Flame-retardant sealing material

Abstract

A flame-retardant sealing material comprising a polyurethane foam formed from a polyurethane starting material containing components such as a polyol component, an isocyanate, a water-repellent agent, and a flame retardant, wherein the polyol component comprises a hydroxyl-terminated prepolymer obtained by the reaction of a polyether polyol and an isocyanate, the water-repellent agent being a polybutadiene polyol or the like, and wherein (1) a non-halogenated, non-condensed phosphate ester or (2) a halogenated, non-condensed phosphate ester, which is liquid at normal temperature, is used as the flame retardant, and wherein the isocyanate index is 100 to 150.

Description

Technical area

[0001] The invention relates to a flame-retardant sealing material with outstanding properties for excluding water. State of the art

[0002] Polyurethane foams that exclude water have been used as waterproofing materials. As a conventional polyurethane foam that excludes water, a polyurethane foam has been proposed that has high water exclusion properties with a holding time of nine hours or longer under a water pressure of 100 mmAq and a low density of 15 kg / m³. 3 up to 40 kg / m 3 (PTL 1).

[0003] The polyurethane foam with high water exclusion properties and low density contains 80 to 100 parts by mass of a hydroxyl-terminated prepolymer obtained by the reaction of a polyether polyol and an isocyanate per 100 parts by mass of the total amount of the polyol, and contains a water-repellent agent containing at least one selected from the group consisting of a polybutadiene polyol, a hydrogenated polyol of a polybutadiene, a polyisoprene polyol, and a hydrogenated polyol of a polyisoprene, and the isocyanate index is 100 to 150.

[0004] However, the flame retardant properties of the conventional polyurethane foam having high water exclusion properties and low density have not been investigated, and it has been required to improve the flame retardant properties thereof for applications requiring low flammability, such as a waterproofing material used in an automobile part or the like wherein the low flammability is required.

[0005] In view of environmental protection, non-halogen types that do not use a halogen compound have also recently been proposed as low-flammability polyurethane foams used for buffer materials, soundproofing materials, and the like. Non-halogen low-flammability polyurethane foams include a polyurethane foam containing a polyol and a phthalate ester polyol, and containing melamine powder with an average particle size of 0.5 μm or less as a flame retardant (PTL 2), a polyurethane foam containing a phthalate ester-based polyol, a phosphate ester-type flame retardant, melamine powder with an average particle size of 0.1 to 0.5 μm, and an inorganic compound hydrate (PTL 3), and a polyurethane foam containing melamine and a condensed phosphate ester-type flame retardant (PTL 4).Polyurethane foams, flame retardants and polyurethane foams containing various flame retardants are disclosed in various documents (PTL 5 - 9).

[0006] However, because the conventional low-flammability polyurethane foams used for buffer materials, soundproofing materials, and the like are not used for the purpose of excluding water, their water-exclusion properties have not been investigated.

[0007] Polyurethane foam is produced by mixing a foaming agent, a catalyst, and a flame retardant with a liquid polyol, then mixing a liquid isocyanate therewith to react the polyol and isocyanate, and then foaming the materials. If the materials are not mixed well, a good cell state is not achieved, and foaming failure sometimes occurs. Therefore, to maintain a good foam state, all raw materials used for polyurethane foam are preferably liquid.

[0008] Thus, although attempts have been made to improve flame-retardant properties by using a flame retardant that is solid at ordinary temperature and used for a polyurethane foam with low flammability (e.g., melamine) as a raw material of a conventional polyurethane foam capable of excluding water, or by using a solid flame retardant (e.g., melamine) and a liquid flame retardant (e.g., a condensed phosphate ester type flame retardant), the amount of the solid flame retardant used has been limited to obtain a foam with good foaming condition, and it has not been possible to obtain both excellent water-exclusion properties and favorable low flammability.

[0009] In addition, when a condensed phosphate ester type flame retardant, which is liquid at conventional temperature, was used, the water exclusion property was unproblematic under a water pressure of about 50 mmAq, but there was a phenomenon that the water exclusion property deteriorated remarkably under a water pressure of 100 mmAq.

[0010] Thus, it has been impossible to obtain a halogen-free flame-retardant sealing material that exhibits water exclusion properties at 100 mmAq and that can withstand the flammability test according to FMVSS302 (Federal Motor Vehicle Safety Standard No. 302). When a liquid phosphate ester-type flame retardant is used, increasing its amount to improve flame-retardant properties also leads to a deterioration in fogging properties and easily causes clouding in cases where the material is molded with a transparent material such as glass. Thus, it has been impossible to obtain a flame-retardant sealing material with good fogging properties. Literature listPatent literature PTL 1: JP 2010-144066 A PTL 2: JP 2007-002036 A PTL 3: JP 2007-091866 A PTL 4: JP 2011-184601 A PTL 5: JP 2010-247532 A PTL 6: JP 2009-51996 A PTL 7: EP 1973965 B1 PTL 8: DE 603 ​​16 431 T2 PTL 9: EP 0307987 B1 Summary of the inventionTechnical problem

[0011] The invention has been made in view of the above points, and the invention aims to provide a flame-retardant sealing material having excellent water-exclusion properties and excellent flame retardancy (low flammability), and also aims to provide a flame-retardant sealing material having good fogging properties. Solution to the problem

[0012] The invention is defined in the claims. Advantageous effects of the invention

[0013] The polyol component of the flame-retardant sealing material of the present invention contains a hydroxyl-terminated prepolymer obtained by reacting a polyether polyol and an isocyanate, either alone or in a mixture of the hydroxyl-terminated prepolymer and another polyol. Because the hydroxyl-terminated prepolymer obtained by reacting a polyether polyol and an isocyanate is contained in an amount of 80 to 100 parts by mass per 100 parts by mass of the polyol component, the viscosity of the polyurethane starting material is high, and the cells become fine during foam formation. Furthermore, because the amount of film (mirror) covering the cell network of the polyurethane foam is increased, the permeability decreases, making it difficult for water to penetrate into the cells, resulting in improved water-separating properties.When polyether polyols are used as the hydroxyl-terminated prepolymer and as the polyol different from the hydroxyl-terminated prepolymer constituting the polyol component, the hydrolysis resistance is good because the polyol component contains only polyether polyols.

[0014] As the water repellent for the flame-retardant sealing material of the present invention, at least one selected from the group consisting of a polybutadiene polyol, a hydrogenated polyol of a polybutadiene, a polyisoprene polyol, and a hydrogenated polyol of a polyisoprene is used. Thus, the water repellent is incorporated into the resin network of the foam, and the water repellent does not bleed out. Also, the risk of foam deterioration over time or deterioration of the water repellent properties is low, and good water-exclusion property can be maintained for a long period of time. Moreover, because the isocyanate index is 100 to 150, the polyol component and the water repellent completely resinify, and a secondary crosslinking reaction (allophanate bond, biuret bond, or the like) of the isocyanate occurs because the isocyanate is present in excess.The water-repellent properties of the foam also continue to improve, and the water-exclusion properties continue to improve.

[0015] Because a non-halogenated, non-condensed phosphate ester which is liquid at ordinary temperature, which is included in an amount of 6 to 13 parts by mass per 100 parts by mass of the polyol component and which is isopropylated triaryl phosphate, or a halogen-containing, non-condensed phosphate ester which is liquid at ordinary temperature, which has a weight-average molecular weight of 400 or more, which is included in an amount of 3 to 25 parts by mass per 100 parts by mass of the polyol component and which is tris(1,3-dichloro-2-propyl)phosphate, is used as the flame retardant, the flame-retardant sealing material of the invention has good properties for excluding water under a water pressure of 100 mmAq without deteriorating the water exclusion properties, and has excellent flame retardancy that passes the flammability test according to FMVSS302.

[0016] More specifically, when a non-halogenated, non-condensed phosphate ester which is liquid at ordinary temperature and is isopropylated triaryl phosphate is used as the flame retardant, the flame retardant is contained in an amount of 6 to 13 parts by mass per 100 parts by mass of the polyol component, whereas when a halogen-containing, non-condensed phosphate ester which is liquid at ordinary temperature and has a weight-average molecular weight of 400 or more and is tris(1,3-dichloro-2-propyl)phosphate is used as the flame retardant, the flame retardant is contained in an amount of 3 to 25 parts by mass per 100 parts by mass of the polyol component.

[0017] Because the halogen-containing non-condensed phosphate ester has a weight-average molecular weight of 400 or greater, the flame-retardant property can be improved even when the amount of the halogen-containing non-condensed phosphate ester is small, and the deterioration of the fogging property caused when the amount of the liquid phosphate ester is increased to improve the flame retardancy can be avoided. Short description of the drawings [ Fig. 1] is a top view of a sample for measuring water exclusion properties. [ Fig. 2] is a figure illustrating the method for measuring the water exclusion property. Description of embodiments

[0018] The invention is described in detail below.

[0019] In the present invention, the flame-retardant sealing material of the present invention is sometimes referred to as a waterproofing material.

[0020] The flame-retardant sealing material of the present invention comprises a polyurethane foam formed from a polyurethane starting material containing a polyol component, an isocyanate, a foaming agent, a catalyst, a water repellent, and a flame retardant.

[0021] The polyol component contains 80 to 100 parts by mass of a hydroxyl-terminated prepolymer obtained by the reaction of a polyether polyol and an isocyanate, per 100 parts by mass of the polyol component. Because the hydroxyl-terminated prepolymer is contained in an amount of 80 to 100 parts by mass, the viscosity of the polyurethane foam raw material is high, and the cells become fine during foam formation. Furthermore, because the amount of the mirror covering the cell network of the polyurethane foam is increased and the permeability is reduced, the water-exclusion properties improve. If the amount of the hydroxyl-terminated prepolymer is lower than the above range, it becomes difficult to make the cells of the polyurethane foam fine, and the permeability is reduced, and the water-exclusion properties deteriorate.

[0022] The polyether polyol used to prepare the hydroxyl-terminated prepolymer of the present invention is a bifunctional or higher polyether polyol, and to obtain a polyurethane foam with finer cells, a trifunctional or higher polyether polyol is preferred. The bifunctional or higher polyether polyol is not particularly limited, and, for example, a polyether polyol obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to a starting material such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hydroquinone, water, resorcinol, bisphenol A, hydrogenated bisphenol A, glycerin, trimethylolpropane, pentaerythritol, monoethanolamine, diethanolamine, triethanolamine, tripropanolamine, ethylenediamine, 1,6-hexanediamine, tolylenediamine, diphenylmethanediamine, triethylenetetramine, sorbitol, mannitol, or dulcitol, or the like, can be used.

[0023] The isocyanate used to prepare the hydroxyl-terminated prepolymer of the present invention is a bifunctional or higher-functional isocyanate. The bifunctional or higher-functional isocyanate is not particularly limited and can be any of aromatic, alicyclic, and aliphatic isocyanates. One of the isocyanates can be used alone, or a combination of two or more can be used.

[0024] Examples of the bifunctional isocyanate include aromatic isocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane dianate, 2,2'-diphenylenemethane diisocyanate, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate or 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, alicyclic isocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate or methylcyclohexane diisocyanate, and aliphatic isocyanates such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate or lysine diisocyanate.

[0025] Examples of tri- or higher functional isocyanates include tris(4-phenyl isocyanate)thiophosphite, triphenylmethane triisocyanate, tolylene diisocyanate trimer, polymethylene polyphenyl isocyanate and diphenyl ether 2,4,4'-triisocyanate, as well as polyfunctional aromatic isocyanates, polyfunctional aliphatic isocyanates, block-type isocyanates and the like.

[0026] The hydroxyl-terminated prepolymer is obtained by a known method for producing a prepolymer from the polyether polyol and the isocyanate. Specifically, the hydroxyl-terminated prepolymer can be obtained by introducing a given amount of the polyether polyol into a tank heated to a given temperature (e.g., 80°C), introducing given amounts of the isocyanate and a known catalyst for polyurethane foam described below while stirring the tank filled with nitrogen, and reacting the materials.

[0027] The polyol used to prepare the hydroxyl-terminated prepolymer is a polyether polyol having a molecular weight of 300 to 10,000, more preferably a molecular weight of 1,000 to 8,000, and further preferably a molecular weight of 2,000 to 5,000. The isocyanate used to prepare the hydroxyl-terminated prepolymer is not particularly limited as long as preparation is not difficult due to the viscosity of the hydroxyl-terminated prepolymer, but tolylene diisocyanate is suitable. The viscosity of the hydroxyl-terminated prepolymer at 30°C is 2,000 to 30,000 mPa s, more preferably 4,000 to 28,000 mPa s, and further preferably 8,000 to 25,000 mPa s.

[0028] When the amount of the hydroxyl-terminated prepolymer contained per 100 parts by mass of the polyol component is less than 100 parts by mass, the polyol to be used in combination for the polyol component is not particularly limited, and a polyether polyol, a polymer polyol obtained by graft polymerization of a polyether polyol and styrene, acrylonitrile, or the like, a polyether ester polyol, or a polyester polyol can be used. In particular, a polyether polyol is preferred, and the polyether polyol used as a starting material for preparing the hydroxyl-terminated prepolymer is more preferably used in combination. When a polyester polyol is used as the polyol to be used in combination for the polyol component to obtain a flame-retardant sealing material having excellent hydrolysis resistance, a bi- or higher-functional polyester polyol obtained by condensation of a branched diol, such as3-methyl-1,5-pentanediol or 2-methyl-1,8-octanediol, and a dicarboxylic acid such as adipic acid (aliphatic acid), dimer acid (alicyclic acid) or phthalic acid (aromatic acid), a polyester polyol obtained by ring-opening polymerization of a polycarbonate diol or a lactone such as caprocatone, and the like are preferred.

[0029] As the isocyanate to be reacted with the polyol component, one of known aromatic, alicyclic, and aliphatic isocyanates for polyurethane foam is used alone, or a combination of two or more thereof is used. Examples of aromatic isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane dianate, 2,2'-diphenylene methane diisocyanate, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisonate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, and the like. Examples of alicyclic isocyanates include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate, and the like; and examples of aliphatic isocyanates include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexane diisocyanate, and the like.

[0030] Water is preferably used as the foaming agent. The amount is preferably about 1.5 to 6 parts by mass per 100 parts by mass of the polyol component, and the amount is more preferably 3 to 5 parts by mass. If the amount is less than 1.5 parts by mass, the deformation following the sealed object and the sealing properties deteriorate, whereas if the amount is more than 6 parts by mass, the calorific value is high and the formation is difficult.

[0031] Known catalysts for polyurethane foam can be used as the catalyst. Examples include amine catalysts such as triethylamine, triethylenediamine, diethanolamine, dimethylaminomorpholine, N-ethylmorpholine, or tetramethylguanidine; tin catalysts such as octyltin or dibutyltin dilaurate; and metal catalysts such as phenylmercuric propionate or lead octenoate (also called organometallic catalysts). The general amount of the catalyst is about 0.2 to 5 parts by mass per 100 parts by mass of the polyol.

[0032] The water-repellent agent contains at least one selected from the group consisting of a polybutadiene polyol, a hydrogenated polyol of a polybutadiene, a polyisoprene polyol, and a hydrogenated polyol of a polyisoprene. The polyol used as the water-repellent agent has a molecular weight of 500 to 6,000, more preferably a molecular weight of 1,000 to 5,000, and further preferably a molecular weight of 1,000 to 3,500, and the polyol has a hydroxyl value of 15 to 120 mgKOH / g, more preferably a hydroxyl value of 25 to 110 mgKOH / g, and further preferably a hydroxyl value of 35 to 70 mgKOH / g. The number of functional groups is 1.6 or more, and more preferably two or more.When the polyol is used as a water repellent, the water repellent is incorporated into the resin network, and the risk of foam deterioration over time or deterioration of water repellent properties due to bleed-out of the water repellent is low. Also, good water-exclusion properties can be maintained for a long period of time. The polyol of the water repellent is independent of the polyol component, and the amount per 100 parts by mass of the polyol component is preferably 3 to 35 parts by mass, more preferably 5 to 20 parts by mass, and further preferably 10 to 15 parts by mass.When the amount is less than 3 parts by mass, the effect of improving the water-exclusion properties is sometimes small, whereas sometimes the effect of further improving the water-exclusion properties is not obtained even if the polyol is used in an amount exceeding 35 parts by mass.

[0033] Polyurethane foam, generally used as a sealing material, is compressed between different materials, such as a metal and a thermoplastic resin or a thermosetting resin, when the polyurethane foam is used. Thus, the sealing material itself should adhere to both metal and resin. In actual use, if the polyurethane foam contains a compound that can form a volatile organic compound (VOC), the compound sometimes leads to adverse effects, such as chemical attack or bleeding, on the metal surface or the resin surface. When polyurethane foam is compressed between transparent materials, such as glass, and used therein, defects such as clouding such as fogging may also be caused.

[0034] By selecting the water repellent agent of the flame-retardant sealing material of the present invention, the eluted material amount is very low, namely 5% or less, in the Soxhlet extraction method using acetone (extraction time: 8 hours), and defects are not caused. The eluted material amounts of the sealing materials currently generally used are about 10 to 15%, and the eluted material amount of the present invention of 5% or less is substantially comparable to the performance characteristics of general-purpose polyurethane foams that do not contain a water repellent agent.

[0035] As the flame retardant, a non-halogenated, non-condensed phosphate ester which is liquid at ordinary temperature or a halogen-containing, non-condensed phosphate ester which is liquid at ordinary temperature is used, as defined in claims 1 and 3, respectively.

[0036] In the case of the halogen-containing non-condensed phosphate ester, the added amount of flame retardant is 3 to 25 parts by mass per 100 parts by mass of the polyol component. If the amount is less than 3 parts by mass, the flame-retardant sealant sometimes fails the flammability test according to FMVSS302. Whereas, if the amount is more than 25 parts by mass, water sometimes penetrates in less than nine hours in the water exclusion test under a water pressure of 100 mmAq, and sometimes good water-sealing properties cannot be maintained under a water pressure of 100 mmAq.

[0037] The non-halogenated, non-condensed phosphate ester is isopropylated triaryl phosphate.

[0038] In the case of non-halogenated, non-condensed phosphate ester, which is liquid at normal temperatures, as a flame retardant, the added amount of flame retardant is 6 to 13 parts by mass per 100 parts by mass of the polyol component. If the amount is less than 6 parts by mass, the flame-retardant sealant sometimes fails the flammability test according to FMVSS302. Whereas, if the amount is more than 13 parts by mass, water sometimes penetrates in less than nine hours in the water exclusion test under a water pressure of 100 mmAq, and sometimes good water exclusion properties cannot be obtained under a water pressure of 100 mmAq.

[0039] Condensed phosphate esters used as flame retardants are generally susceptible to hydrolysis, and it is speculated that the condensed phosphate ester is easily decomposed by heat and moisture during foaming. The resulting decomposition product significantly impairs the water-exclusion properties. On the other hand, the halogen-containing, non-condensed phosphate ester, which is liquid at normal temperatures, is not easily decomposed, and thus, the water-exclusion performance is assumed to be less likely to deteriorate. The halogen-containing, non-condensed phosphate ester may evaporate if the molecular weight is low, and the fogging properties deteriorate (there is a tendency to cause turbidity).Thus, the weight-average molecular weight is 400 or more, and the halogen-containing non-condensed phosphate ester is tris(1,3-dichloro-2-propyl)phosphate.

[0040] When using a halogen-containing non-condensed phosphate ester, which is liquid at normal temperatures, as a flame retardant, the added amount of flame retardant is 3 to 25 parts by mass per 100 parts by mass of the polyol component. If the amount is less than 3 parts by mass, the flame-retardant sealant sometimes fails the flammability test according to FMVSS302. However, if the amount exceeds 25 parts by mass, water sometimes penetrates in less than nine hours in the water exclusion test under a water pressure of 100 mmAq, and sometimes good water exclusion properties cannot be obtained under a water pressure of 100 mmAq.Furthermore, when the added amount of the flame retardant is within the range of 3 to 12 parts by mass per 100 parts by mass of the polyol component, a further improved fogging property can be obtained in addition to high water-exclusion properties and the outstanding flame retardancy.

[0041] The isocyanate index is 100 to 150, more preferably 105 to 140, and further preferably 110 to 130. When the isocyanate index is 100 to 150, the polyol component and the water-repellent agent completely resinify, and a secondary crosslinking reaction (allophanate bond, buiret bond, or the like) of the isocyanate occurs because the isocyanate is present in excess. Also, the water repellency of the foam further improves, and the water-exclusion properties further improve. When the isocyanate index is less than 100, the water-exclusion performance deteriorates. It is not necessary to specifically restrict the upper limit of the isocyanate index. However, when the isocyanate index exceeds 150, the heating temperature generated in the polyurethane foam during foaming becomes high (especially when forming a soft slabstock foam), and there is a risk of scorching or spontaneous combustion.In this regard, the isocyanate index is an index used in the field of polyurethanes, and is a value of the equivalent ratio of the isocyanate groups of the polyisocyanate to the active hydrogen groups in the raw material (e.g., the active hydrogen groups contained in the hydroxyl groups of the polyol, the active hydrogen groups of water or the like as a foaming agent, and the like), expressed as a percentage [equivalent of NCO groups / equivalent of active hydrogen groups × 100].

[0042] Additionally, additives such as a foam stabilizer and a pigment can be used appropriately. The foam stabilizer is a foam stabilizer used for polyurethane foam and can be a silicone-type foam stabilizer, a fluorine-containing compound-type foam stabilizer, or a well-known surfactant. A pigment is used according to the desired color.

[0043] The polyurethane foam is produced by a known foaming process in which a polyurethane starting material containing the polyol component, the isocyanate, the foaming agent, the catalyst, the water-repellent agent, the flame retardant, and the optional additives is stirred and mixed to react the polyol component and the isocyanate, and the material is foamed. The density of the polyurethane foam according to the invention is preferably 15 to 40 kg / m³ 3 , and in particular, the density is more preferably 20 to 35 kg / m 3 . If the density of the polyurethane foam is 15 to 40 kg / m 3 is, the material cost can be reduced because excellent waterproofing properties and low flammability can be obtained at low density, and the weight of the flame-retardant sealing material can be reduced.

[0044] The flame-retardant sealing material of the present invention is used after being processed into a thickness and a shape (e.g., a strip) according to the use by punching or the like. The flame-retardant sealing material of the present invention has a holding time of nine hours or longer, and more preferably 24 hours or longer, under a water pressure of 100 mmAq and has very good water-exclusion properties. The holding time under a water pressure of 100 mmAq is the period of time during which the water pressure of 100 mmAq is maintained when a sample for measuring the water-exclusion property (50) prepared by punching a U-shaped mold having the Fig. 1 size made of a flame-retardant sealing material with a thickness of 10 mm, between two acrylic resin plates (71 and 71) in a 50% compression state, as shown in Fig.2, and water is introduced into the U-shaped test sample (50) in such a way that the water pressure is 100 mAq.

[0045] The flame-retardant sealing material of the invention also has low flammability, passing the flammability test according to FMVSS302. In the FMVSS302 flammability test, the average burning rate and maximum burning rate of 10 test pieces are measured, and the sample is considered to have passed the test if any of the following (1) to (3) applies.

[0046] (1) The test piece does not burn, or the test piece burns, but the fire goes out before reaching the reference line for the start of burning (burning rate 0). (2) The fire extends beyond the reference line for the start of burning, but the fire goes out within 50.8 mm of the reference line for the start of burning and within 60 seconds (self-extinguishing (SE)). (3) The fire extends beyond the reference line for the start of burning, and the burning rate is 100 mm / min or less. Examples

[0047] The results of evaluation tests using the inventive examples and comparative examples are shown below, and the invention will be described in more detail. However, the invention is not limited to these examples. [Examples 1-1 to 1-20 and Comparative Examples 1-1 to 1-11]

[0048] Waterproofing materials containing the polyurethane foams of Examples and Comparative Examples were prepared using polyurethane raw materials with the compositions shown in Table 1-1 and Table 1-2. The components shown in Table 1-1 and Table 1-2 are as follows. In Table 1-1 and Table 1-2, the foaming property is A when good foam was obtained, and the foaming property is B when the foam was poor or could not be obtained. • Polyol A1: Hydroxyl-terminated prepolymer, synthesized by reacting a mixture of the following Polyol A2 / the following isocyanate = 2 mol / 1 mol in the presence of a metal catalyst at 80°C for about two hours, hydroxyl value 33 mgKOH / g, viscosity 17,000 mPa·s (30°C) • Polyol A2: Polyether polyol, molecular weight 3,000, number of functional groups 3, hydroxyl value 56 mgKOH / g, trade name GP-3000, manufactured by Sanyo Chemical Industries, Ltd. • Polyol A3: Polyester polyol, molecular weight 2,000, number of functional groups 3, hydroxyl value 84 mgKOH / g, trade name F-2010 (obtained by condensation polymerization of trimethylolpropane with 3-methyl-1,5-pentanediol and adipic acid), manufactured by Kuraray Co., Ltd. • Water repellent agent C1: Polybutadiene polyol, MW = 2100, number of functional groups 2, trade name KRASOL LBH-P2000, manufactured by Cray Valley • Water repellent C2: hydrogenated polybutadiene polyol, MW = 3,100, number of functional groups 2, trade name HLBH-P3000, manufactured by Cray Valley • Water repellent C3: Polybutadiene polyol, MW = 1,200, number of functional groups 2.3, trade name R-15HT, manufactured by Idemitsu Kosan Co., Ltd. • Water repellent C4: Isoprene polyol, MW = 2,500, number of functional groups 2.1, trade name Roly ip, manufactured by Idemitsu Kosan Co., Ltd. • Water repellent C5: hydrogenated isoprene polyol, MW = 2,500, number of functional groups 2.3, trade name Epol, manufactured by Idemitsu Kosan Co., Ltd. • Water repellent C6: Liquid petroleum resin, MW = 2,500, trade name SAS-LH, manufactured by Nippon Oil Corporation • Foaming agent D: Water • Foam stabilizer E: silicone type, trade name SZ-1919, manufactured by Dow Corning Toray Co., Ltd. • Catalyst F1-1: reactive tertiary amine, trade name Kaolizer No. 51, manufactured by Kao Corporation • Catalyst F2: Octyltin, trade name MRH-110, manufactured by Johoku Chemical Co., Ltd. • Flame retardant G1-1: isopropylated triarylphoshat, trade name REOFOS 35, viscosity 44 mm 2 / s, 25°C, manufactured by Ajinomoto Fine-Techno Co., Inc. • Flame retardant G1-2: isopropylated triarylphoshat, trade name REOFOS 50, viscosity 50 mm 2 / s, 25°C, manufactured by Ajinomoto Fine-Techno Co., Inc. • Flame retardant G1-3: isopropylated triarylphoshat, trade name REOFOS 65, viscosity 61 mm 2 / s, 25°C, manufactured by Ajinomoto Fine-Techno Co., Inc. • Flame retardant G1-4: isopropylated triarylphoshat, trade name REOFOS 95, viscosity 93 mm 2 / s, 25°C, manufactured by Ajinomoto Fine-Techno Co., Inc. • Flame retardant G1-5: isopropylated triarylphoshat, trade name REOFOS 110, viscosity 120 mm 2 / s, 25°C, manufactured by Ajinomoto Fine-Techno Co., Inc. • Flame retardant G1-6: aliphatic condensed phosphate ester, trade name DAIGUARD-880, manufactured by Daihachi Kogyo Co., Ltd. • Flame retardant G1-7: condensed phosphate ester, trade name Fyrol PNX-S, manufactured by ICL-IP • Isocyanate: 2,4-TDI / 2,6-TDI = 80 / 20, trade name T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.

[0049] In Table 1-1 and Table 1-2 below, the catalyst F1-1, the flame retardants G1-1 to G1-7, Examples 1-1 to 1-20 and Comparative Examples 1-1 to 1-11 are simply referred to as F1, G1 to G7, Examples 1 to 20 and Comparative Examples 1 to 11. [Table 1] Table 1-1 (The values ​​of the components are given in parts by mass) Example 1 2 3 4 5 6 7 8 9 10 Polyol component A1 100 100 100 100 100 100 100 100 100 100 A2 Water repellent C C1 12 12 12 12 12 12 12 12 C2 12 C3 12 C4 C5 C6 Foaming agent D 3,6 3,6 3, 6 3, 6 3, 6 3, 6 3, 6 3, 6 3, 6 3, 6 Foam stabilizer E E1 1 1 1 1 1 1 1 1 1 1 Catalyst F F1 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0, 3 F2 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3 Flame retardant G G1 10 G2 10 G3 6 10 13 10 10 10 G4 10 G5 10 G6 G7 Isocyanate 50,1 50,1 50,1 50,1 50,1 50,1 50,1 50,1 49,7 51,0 Isocyanate index 120 120 120 120 120 120 120 120 120 120 Foaming properties A A A A A A A A A A density kg / m 3 28 29 30 29 29 29 29 29 28 29 25 mmAq water exclusion property A A A A A A A A A A 50 mmAq water exclusion property A A A A A A A A A A 100 mmAq water exclusion property AA AA AA AA AA AA AA AA AA AA 100 mmAq water penetration time 24< 24< 24< 24< 24< 24< 24< 24< 24< 24< FMVSS302 flame retardancy A A A A A A A A A A [Table 1] (continued) Table 1-1 (continued) (The values ​​of the components are given in parts by mass) Example 11 12 13 14 15 16 17 18 19 20 Polyol component A1 100 100 100 100 100 100 100 100 100 80 A2 20 Water repellent C C1 3 35 12 12 12 12 12 12 C2 C3 C4 12 C5 12 C6 Foaming agent D 3, 6 3,6 3, 6 3, 6 3, 6 3, 6 3, 6 4,0 3,2 3,6 Foam stabilizer E E1 1 1 1 1 1 1 1 1 1 1 Catalyst F F1 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0, 3 F2 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3 Flame retardant G G1 G2 G3 10 10 10 10 10 10 10 10 10 10 G4 G5 G6 G7 Isocyanate 49,9 49,9 49,2 52,4 41, 8 45,9 62,6 54,7 45,6 51,0 Isocyanate index 120 120 120 120 100 110 150 120 120 120 Foaming properties A A A A A A A A A A density kg / m 3 29 29 24 40 30 30 35 22 39 31 25 mmAq water exclusion property A A A A A A A A A A 50 mmAq water exclusion property A A A A A A A A A A 100 mmAq water exclusion property AA AA A AA A AA AA AA AA A 100 mmAq water penetration time 24< 24< 18 24< 9 24< 24< 24< 24< 13 FMVSS302 flame retardancy A A A A A A A A A A

[0050] The density (kg / m 3 , JIS K 7222), the water exclusion properties and flame retardancy of each waterproofing material of the examples and comparative examples were measured. The water exclusion properties were determined by the Fig. 1 and Fig.2 were measured under a water pressure of 25 mmAq, a water pressure of 50 mmAq, and a water pressure of 100 mmAq. The water exclusion properties under a water pressure of 25 mmAq were determined to be (A) passed when water did not leak out for 24 hours or more after introducing water into the waterproofing material (50) from above in such a manner that the water pressure was 25 mmAq, and the water exclusion properties were determined to be (B) failed when water leaked out in less than 24 hours. The water exclusion properties under a water pressure of 50 mmAq were rated as (A) passed if water did not leak out for 24 hours or more after introducing water into the waterproofing material (50) from above in such a way that the water pressure was 50 mmAq, and the water exclusion properties were rated as (B) failed if water leaked out in less than 24 hours.The water exclusion performance under a water pressure of 100 mmAq was rated as (AA) best when water did not leak for 24 hours or more after introducing water into the waterproofing material (50) from above in such a way that the water pressure was 100 mmAq, and the water exclusion performance was rated as (A) pass when water did not leak for nine hours or more and less than 24 hours; and the water exclusion performance was rated as (B) fail when water leaked in less than nine hours. The average burning rate and maximum burning rate of 10 test pieces were measured according to the FMVSS302 flammability test. The flame retardancy was rated as (A) pass when any of the criteria (1) to (3) were met, and the flame retardancy was rated as (B) fail when none of the criteria were met.The measurement results are given at the end of Table 1-1 and Table 1-2.

[0051] As can be seen from the measurement results in Table 1-1, the non-halogenated waterproofing materials of the examples all passed the water exclusion property test under a water pressure of 100 mmAq and passed the FMVSS302 flammability test in terms of flame retardancy.

[0052] In contrast, Comparative Example 1-1 shown in Table 1-2 is an example in which no flame retardant was used, and Comparative Example 1-2 is an example in which the amount of flame retardant G1-3 (isopropylated triaryl phosphate, trade name REOFOS 65) was 5 parts by mass. Comparative Example 1-1 and Comparative Example 1-2 both failed the FMVSS302 flammability test and exhibited poor flame retardancy.

[0053] Comparative Example 1-3 is an example in which the amount of the flame retardant G1-3 (isopropylated triaryl phosphate, trade name REOFOS 65) was 15 parts by mass, and Comparative Example 1-3 failed the water exclusion property test under a water pressure of 100 mmAq.

[0054] Comparative Example 1-4 is an example in which the amount of the flame retardant G1-2 (isopropylated triaryl phosphate, trade name REOFOS 50) was 5 mass parts, and 2 mass parts of the flame retardant G1-6 (aliphatic condensed phosphate ester, trade name DAIGUARD-880) was used in combination, and Comparative Example 1-4 failed both the water exclusion property test under a water pressure of 50 mmAq and a water pressure of 100 mmAq.

[0055] Comparative Example 1-5 is an example in which 5 mass parts of the flame retardant G1-6 (aliphatic condensed phosphate ester, trade name DAIGUARD-880) was used alone as a flame retardant, and Comparative Example 1-5 failed both the water exclusion property test under a water pressure of 50 mmAq and a water pressure of 100 mmAq.

[0056] Comparative Example 1-6 is an example in which 10 parts by mass of flame retardant G1-7 (condensed phosphate ester, trade name Fyrol PNX-S) was used alone as the flame retardant. In Comparative Example 1-6, the foaming reaction was inhibited, and no foam could be obtained.

[0057] Comparative Example 1-7 is an example that does not contain a water repellent and failed the water exclusion property test under a water pressure of 25 mmAq, under a water pressure of 50 mmAq, and under a water pressure of 100 mmAq.

[0058] Comparative Example 1-8 is an example in which the polyol component did not contain a prepolymer and the polyol component was 100% polyether polyol, and Comparative Example 1-8 did not pass any of the water exclusion property tests under a water pressure of 25 mmAq, under a water pressure of 50 mmAq, and under a water pressure of 100 mmAq.

[0059] Comparative Example 1-9 is an example in which the prepolymer was contained in an amount of 75 parts by mass per 100 parts by mass of the polyol component, and Comparative Example 1-9 failed both the water exclusion property tests under a water pressure of 50 mmAq and under a water pressure of 100 mmAq.

[0060] Comparative Example 1-10 is an example wherein the isocyanate index was 95, and Comparative Example 1-10 did not include any of the water exclusion property tests under a water pressure of 25 mmAq, under a water pressure of 50 mmAq, and under a water pressure of 100 mmAq.

[0061] Comparative Example 1-11 is an example in which a liquid petroleum resin was used as a water repellent, and Comparative Example 1-11 failed both the water exclusion property test under a water pressure of 50 mmAq and a water pressure of 100 mmAq.

[0062] As explained above, the waterproofing materials of the examples are non-halogenated waterproofing materials having excellent water exclusion properties and excellent flame retardancy (low flammability), and they are suitable as waterproofing materials used in a part of an automobile or the like in which low flammability is required. [Examples 2-1 to 2-17 and Comparative Examples 2-1 to 2-19]

[0063] The flame-retardant sealing materials containing the polyurethane foams of Examples and Comparative Examples were prepared using polyurethane raw materials with the compositions shown in Table 2-1 and Table 2-2. The components shown in Table 2-1 and Table 2-2 are as follows. In Table 2-1 and Table 2-2, the foaming property is rated as A when good foam was obtained, and the foaming property is rated as B when the foam was poor or could not be obtained.

[0064] As polyols A1 and A2, water repellents C1 to C6, foaming agent D, foam stabilizer E, catalyst F2 and the isocyanate, those used in Examples 1-1 to 1-20 and Comparative Examples 1-1 to 1-11 described above were used. • Catalyst F2-1: reactive tertiary amine, trade name Kaolizer No. 81, manufactured by Kao Corporation • Flame retardant G2-1: Tris(1,3-dichloro-2-propyl)phosphate, Mw = 431, trade name WR-30-LV, manufactured by Albemarle Japan Corporation • Flame retardant G2-2: isopropylated triaryl phosphate, Mw = 500, trade name REOFOS 50, viscosity of 50 mm 2 / s, 25°C, manufactured by Ajinomoto Fine-Techno Co., Inc. • Flame retardant G2-3: isopropylated triaryl phosphate, Mw = 650, trade name REOFOS 65, viscosity of 61 mm 2 / s, 25°C, manufactured by Ajinomoto Fine-Techno Co., Inc. • Flame retardant G2-4: halogen-containing condensed phosphate ester, trade name CR504L, manufactured by Daihachi Kogyo Co., Ltd. • Flame retardant G2-5: halogen-containing condensed phosphate ester, trade name CR570, manufactured by Daihachi Kogyo Co., Ltd. • Flame retardant G2-6: aliphatic condensed phosphate ester, trade name DAIGUARD-880, manufactured by Daihachi Kogyo Co., Ltd. • Flame retardant G2-7: condensed phosphate ester, trade name Fyrol PNX-S, manufactured by ICL-IP • Flame retardant G2-8: Tris(chloroethyl)phosphate, Mw = 285, trade name CLP, manufactured by Daihachi Kogyo Co., Ltd. • Flame retardant G2-9: Tris(chloropropyl)phosphate, Mw = 328, trade name TMCPP, manufactured by Daihachi Kogyo Co., Ltd. • Flame retardant G2-10: Tricresyl phosphate, Mw = 368, trade name TCP, manufactured by Daihachi Kogyo Co., Ltd.

[0065] In Tables 2-1 and 2-2 below, the catalyst F2-1, the flame retardants G2-1 to G2-10, Examples 2-1 to 2-17 and Comparative Examples 2-1 to 2-19 are referred to as F1, G1 to G10, Examples 1 to 17 and Comparative Examples 1 to 19 for convenience. [Table 3] [Table 3] Continued Table 2-1 (continued) (The values ​​of the components are given in parts by mass) Example 11 12 13 14 15 16 17 Polyol component A1 100 100 100 100 100 100 80 A2 20 Water repellent C1 35 12 12 12 12 12 12 C2 C3 C4 C5 C6 foaming agent D 3, 6 3,6 3, 6 3, 6 3, 6 3, 6 3, 6 foam stabilizer E 1 1 1 1 1 1 1 catalyst F1 0,3 0,3 0,3 0,3 0,3 0,3 0, 3 F2 0,3 0,3 0,3 0,3 0,3 0,3 0,3 Flame retardants G1 10 10 10 10 10 10 10 G2 G3 G4 G5 G6 G7 G8 G9 G10 Isocyanate 52,4 41, 8 45,9 62,6 54,7 45,6 51,0 Isocyanate index 120 100 110 150 120 120 120 Foaming properties A A A A A A A density kg / m 3 40 30 30 35 22 39 31 25 mmAq water exclusion property A A A A A A A 50 mmAq water exclusion property A A A A A A A 100 mmAq water exclusion property AA A AA AA AA AA A 100 mmAq water penetration time 24< 9 24< 24< 24< 24< 13 FMVSS302 flame retardancy A A A A A A A Fogging properties AA AA AA AA AA AA AA

[0061] [Table 4] [Table 4] Continued Table 2-2 (continued) (The values ​​of the components are given in parts by mass) Comparison example 11 12 13 14 15 16 17 18 19 Polyol component A1 100 100 100 100 100 75 100 100 A2 100 25 Water repellent C1 12 12 12 12 12 12 12 C2 C3 C4 C5 C6 25 foaming agent D 3,6 3,6 3,6 3,6 3,6 3,6 3,6 3,6 3,6 foam stabilizer E 1 1 1 1 1 1 1 1 1 catalyst F1 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0, 3 F2 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3 0,3 Flame retardants G1 10 10 10 10 10 G2 G3 G4 G5 G6 G7 10 G8 5 G9 5 G10 5 Isocyanate 50,1 50,1 50,1 48, 9 54,4 51,2 39,7 48, 9 Isocyanate index 120 120 120 120 120 120 95 120 Foaming properties widely inhibited reaction A A A A A A A A density kg / m 3 - 28 29 28 28 30 31 29 35 25 mmAq water exclusion property - A A A B B A B A 50 mmAq water exclusion property - A A A B B B B B 100 mmAq water exclusion property - AA AA AA B B B B B 100 mmAq water penetration time 24< 24< 24< 1 <1 5 <1 4 FMVSS302 flame retardancy - A A B A A A A A Fogging properties - B B B AA AA AA AA B

[0066] The density (kg / m 3 (JIS K 7222), the water exclusion properties, flame retardancy, and fogging properties of each flame-retardant waterproofing material of the examples and comparative examples were measured. The water exclusion properties and flame retardancy were measured in a similar manner to Examples 1-1 to 1-20 and Comparative Examples 1-1 to 1-11 described above.

[0067] The fogging property was measured according to DIN75201 and determined as (AA) best when the glass haze value was 90 or more after three hours, (A) pass when the glass haze value was more than 80 and less than 90, and (B) fail when the glass haze value was 80 or less.

[0068] The measurement results are shown at the end of Table 2-1 and Table 2-2.

[0069] As can be seen from the measurement results in Table 2-1, the flame-retardant waterproofing materials of the examples all passed the water exclusion property test under a water pressure of 100 mmAq, passed the FMVSS302 flammability test for flame retardancy, and passed the fogging property test (including the best rating). In particular, Examples 2-1 to 2-3 and 2-6 to 2-17, in which the flame retardant was contained in an amount of 3 to 12 parts by mass per 100 parts by mass of the polyol component, exhibited the best fogging properties in addition to good water exclusion properties and outstanding flame retardancy.Furthermore, Examples 2-1 to 2-9, 2-11 and 2-13 to 2-16, which had an isocyanate index of 110 to 150 and contained a hydroxyl-terminated prepolymer obtained by the reaction of a polyether polyol and an isocyanate as the only polyol component, and wherein the amount of the water-repellent agent added was 5 to 35 parts by mass per 100 parts by mass of the polyol component, had water exclusion properties of the best evaluation under a water pressure of 100 minaq.

[0070] On the other hand, Comparative Example 2-1 shown in Table 2-2 is an example in which no flame retardant was used, and Comparative Example 2-2 is an example in which the amount of flame retardant G2-1 (tris(1,3-dichloro-2-propyl)phosphate, trade name WR-30-LV) was 2 parts by mass. Comparative Example 2-1 and Comparative Example 2-2 both failed the flammability test according to FMVSS302 and exhibited poor flame-retardant properties.

[0071] Comparative Example 2-3 is an example in which the amount of flame retardant G2-1 (tris(1,3-dichloro-2-propyl)phosphate, trade name WR-30-LV) was 30 parts by mass. Comparative Example 2-3 failed the water exclusion property test under a water pressure of 100 mmAq and failed the fogging property test.

[0072] Comparative Example 2-4 is an example in which 5 parts by mass of a non-halogenated, non-condensed flame retardant G2-3 (isopropylated triaryl phosphate, trade name REOFOS 65) was used as the flame retardant. Comparative Example 2-4 failed the FMVSS302 flammability test and exhibited poor flame-retardant properties.

[0073] Comparative Example 2-5 is an example in which 15 mass parts of a non-halogenated, non-condensed flame retardant G2-3 (isopropylated triaryl phosphate, trade name REOFOS 65) was used as a flame retardant, and Comparative Example 2-5 failed the water exclusion property test under a water pressure of 100 mmAq.

[0074] Comparative Example 2-6 is an example in which 5 mass parts of flame retardant G2-4 (halogen-containing condensed phosphate ester, trade name CR504L) was used as a flame retardant, and Comparative Example 2-6 failed the water exclusion property test under a water pressure of 100 mmAq.

[0075] Comparative Example 2-7 is an example in which 15 parts by mass of the flame retardant G2-4 (halogen-containing condensed phosphate ester, trade name CR504L) was used as a flame retardant, and Comparative Example 2-7 failed both the water exclusion property tests under a water pressure of 50 mmAq and a water pressure of 100 mmAq.

[0076] Comparative Example 2-8 is an example in which 15 parts by mass of flame retardant G2-5 (halogen-containing condensed phosphate ester, trade name CR507L) was used as the flame retardant. Comparative Example 2-8 failed both the water exclusion property test under a water pressure of 50 mmAq and a water pressure of 100 mmAq, and (B) failed the fogging property test.

[0077] Comparative Example 2-9 is an example in which 5 mass parts of a non-halogenated, non-condensed flame retardant G2-2 (isopropylated triaryl phosphate, trade name REOFOS 50) and 2 mass parts of the flame retardant G2-6 (aliphatic condensed phosphate ester, trade name DAIGUARD-880) were used in combination as a flame retardant, and Comparative Example 2-9 failed both the water exclusion property test under a water pressure of 50 mmAq and a water pressure of 100 mmAq.

[0078] Comparative Example 2-10 is an example in which 5 mass parts of the flame retardant G2-6 (aliphatic condensed phosphate ester, trade name DAIGUARD-880) was used as a flame retardant, and Comparative Example 2-10 failed both the water exclusion property test under a water pressure of 50 mmAq and a water pressure of 100 mmAq.

[0079] Comparative Example 2-11 is an example in which 10 parts by mass of flame retardant G2-7 (condensed phosphate ester, trade name Fyrol PNX-S) was used as the flame retardant. In Comparative Example 2-11, the foaming reaction was inhibited, and no foam could be obtained.

[0080] Comparative Example 2-12 is an example in which 5 mass parts of the flame retardant G2-8 (tris(chloroethyl)phosphate, trade name CLP) was used as a flame retardant, and Comparative Example 2-12 (B) failed the fogging property test.

[0081] Comparative Example 2-13 is an example in which 5 mass parts of the flame retardant G2-9 (tris(chloropropyl)phosphate, trade name TMCPP) was used as a flame retardant, and Comparative Example 2-13 (B) failed the fogging property test.

[0082] Comparative Example 2-14 is an example in which 5 parts by mass of the flame retardant G2-10 (tricresyl phosphate, trade name TCP) was used as the flame retardant. Comparative Example 2-14 failed the FMVSS302 flammability test and (B) also failed the fogging property test.

[0083] Comparative Example 2-15 is an example that did not contain a water repellent and failed all water exclusion property tests under a water pressure of 25 mmAq, under a water pressure of 50 mmAq, and under a water pressure of 100 mmAq.

[0084] Comparative Example 2-16 is an example in which the polyol component did not contain a prepolymer and the polyol component was 100% polyether polyol, and Comparative Example 2-16 did not pass any of the water exclusion property tests under a water pressure of 25 mmAq, under a water pressure of 50 mmAq, and under a water pressure of 100 mmAq.

[0085] Comparative Example 2-17 is an example in which the prepolymer was contained in an amount of 75 parts by mass per 100 parts by mass of the polyol component, and Comparative Example 2-17 failed both the water exclusion property test under a water pressure of 50 mmAq and a water pressure of 100 mmAq.

[0086] Comparative Example 2-18 is an example wherein the isocyanate index was 95, and Comparative Example 2-18 failed any of the water exclusion property tests under a water pressure of 25 mmAq, under a water pressure of 50 mmAq, and under a water pressure of 100 mmAq.

[0087] Comparative Example 2-19 is an example in which a liquid petroleum resin was used as a water repellent, and Comparative Example 2-19 did not pass any of the water exclusion property tests under a water pressure of 50 mmAq and under a water pressure of 100 mmAq.

[0088] As explained above, the flame-retardant sealing materials of Examples had excellent water exclusion properties, excellent flame retardancy (low flammability), and good fogging properties, and are suitable as a flame-retardant sealing material used as a part in an automobile or the like in which low flammability is required. List of reference symbols 50 Flame-retardant sealing material 71 acrylic resin board

Claims

[1] A flame-retardant sealing material comprising a polyurethane foam formed from a polyurethane starting material containing a polyol component, an isocyanate, a foaming agent, a catalyst, a water repellent and a flame retardant, wherein the polyol component contains, per 100 parts by mass, 80 to 100 parts by mass of a hydroxyl-terminated prepolymer obtained by the reaction of a polyether polyol and an isocyanate, wherein the water-repellent agent contains at least one selected from the group consisting of a polybutadiene polyol, a hydrogenated polyol of a polybutadiene, a polyisoprene polyol and a hydrogenated polyol of a polyisoprene, wherein the flame retardant is a non-halogenated, non-condensed phosphate ester which is liquid at conventional temperature, the isocyanate index is 100 to 150, the flame-retardant sealing material comprises the flame retardant in an amount of 6 to 13 parts by mass per 100 parts by mass of the polyol component, and the flame retardant is isopropylated triaryl phosphate. [2] A flame-retardant sealing material according to claim 1, which comprises the flame retardant in an amount of 6 to 10 parts by mass per 100 parts by mass of the polyol component. [3] A flame-retardant sealing material comprising a polyurethane foam formed from a polyurethane starting material containing a polyol component, an isocyanate, a foaming agent, a catalyst, a water repellent and a flame retardant, wherein the polyol component contains, per 100 parts by mass, 80 to 100 parts by mass of a hydroxyl-terminated prepolymer obtained by the reaction of a polyether polyol and an isocyanate, wherein the water-repellent agent contains at least one selected from the group consisting of a polybutadiene polyol, a hydrogenated polyol of a polybutadiene, a polyisoprene polyol and a hydrogenated polyol of a polyisoprene, wherein the flame retardant is a halogen-containing, non-condensed phosphate ester which is liquid at conventional temperature, the isocyanate index is 100 to 150, the flame retardant has a weight-average molecular weight of 400 or more, the flame-retardant sealing material comprises the flame retardant in an amount of 3 to 25 parts by mass per 100 parts by mass of the polyol component, and the flame retardant is tris(1,3-dichloro-2-propyl)phosphate.

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