <2>Regarding incombustible performance

[0045] As described above, the polyurethane resin composition of the present invention determines the compounding of each material in such a way that it has at least quasi-incombustibility in the heat release test according to ISO-5660, that is, in Table 1 below, it belongs to incombustible materials and quasi-incombustible materials.

[0046] [Table 1]

[0047]

[0048] The most suitable compounding ratio of each material can be appropriately guided by experiments.

[0049] The following will explain the details of each material.

[0050] <3>Polyisocyanate compound

[0051] The polyisocyanate compound is a material used as the main agent for the polyurethane resin composition of the present invention.

[0052] Examples of the polyisocyanate compound include aromatic polyisocyanates, alicyclic polyisocyanates, aliphatic polyisocyanates, and the like.

[0053] Examples of the aforementioned aromatic polyisocyanates include phthalic diisocyanate, toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and the like.

[0054] Examples of the aforementioned alicyclic polyisocyanates include cyclohexylidene diisocyanate, methylcyclohexylidene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, dimethyldicyclohexylmethane diisocyanate, and the like.

[0055] Examples of the aforementioned aliphatic polyisocyanates include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and the like.

[0056] One or more of the aforementioned polyisocyanate compounds can be used.

[0057] For reasons such as ease of use and availability, the main component of the aforementioned polyurethane resin composition is preferably diphenylmethane diisocyanate.

[0058] The content (% by weight) of the aforementioned isocyanate compound in the polyurethane resin composition is preferably 20 to 80%. When it is less than 20%, the flame retardancy deteriorates, and when it exceeds 80%, the adhesiveness to the skeleton and the like deteriorates.

[0059] <4>Polyol compound

[0060] The polyol compound is a material used as a curing agent for the polyurethane resin composition of the present invention.

[0061] The polyol compound includes an ester-based polyol compound or an ether-based polyol compound and combinations thereof.

[0062] <4.1>Ester-based polyol compound

[0063] Examples of the ester-based polyol compound include polymers obtained by dehydration condensation of polyacids and polyols, polymers obtained by ring-opening polymerization of lactones such as ε-caprolactone and α-methyl-ε-caprolactone, and condensates of hydroxycarboxylic acids and the above polyols.

[0064] Here, specific examples of the aforementioned polyacids include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, succinic acid, etc. From the perspective of flame retardancy, terephthalic acid modification is preferred, and from the perspective of adhesiveness, fatty acid modification is preferred.

[0065] The content (by weight %) of the aforementioned ester compound in the polyurethane resin composition is preferably 20 to 80%. When it is less than 20%, the adhesiveness to the skeleton and the like deteriorates. When it exceeds 80%, the resin strength decreases, and problems such as shrinkage may occur.

[0066] <4.2>Other polyol compounds

[0067] Examples of other polyol compounds include polycaprolactone polyol, polycarbonate polyol, aromatic polyol, alicyclic polyol, aliphatic polyol, polymer polyol, polyether polyol, and the like.

[0068] Examples of the aforementioned polycaprolactone polyol include polypropylene carbonate diol, polycaprolactone diol, polyvalerolactone diol, and the like.

[0069] Examples of the aforementioned polycarbonate polyol include polyols obtained by the dealcoholization reaction of hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, octylene glycol, nonylene glycol, and the like with diethyl carbonate, dipropyl carbonate, and the like.

[0070] Examples of the aforementioned aromatic polyol include bisphenol A, bisphenol F, phenol novolac, cresol novolac, and the like.

[0071] Examples of the aforementioned alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophorone diol, dicyclohexylmethane diol, dimethyldicyclohexylmethane diol, and the like.

[0072] Examples of the aforementioned aliphatic polyol include ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, and the like.

[0073] Specific examples of the aforementioned polyol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, diethylene glycol, 1,6-hexylene glycol, neopentyl glycol, and the like.

[0074] In addition, specific examples of the aforementioned hydroxycarboxylic acid include castor oil, reaction products of castor oil and ethylene glycol, and the like.

[0075] From the aspect of flame retardancy, aromatic polyol is preferred.

[0076] <5>Trimerization catalyst

[0077] The trimerization catalyst is a material for causing the isocyanate groups contained in the polyisocyanate compound to react for trimerization and promoting the formation of the isocyanurate ring.

[0078] As a trimerization catalyst, for example, as a catalyst, nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, 2,4,6-tris(dialkylaminoalkyl)hexahydro-s-triazine, etc., carboxylate metal salts such as potassium acetate, potassium 2-ethylhexanoate, potassium octanoate, etc., tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, triphenylammonium salt, etc., quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetraphenylammonium salt, etc. can be used.

[0079] From the viewpoints of adhesion and flame retardancy at low temperatures, a combination of an alkyl metal carboxylate and a quaternary ammonium salt is preferred.

[0080] The content (weight %) of the aforementioned trimerization catalyst in the polyurethane resin composition relative to the polyurethane resin is preferably 1 to 20%. If it is less than 1%, the flame retardancy deteriorates. If it exceeds 20%, there may be problems such as clogging of the mixing part of the spray gun due to too fast reaction.

[0081] <6>Additives

[0082] The additive is an element for imparting flame retardancy to the polyurethane resin composition of the present invention.

[0083] For the additive, red phosphorus is used as an essential component, and in addition to red phosphorus, at least any one of a phosphate flame retardant and a chlorine-containing flame retardant is combined to constitute it.

[0084] <6.1>Red phosphorus

[0085] Red phosphorus is an element for suppressing the total heat release amount during combustion.

[0086] There is no limitation on the red phosphorus used in the present invention, and commercially available products can be appropriately selected for use. However, considering the production of the polyol liquid, red phosphorus obtained by surface-treating red phosphorus, which is a dangerous substance of the second category under the Fire Service Act, with a thermoplastic plastic or the like and having improved oxidation resistance, safety, and stability is preferably used.

[0087] The content (weight %) of the aforementioned red phosphorus in the polyurethane resin composition relative to the polyurethane resin is preferably 0.3 to 25%. If it is less than 0.3%, the flame retardancy deteriorates. If it exceeds 25%, there may be problems such as clogging of the mixing part of the spray gun.

[0088] <6.2>Phosphate flame retardant

[0089] The phosphate flame retardant is an element for further suppressing the total heat release amount by combining with red phosphorus.

[0090] The phosphate flame retardant used in the present invention contains phosphoric acid.

[0091] As the aforementioned phosphate flame retardant, for example, phosphates containing the aforementioned various phosphoric acids and salts of at least one metal or compound selected from metals in Groups IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines can be cited.

[0092] As the metals in Groups IA to IVB of the periodic table, lithium, sodium, calcium, barium, iron(II), iron(III), aluminum, etc. can be cited.

[0093] In addition, as the aforementioned aliphatic amines, methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, piperazine, etc. can be cited.

[0094] In addition, as the aforementioned aromatic amines, pyridine, triazine, melamine, ammonium, etc. can be cited.

[0095] It should be noted that for the above-mentioned phosphate flame retardants, known water resistance improvement treatments such as silane coupling agent treatment and covering with melamine resin can be added, and known foaming aids such as melamine and pentaerythritol can also be added.

[0096] In addition, as specific examples of the aforementioned phosphate flame retardants, monophosphates, pyrophosphates, polyphosphates, etc. can be cited.

[0097] As the aforementioned monophosphates, there is no particular limitation, and for example, ammonium salts such as ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium salts such as sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium hypophosphite, sodium phosphite, potassium salts such as potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium hypophosphite, potassium phosphite, lithium salts such as lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, lithium hypophosphite, lithium phosphite, barium salts such as barium dihydrogen phosphate, barium hydrogen phosphate, barium phosphate, barium hypophosphite, magnesium salts such as magnesium hydrogen phosphate, magnesium phosphate, trimagnesium phosphate, magnesium hypophosphite, calcium salts such as calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, calcium hypophosphite, zinc salts such as zinc phosphate, zinc phosphite, zinc hypophosphite, etc. can be cited.

[0098] In addition, as the aforementioned polyphosphates, there is no particular limitation, and for example, ammonium polyphosphate, piperazine polyphosphate, melamine polyphosphate, ammonium polyphosphate amide, aluminum polyphosphate, etc. can be cited.

[0099] Among them, in order to improve the self-extinguishing property of the aforementioned phosphate flame retardant, polyphosphates are preferably used, and ammonium polyphosphate and aluminum phosphite that form a foaming layer when heated are more preferably used.

[0100] The aforementioned phosphate flame retardant can be used singly or in combination of two or more.

[0101] The content (wt%) of the aforementioned phosphate flame retardant in the polyurethane resin composition relative to the polyurethane resin is preferably 0.3 to 25%. When it is less than 0.3%, the flame retardancy deteriorates. When it exceeds 25%, there may be problems such as clogging of the mixing part of the spray gun and powder sedimentation of the stirred raw materials in a short time.

[0102] <6.3>Chlorinated flame retardant

[0103] The chlorinated flame retardant is an element for suppressing the maximum heat release rate in the initial stage of combustion.

[0104] As the chlorinated flame retardant, the following 5 kinds of flame retardants are mostly used.

[0105] (a) Tris(2-chloroethyl) phosphate (TCEP) CAS No. 115-96-8

[0106] (b) Tris(β-chloropropyl) phosphate (TCPP) CAS No. 13674-84-5

[0107] (c) Tris(dichloropropyl) phosphate (TDCP) CAS No. 13674-87-8

[0108] (d) Tetrakis(2-chloroethyl) dichloroisopentyl diphosphate (V6) CAS No. 38051-10-4

[0109] (e) Polyoxyalkylene bis(dichloroalkyl) phosphate (CR-504L) CAS No. 184530-92-5

[0110] The content (wt%) of the aforementioned chlorinated flame retardant in the polyurethane resin composition relative to the polyurethane resin is preferably 2 to 30%. When it is less than 2%, the flame retardancy deteriorates. When it exceeds 30%, the resin strength decreases, and problems such as shrinkage may occur.

[0111] <7>Non-silicon surface conditioner

[0112] As the non-silicon surface conditioner, for example, acrylic surface conditioners can be cited.

[0113] The acrylic surface conditioner is a solvent-free surface conditioner with an acrylic polymer as the main component, and has the function of increasing the surface free energy of the cured resin.

[0114] The acrylic surface conditioner increases the surface free energy of the applied coating film by incorporating a highly polar part into the molecule, and is effective in improving the wettability and adhesion to the surface coating and imparting hydrophilicity.

[0115] In addition, since the acrylic-based surface conditioner is a solvent-free liquid product, it is easy to add and can be applied not only to solvent-based coatings but also to solvent-free coatings.

[0116] It should be noted that in the present invention, the surface conditioner is made non-silicon-based to prevent the deterioration of adhesiveness during lamination, prevent peeling, and prevent curling.

[0117] The content of the aforementioned non-silicon-based surface conditioner in the polyurethane resin composition is preferably 0.2 to 10%. If it is less than 0.2%, the specified foaming ratio cannot be obtained. If it exceeds 10%, the resin strength decreases, and problems such as shrinkage may occur.

[0118] <8>Regarding the foam stabilizer (reason for not containing in the formulation)

[0119] The foam stabilizer has the function of adjusting the surface tension when producing a foam by using the surface tension to close the blowing agent. For a formulation without a foam stabilizer, a resin mass will be formed instead of a foam. Therefore, it is considered an essential component in the technical field of the present invention.

[0120] On the other hand, when using a foam stabilizer, there are also the following disadvantages: the self-adhesion of polyurethane decreases, cyclic siloxanes are generated, or there are adverse effects on foamability due to the combination with HFO blowing agents, etc.

[0121] Therefore, when using the polyurethane resin composition of the present invention, even without a foam stabilizer, a foam that has no problem as a heat insulating material for buildings can be formed by selecting the formulation conditions of other materials.

[0122] <9>Others

[0123] In addition, the polyurethane resin composition of the present invention may also contain the following materials.

[0124] <9.1>Blowing agent

[0125] The blowing agent is a material that enables good foaming when a polyisocyanate compound (the first component) and other components (the second component) are mixed to form a foam.

[0126] The foaming agent promotes the foaming of the polyurethane resin. Examples of the foaming agent include, for example, water; low-boiling hydrocarbons such as propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane; chlorinated aliphatic hydrocarbon compounds such as dichloroethane, chloropropane, chloroisopropane, chlorobutane, chloroisobutane, chloropentane, and chloroisopentane; fluorine compounds such as CHF3, CH2F2, and CH3F; hydrochlorofluorocarbon compounds such as trichloromonofluoromethane, trichlorotrifluoroethane, dichloromonofluoroethane (e.g., HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)); hydrofluorocarbons such as HFC-245fa (1,1,1,3,3-pentafluoropropane) and HFC-365mfc (1,1,1,3,3-pentafluorobutane); hydrofluoroolefins such as HFO-1233zd ((E)-1-chloro-3,3,3-trifluoropropene); ether compounds such as diisopropyl ether, or organic physical foaming agents such as mixtures of these compounds, and inorganic physical foaming agents such as nitrogen, oxygen, argon, and carbon dioxide gas, etc.

[0127] From the viewpoints of environmental impact and excellent heat insulation performance, as the foaming agent, a hydrofluoroolefin (HFO) is preferably contained.

[0128] The content of the foaming agent is not particularly limited. It is preferably 0.3 parts by weight to 112 parts by weight, more preferably in the range of 0.3 parts by weight to 67 parts by weight, further preferably in the range of 1.8 parts by weight to 67 parts by weight, and most preferably in the range of 3.7 parts by weight to 37 parts by weight with respect to 100 parts by weight of the polyol. In the foaming polyurethane composition, it can be in the range of 0.1 parts by weight to 30 parts by weight, more preferably in the range of 0.1 parts by weight to 18 parts by weight, further preferably in the range of 0.5 parts by weight to 18 parts by weight, and most preferably in the range of 1 part by weight to 10 parts by weight with respect to 100 parts by weight of the polyurethane resin.

[0129] When the amount of the foaming agent is above the above lower limit value, foaming is promoted, and the density of the obtained molded body can be reduced. When it is below the above upper limit value, it is possible to prevent the case where the foam does not foam and no foam body is formed.

[0130] In addition, in the present invention, one or more of the aforementioned foaming agents can be used.

[0131] <9.2> Polyurethane foaming catalyst

[0132] The polyurethane foaming catalyst is a material that particularly promotes the reaction of the isocyanate compound and water. Specifically, by using the carbon dioxide generated by the reaction of isocyanate and water, the foaming of the stock solution is promoted.

[0133] As a foaming catalyst, specifically, chain tertiary amines such as bis(2-dimethylaminoethyl) ether and N,N-dimethylalkylamine, and acid-terminated foaming catalysts obtained by neutralizing a tertiary amine resin composition with a carboxylic acid can be cited.

[0134] From the viewpoint of not causing decomposition of HFC and HFO, it is preferable to use an acid-terminated foaming catalyst.

[0135] The content (weight %) of the aforementioned polyurethane-forming foaming catalyst in the polyurethane resin composition with respect to the polyurethane resin is preferably 0.1 to 10%. If it is less than 0.1%, a specified foaming ratio cannot be obtained, and if it exceeds 10%, there may be problems such as blockage of the mixing part of the spray gun due to too fast reaction.

[0136] <9.3>Polyurethane-forming metal catalyst

[0137] The polyurethane-forming metal catalyst is a material for promoting the reaction between an isocyanate compound and a polyol compound.

[0138] As the polyurethane-forming metal catalyst, metal salts containing lead, tin, bismuth, copper, zinc, cobalt, nickel, etc. can be cited. Organic acid metal salts containing lead, tin, bismuth, copper, zinc, cobalt, nickel, etc. are preferably used, and it has the effect of not causing decomposition of HFC and HFO blowing agents caused by amine-based polyurethane catalysts.

[0139] The content (weight %) of the aforementioned polyurethane-forming metal catalyst with respect to the polyurethane resin is preferably 0.1 to 10%. If it is less than 0.1%, a specified foaming ratio cannot be obtained, and if it exceeds 10%, there may be problems such as blockage of the mixing part of the spray gun due to too fast reaction.

[0140] <9.4>Adhesion promoter

[0141] The adhesion promoter is a material for improving the adhesiveness of the polyurethane resin composition of the present invention.

[0142] As the adhesion promoter, cyclic esters, etc. can be cited, for example.

[0143] For the adhesion promoter, by promoting the polymerization on the foam surface, the friability of the surface that is likely to occur under high-index and / or high-water-content formulations is suppressed. In addition, appropriate foam adhesiveness can be achieved even during spray foam coating in a low-temperature environment.

[0144] <9.5>Dispersant

[0145] The dispersant is a material for making the dispersibility of the flame retardant good.

[0146] As the dispersant, alkylammonium salts of acidic copolymers having hydroxyl groups, etc. can be cited, for example.

[0147] By containing a dispersant, the wetting and dispersion rate of red phosphorus and phosphate flame retardant fillers during dispersion is improved, and the viscosity is reduced. Therefore, the compounding amount of the fillers can be increased.

[0148] Moreover, if the compounding amount of the fillers is increased, the flame retardancy is improved.

[0149] In addition, an effect can be obtained in which the time for the fillers to settle to the bottom of the container after being stirred and mixed with stirring blades or the like is significantly delayed.

[0150] The content (weight %) of the aforementioned dispersant in the polyurethane resin composition relative to the polyurethane resin is preferably 0.1 to 10%. If it is less than 0.1%, the dispersibility of the fillers will not be improved. If it exceeds 10%, the resin strength will decrease, and problems such as shrinkage may occur.

[0151] Examples

[0152] The present invention will be described in detail below with reference to the examples. It should be noted that the present invention is not limited by any of the following examples.

[0153] <1>Experimental conditions

[0154] Various tests were conducted on examples of foams based on the polyurethane resin composition of the present invention and comparative examples based on the prior art.

[0155] The details of each component used in the examples and comparative examples are described below.

[0156] In addition, the numerical values of each component are expressed in parts by weight.

[0157] (1) Polyol compounds

[0158] ·A-1: Terephthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: MAXIMOL RFK-505, hydroxyl value = 250 mgKOH / g)

[0159] ·A-2: Terephthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: MAXIMOL RFK-509, hydroxyl value = 200 mgKOH / g)

[0160] ·A-3: Aliphatic-modified terephthalic acid-based polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: MAXIMOL RLK-087, hydroxyl value = 200 mgKOH / g)

[0161] ·A-4: Mannich-based polyol (manufactured by Asahi Glass Co., Ltd., product name: EXCENOL NB-615, hydroxyl value = 579 mgKOH / g)

[0162] (2) Trimerization catalyst

[0163] · B-1: Potassium octanoate (manufactured by Evonik, product name: DABCO K-15)

[0164] · B-2: Quaternary ammonium salt (manufactured by Evonik, product name: TMR-7)

[0165] (3) Polyurethane foaming catalyst

[0166] · C: Tertiary amine salt (manufactured by Evonik, product name: POLYCAT 201)

[0167] (4) Metal resinification catalyst

[0168] · D: Bismuth octanoate (manufactured by Shepherd Chemical Company, product name: Bicat 8210)

[0169] (5) Blowing agent

[0170] · E-1: Water

[0171] · E-2: HFO-1233zd (manufactured by Honeywell, product name: Solstice LBA)

[0172] · E-3: HFO-1336mzz (manufactured by Chemours, product name: OPTEON1100)

[0173] (6) Silicone foam stabilizer

[0174] F: Siloxane (manufactured by Dow Corning Toray Co., Ltd., product name: SH-193)

[0175] (7) Additive

[0176] · G-1: Red phosphorus (manufactured by Phosphorus Chemical Industry Co., Ltd., product name: RINKA FE140)

[0177] · G-2: Ammonium polyphosphate (manufactured by Taihei Chemical Industry Co., Ltd., product name: TAIEN CII)

[0178] · G-3: Aluminum phosphite (manufactured by Taihei Chemical Industry Co., Ltd., product name: APA100)

[0179] · G-4: Chlorinated phosphate ester tris(β-chloropropyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name: TMCPP)

[0180] (8) Adhesion promoter

[0181] ·H: Cyclic ester (manufactured by Momentive Performance Materials, product name: AP)

[0182] (9) Dispersant

[0183] ·I: Alkyl ammonium salt of wetting dispersant acidic copolymer (manufactured by BYK-Chemie Japan, product name: BYK-W969)

[0184] (10) Surface conditioner

[0185] ·J-1: Acrylic polymer (manufactured by Kusumoto Chemical Co., Ltd., product name: SEI-W01)

[0186] ·J-2: Acrylic polymer (manufactured by Kusumoto Chemical Co., Ltd., product name: SEI-1501)

[0187] ·J-3: Anionic polymer (manufactured by Kusumoto Chemical Co., Ltd., product name: AQ-360)

[0188] ·J-4: Vinyl polymer (manufactured by Kusumoto Chemical Co., Ltd., product name: UVX-190)

[0189] (11) Polyisocyanate

[0190] ·K: Polymeric MDI (manufactured by TOSOH CORPORATION, product name: Milionate MR-200)

[0191] <2>Evaluation method of adhesiveness

[0192] Regarding the evaluation of adhesiveness, taking the adhesive strength of 80 kPa or more obtained by the measurement method of adhesive strength using JIS A9526 as the standard, “○” is regarded as appropriate and “×” is regarded as inappropriate.

[0193] <3>Evaluation method of flame retardancy

[0194] Regarding the evaluation of non-combustibility, for the foams based on each example, samples for cone calorimeter test were prepared respectively, and in the heat release test according to the test method of ISO-5660, the total heat release, the maximum heat release rate, quasi-non-combustibility and non-combustibility were evaluated.

[0195] <4>Test outline

[0196] The outline of the heat release test is as described below.

[0197] The aforementioned foam was cut into 10 cm in length, 10 cm in width and 5 cm in thickness to prepare samples for cone calorimeter test.

[0198] [Manual]

[0199] Weigh the polyol liquid and isocyanate liquid that have been pre-mixed as shown in the composition table into a 1-liter disposable cup. After reaching a liquid temperature of 15°C, stir and mix for 3 to 8 seconds using a stirring drill bit with a cage mixer at 2800 rpm. Inject the obtained raw material liquid into a box with dimensions of 200×200×unrestricted height to make a test piece.

[0200] To confirm the adhesiveness during lamination, perform the above injection two or more times.

[0201] [Spray]

[0202] Prepare the polyol liquid and isocyanate liquid that have been pre-mixed as shown in the composition table in a 200-liter metal barrel, and make test pieces under the following conditions.

[0203] Spraying equipment: Model A-25 made by GRACO

[0204] Spray gun: AP AR4242 made by GRACO

[0205] Raw material temperature: 60°C

[0206] Method for making test pieces: According to JISA9526

[0207] Use the above-mentioned cone calorimeter test sample, and according to the test method of ISO-5660, conduct the measurement of the total heat release and the maximum heat release rate based on the cone calorimeter test when heating at a radiant heat intensity of 50 kW / m 2 for 20 minutes, and the confirmation of the residue state.

[0208] <5>Test results

[0209] The test results for each example and comparative example are shown in Tables 2 and 3. The comparison tables for extracting the test results of the following items are as Figures 1 to 7 shown.

[0210] [Table 2]

[0211]

[0212] [Table 3]

[0213]

[0214] <5.1>Presence or absence of foam stabilizer (Comparative Examples 1 and 2, and Example 1)

[0215] Figure 1 Show the comparison of experimental results based on the presence or absence of foam stabilizer.

[0216] In the case of the polyurethane resin compositions containing a foam stabilizer (silicone-based foam stabilizer) shown in Comparative Examples 1 and 2, the adhesiveness was not suitable in both cases.

[0217] Example 1 is an example in which the compounding shown in Comparative Example 2 removed the foam stabilizer and a surface conditioner was newly added, and as a result, there was no problem in terms of adhesiveness.

[0218] From this, it is speculated that in the present invention, not containing a foam stabilizer is an important main reason for ensuring adhesiveness.

[0219] <5.2>Difference in the type of surface conditioner (Examples 3 and Comparative Examples 3 and 4)

[0220] Figure 2 The comparison of the experimental results based on the difference in the type of surface material is shown.

[0221] In Example 3, a surface conditioner that is a non-silicone-based acrylic polymer was used, and there was no problem in the evaluation of adhesiveness and non-combustibility.

[0222] On the other hand, when a surface conditioner such as an anionic surfactant or a surface conditioner of a vinyl-based polymer was used as in Comparative Examples 3 and 4, a result in which the cell state of the foam was not preferable was obtained.

[0223] From this, it is speculated that in the present invention, when a surface conditioner is contained, it is preferably a surface conditioner that is a non-silicone-based acrylic polymer.

[0224] <5.3>Presence or absence of an ether-based polyol compound (Examples 10 and 11)

[0225] Figure 3 The comparison of the experimental results based on the presence or absence of an ether-based polyol compound is shown.

[0226] When Example 10 in which an ester-based polyol compound was selected as the polyol compound and Example 11 in which an ether-based polyol compound was further added to Example 10 were compared, there was no problem in the evaluation of adhesiveness, non-combustibility, and quasi-non-combustibility in either case, and there was no large difference between the two.

[0227] From this, it is speculated that in the present invention, there is no obstacle when an ester-based polyol compound and an ether-based polyol compound are used in combination as the polyol compound.

[0228] <5.4>Presence or absence of an adhesion promoter (Examples 8 and 10)

[0229] Figure 4 The comparison of the experimental results based on the presence or absence of an adhesion promoter is shown.

[0230] Between Example 8 and Example 10, the compounding is different only in the presence or absence of the adhesion promoter, and as a result, there are no problems in the evaluation of adhesiveness, nonflammability, and quasi-nonflammability in any of the examples.

[0231] From this, it is speculated that there is no obstacle in newly adding the adhesion promoter in the present invention.

[0232] <5.5> Presence or absence of polyurethane-forming catalyst or metal-resin-forming catalyst (Examples 14 to 16)

[0233] Figure 5 Shows a comparison of the experimental results based on the presence or absence of the polyurethane-forming catalyst or metal-resin-forming catalyst.

[0234] Between Examples 14 to 16, the compounding is different only in the presence or absence of the polyurethane-forming catalyst and metal-resin-forming catalyst, and as a result, there are no problems in the evaluation of adhesiveness, nonflammability, and quasi-nonflammability in any of the examples.

[0235] From this, it is speculated that there is no obstacle in newly adding the polyurethane-forming catalyst or metal-resin-forming catalyst in the present invention.

[0236] <5.6> Presence or absence of dispersant (Examples 12, 17)

[0237] Figure 6 Shows a comparison of the experimental results based on the presence or absence of the dispersant.

[0238] Between Example 12 and Example 17, the compounding is different only in the presence or absence of the dispersant, and as a result, there are no problems in the evaluation of adhesiveness, nonflammability, and quasi-nonflammability in any of the examples.

[0239] From this, it is speculated that there is no obstacle in newly adding the dispersant in the present invention.

[0240] <5.7> Presence or absence of phosphate-based flame retardant or chlorine-based flame retardant (Examples 18, 19 and Comparative Example 5)

[0241] Figure 7 Shows a comparison of the experimental results based on the presence or absence of the phosphate-based flame retardant or chlorine-based flame retardant.

[0242] For Example 18 containing (G-4) chlorinated phosphate ester as the chlorine-based flame retardant and Example 19 containing ammonium polyphosphate (G-2) as the phosphate-based flame retardant, there are no problems in the evaluation of adhesiveness, nonflammability, and quasi-nonflammability in any of the examples.

[0243] On the other hand, in the example shown in Comparative Example 5 that does not contain any of the phosphate-based flame retardant and chlorine-based flame retardant, in the nonflammability evaluation, the total heat release and the maximum heat release rate are worse than those of the aforementioned Examples 18 and 19, and the residue state is also inappropriate.

[0244] It is thus speculated that in the present invention, by newly adding a phosphate-based flame retardant or a chlorine-based flame retardant, an improvement in flame retardancy can be expected.

Claims

1. A polyurethane resin composition, characterized in that, It is a polyurethane resin composition for forming a foam of a heat insulating material constituting a building, and the foam has at least quasi-incombustibility in the heat release test according to ISO-5660. The polyurethane resin composition contains at least a polyisocyanate compound, an ester-based polyol compound, a trimerization catalyst, an additive, a foaming agent, and a non-silicon-based surface conditioner, and does not contain a foam stabilizer. The non-silicon-based surface conditioner is an acrylic-based surface conditioner. The additive contains red phosphorus as an essential component and is combined with at least any one of a phosphate flame retardant and a chlorine-containing flame retardant. The phosphate flame retardant is selected from one or more of monophosphate, pyrophosphate, and polyphosphate.

2. The polyurethane resin composition according to claim 1, wherein The phosphate flame retardant contains at least any one of ammonium polyphosphate and aluminum phosphite.

3. The polyurethane resin composition according to claim 1 or 2, characterized in that, The chlorine-containing flame retardant is a chlorine-based phosphate ester.

4. The polyurethane resin composition according to claim 1 or 2, characterized in that, The foaming agent contains HFO (hydrofluoroolefin).

5. The polyurethane resin composition according to claim 4, wherein, The foaming agent also contains water.

6. The polyurethane resin composition according to claim 1 or 2, characterized in that, It also contains an ether-based polyol compound.

7. The polyurethane resin composition according to claim 1 or 2, characterized in that, It also contains an adhesion promoter.

8. The polyurethane resin composition according to claim 1 or 2, characterized in that, It also contains at least any one of a polyurethane foaming catalyst and a polyurethane metal catalyst.

9. The polyurethane resin composition according to claim 1 or 2, wherein It also contains a dispersant.

10. A method for insulating a building, characterized in that, It uses the polyurethane resin composition according to any one of claims 1 to 9 as a sprayable heat insulating material for on-site foaming.

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