JP2013249394A - Water sealing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low combustible non-halogen type water sealing material excellent in water cut-off properties.SOLUTION: A water sealing material with a density of 15-40 kg/mis formed from a polyurethane foam raw material including a polyol component, isocyanate, a foaming agent, a catalyst and a water repellent agent. In 100 pts.mass of the polyol component, 80-100 pts.mass of a hydroxy group-terminated prepolymer obtained by a reaction of polyetherpolyol and isocyanate is included. The water repellent agent is at least one selected from a group comprising polybutadienepolyol, polybutadiene hydrogenated polyol, polyisoprenepolyol and polyisoprene hydrogenated polyol. A non-halogen, non-condensed type phosphoric ester liquid at normal temperature is included by 6-13 pts.mass based on 100 pts.mass polyol component as a flame retardant. An isocyanate index is made as 100-150.

Description

  The present invention relates to a non-halogen type water sealing material having excellent water stopping performance and low combustibility.

Conventionally, water-resistant polyurethane foam is used as a water seal material. As a conventional water stopping polyurethane foam, the retention time in the 100mmAq pressure has a high water cut over 9 hours, and density and low-density polyurethane foam which is 15kg ^{/ m 3} ~40kg ^/ m 3 has been proposed ( Patent Document 1).

The high water-stopping and low-density polyurethane foam comprises 80 to 100 parts by mass of a hydroxyl-terminated prepolymer obtained by reaction of polyether polyol and isocyanate in 100 parts by mass of the total amount of polyol, and the water repellent is polybutadiene polyol. And at least one selected from the group of hydrogenated polyols of polybutadiene, polyisoprene polyols, and hydrogenated polyols of polyisoprene, each having an isocyanate index of 100 to 150.
However, conventional high water-stopping and low-density polyurethane foams have not been studied for flame retardancy, and water sealing materials for parts where low flammability is required in applications where low flammability is required, such as automobiles and OA equipment As such, it is necessary to improve flame retardancy.

In recent years, non-halogen-type polyurethane foams that do not use halogen compounds have been proposed as low-combustibility polyurethane foams used for shock-absorbing materials, sound-absorbing materials, and the like from the viewpoint of environmental protection. Non-halogen type low-flammability polyurethane foams that contain phthalate ester polyol in the polyol and melamine powder with an average particle size of 0.5 μm or less as the flame retardant (Patent Document 2), phthalate ester-type polyol, and phosphoric acid One containing an ester flame retardant, a melamine powder having an average particle size of 0.1 to 0.5 μm and a hydrate of an inorganic compound (Patent Document 3), one containing melamine and a condensed phosphate ester flame retardant (Patent Document 4) )
However, conventional low-flammability polyurethane foams used for cushioning materials, sound-absorbing materials and the like are not used for the purpose of water-stopping, and thus water-stopping has not been studied.

  The production of polyurethane foam is carried out by mixing a foaming agent, a catalyst and a flame retardant with a liquid polyol, further mixing a liquid isocyanate, reacting the polyol with the isocyanate, and foaming. In some cases, a good cell state cannot be obtained and foaming failure occurs. Therefore, in order to obtain a good foamed state, all the raw materials used for the polyurethane foam are preferably liquid.

  Therefore, as a raw material for conventional water-stopping polyurethane foam, a flame retardant that is solid at room temperature (for example, melamine) or a solid flame retardant (for example, melamine) and a liquid flame retardant (for example, condensation) In order to obtain a foam with a good foamed state, the amount of solid flame retardant used is limited, excellent water-stopping performance and good Both low flammability could not be obtained.

In addition, when a condensed phosphate ester flame retardant liquid at room temperature was used, there was no problem with the water-stopping property at about 50 mmAq water pressure, but there was a phenomenon that the water-stopping property was significantly reduced at 100 mmAq water pressure.
Thus, it has 100 mmAq water-stop and FMVSS302 (Federal Automotive Safety Standard (Federal)
Motor Vehicle Safety
Standard No 302) A non-halogen low-flammability water sealing material that passed the combustion test could not be obtained.

JP 2010-144066 A JP 2007-002036 A JP 2007-091866 A JP 2011-184601A

  This invention is made | formed in view of the said point, Comprising: It aims at provision of the non-halogen-type water seal material which has the outstanding water stop performance and has the outstanding flame retardance (low combustibility).

  The present invention is a water sealing material comprising a polyurethane foam formed from a polyurethane raw material containing a polyol component, an isocyanate, a foaming agent, a catalyst, a water repellent, and a flame retardant, and the polyol component is contained in 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, and the water repellent is selected from the group consisting of polybutadiene polyol, polybutadiene hydrogenated polyol, polyisoprene polyol, and polyisoprene hydrogenated polyol. It consists of at least one selected, the flame retardant is a non-halogen non-condensed phosphate ester that is liquid at room temperature, contains 6 to 13 parts by mass of the flame retardant with respect to 100 parts by mass of the polyol component, The index is 100-150 It is characterized in.

  In the water sealing material of the present invention, the polyol component is composed of a hydroxyl group-terminated prepolymer alone or a combination of polyols other than the hydroxyl group-terminated prepolymer obtained by the reaction of polyether polyol and isocyanate. Since 100 to 100 parts by mass of a 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, the viscosity of the polyurethane foam raw material is increased, and the cell becomes finer during foam formation. By increasing the film (mirror) that covers the cell skeleton of the polyurethane foam, the air permeability is reduced, it becomes difficult for water to enter the cell, and the water stoppage is improved. When a polyether polyol is used as a hydroxyl group-terminated prepolymer constituting the polyol component and a polyol other than the hydroxyl group-terminated prepolymer, the hydrolysis resistance is improved because the polyol component is composed only of the polyether polyol.

  The water sealing material of the present invention uses at least one selected from the group consisting of polybutadiene polyol, hydrogenated polyol of polybutadiene, polyisoprene polyol, and hydrogenated polyol of polyisoprene as the water repellent. Is taken into the resin skeleton of the foam, and the water repellent bleed does not occur, the foam is less likely to deteriorate over time and the water repellency is reduced, and good water stopping properties can be exhibited over a long period of time. Furthermore, by setting the isocyanate index to 100 to 150, the polyol component and the water repellent are completely resinated, and since the isocyanate is present in excess, secondary crosslinking reaction of the isocyanate (allophanate bond, burette bond, etc.) Occurs, the water repellency of the foam is further increased, and the water stoppage is further improved.

  Furthermore, the water sealing material of the present invention uses a non-halogen non-condensed phosphate ester that is liquid at room temperature as a flame retardant, and contains 6 to 13 parts by mass of the flame retardant with respect to 100 parts by mass of the polyol component. It has a high water-stopping property at 100 mmAq water pressure while suppressing a decrease in aqueous property, and has excellent flame retardancy that can pass FMVSS302 of the combustion test.

It is a top view which shows the sample for water-stopping measurement. It is a figure which shows the water stop measuring method.

  The water sealing material in the present invention comprises a polyurethane foam formed from a polyurethane foam raw material containing a polyol component, an isocyanate, a foaming agent, a catalyst, a water repellent, and a flame retardant.

  The polyol component contains 80 to 100 parts by mass of a hydroxyl group-terminated prepolymer obtained by a reaction between a polyether polyol and an isocyanate in 100 parts by mass of the polyol component. Since 80 to 100 parts by mass of the hydroxyl-terminated prepolymer is contained, the viscosity of the polyurethane foam raw material is increased, the cells are made finer at the time of foam formation, and the number of mirrors covering the cell skeleton of the polyurethane foam is increased, thereby reducing air permeability. Water stoppage is improved. When the amount of the hydroxyl group-terminated prepolymer is less than the above range, it becomes difficult to make the polyurethane foam cells finer and reduce the air permeability, and the water stoppage is lowered.

  The polyether polyol used for the production of the hydroxyl group-terminated prepolymer in the present invention is bifunctional or higher, and trifunctional or higher is preferred to obtain a polyurethane foam with finer cells. The bifunctional or higher functional polyether polyol is not particularly limited. For example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hydroquinone, water, resorcin, bisphenol A, hydrogenated bisphenol A, glycerin, trimethylolpropane, Starting from pentaerythritol, monoethanolamine, diethanolamine, triethanolamine, tripropanolamine, ethylenediamine, 1,6-hexanediamine, tolylenediamine, diphenylmethanediamine, triethylenetetraamine, sorbitol, mannitol, dulcitol, etc. Use polyether polyols obtained by adding alkylene oxides such as oxide and propylene oxide It is possible.

  In addition, the isocyanate used for the production of the hydroxyl-terminated prepolymer in the present invention is bifunctional or higher. Bifunctional or higher isocyanates are not particularly limited, and may be aromatic, alicyclic or aliphatic, and may be used alone or in combination.

  For example, as the bifunctional isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'- Fragrances such as diphenylmethane diate, 2,2'-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisonate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate Alicyclic, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane diisocyanate, butane-1,4-diisocyanate, hexane Diisocyanate, isopropylene diisocyanate, methylene diisocyanate, can be mentioned aliphatic, such as lysine isocyanate.

  Trifunctional or higher isocyanates include tris (4-phenylisocyanate) thiophosphate, triphenylmethane triisocyanate, tolylene diisocyanate trimer, polymethylene polyphenyl isocyanate, diphenyl ether-2,4,4′-triisocyanate, Other examples include polyfunctional aromatic isocyanates, polyfunctional aliphatic isocyanates, and block type isocyanates.

  The hydroxyl-terminated prepolymer can be obtained from the polyether polyol and isocyanate by a known prepolymer production method. Specifically, a predetermined amount of the polyether polyol is charged into a tank heated to a predetermined temperature (for example, 80 ° C.), and a predetermined amount of the isocyanate or the catalyst is charged and reacted while stirring in a state filled with nitrogen. Thus, a hydroxyl group-terminated prepolymer can be obtained.

  The polyol used as the hydroxyl group-terminated prepolymer is a polyether polyol having a molecular weight of 300 to 10,000, more preferably a molecular weight of 1000 to 8000, and still more preferably a molecular weight of 2000 to 5000. The isocyanate is not particularly limited as long as the viscosity of the hydroxyl group-terminated prepolymer does not make the production difficult, but tolylene diisocyanate is effective. The viscosity of the hydroxyl group-terminated prepolymer is 2000 to 30000 mPa · s at 30 ° C., more preferably 4000 to 28000 mPa · s, and still more preferably 8000 to 25000 mPa · s.

  When the amount of the hydroxyl-terminated prepolymer contained in 100 parts by mass of the polyol component is less than 100 parts by mass, the polyol used in combination as the polyol component is not particularly limited, and polyether polyol or polyether polyol and styrene Polymer polyol, polyether ester polyol or polyester polyol obtained by graft polymerization of acrylonitrile or acrylonitrile may be used. In particular, polyether polyol is preferable, and it is more preferable to use together the polyether polyol used as a raw material for producing the hydroxyl-terminated prepolymer. Moreover, when using a polyester polyol as a polyol used together as the polyol component, in order to obtain a water sealing material excellent in hydrolysis resistance, 3-methyl-1,5-pentanediol or 2-methyl-1 , 8-octanediol and the like having a bifunctional or higher functionality obtained by condensing a dicarboxylic acid such as adipic acid (aliphatic), dimer acid (alicyclic), and phthalic acid (aromatic). Polyester polyols obtained by ring-opening polymerization of various lactones such as polyester polyol, polycarbonate diol, and caprolactone are preferred.

  As the isocyanate to be reacted with the polyol component, known aromatic, alicyclic and aliphatic isocyanates for polyurethane foam may be used alone or in combination. For example, 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′-diphenylmethane diisocyanate, xylylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisonate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, and the like Examples of cyclic isocyanates include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and methylcyclohexane diisocyanate. Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, can be mentioned methyl cyclohexane diisocyanate.

  As the foaming agent, water is suitable. About 1.5-6 mass parts is suitable with respect to 100 mass parts of polyol components, and 3-5 mass parts is especially suitable. If the amount is less than 1.5 parts by mass, the deformability following the object to be sealed is lowered and the sealing property is deteriorated. If the amount is larger than 6 parts by mass, the amount of heat generation is large and molding is difficult.

  As the catalyst, those known for polyurethane foam can be used. For example, amine catalysts such as triethylamine, triethylenediamine, diethanolamine, dimethylaminomorpholine, N-ethylmorpholine, tetramethylguanidine, stannous octoate, Examples thereof include tin catalysts such as dibutyltin dilaurate, and metal catalysts (also referred to as organometallic catalysts) such as phenylmercury propionate or lead octenoate. The general amount of the catalyst is about 0.2 to 5 parts by mass with respect to 100 parts by mass of the polyol.

  The water repellent is at least one selected from the group consisting of polybutadiene polyol, hydrogenated polyol of polybutadiene, polyisoprene polyol, and hydrogenated polyol of polyisoprene. The polyol used as the water repellent has a molecular weight of 500 to 6000, more preferably a molecular weight of 1000 to 5000, still more preferably a molecular weight of 1000 to 3500, and a hydroxyl value of 15 to 120 mgKOH / g, more preferably a hydroxyl value. It is 25-110 mgKOH / g, More preferably, it is 35-70 mgKOH / g. The number of functional groups is 1.6 or more, more preferably 2 or more. By using the polyol as a water repellent, the water repellent is incorporated into the resin skeleton, and there is little risk of deterioration of the foam over time or water repellency due to bleed of the water repellent. It becomes possible to exhibit aqueous properties. The polyol of the water repellent is separate from the polyol component, and is 3 to 30 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 10 to 15 parts by mass with respect to 100 parts by mass of the polyol component. Part addition amount is preferred. If the amount is less than 3 parts by mass, the effect of improving the water-stopping performance is reduced. On the other hand, even if the amount of addition exceeds 30 parts by mass, the effect of improving the water-stopping property is not so much seen.

In general, polyurethane foam used as a water-stopping material is compressed between different materials such as metal and thermoplastic resin or thermosetting resin, so the water-stopping material itself is against both the metal and the above resin. Must adhere to each other.
In actual use, if the polyurethane foam contains a compound capable of causing an organic volatile substance (VOC), the metal surface or the resin surface may be adversely affected by chemical attack or bleed. In addition, when used after being compressed with a transparent material such as glass, a problem of fogging such as fogging occurs.

  In the water sealing material of the present invention, by selecting a water repellent, the amount of eluate is very small at 5% or less in the Soxhlet extraction method with acetone (extraction time 8 hours), and the above-mentioned problems do not occur. At present, the amount of eluate of a water seal material that is generally used is about 10 to 15%, and that the amount of eluate of the present invention is 5% or less is substantially equal to a general-purpose polyurethane foam that does not contain a water repellent. The performance is equivalent.

  As the flame retardant, a non-halogen non-condensed phosphate ester is used. Non-halogen non-condensable phosphate esters include, for example, triaryl phosphates (aliphatic phosphate esters) such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl Examples thereof include triaryl phosphates (aromatic phosphate esters) such as phosphate and cresyl diphenyl phosphate. Among triaryl phosphates (aromatic phosphate esters), triaryl isopropylate is preferable. As for the addition amount of the said flame retardant, 6-13 mass parts is preferable with respect to 100 mass parts of said polyol components. If it is less than 6 parts by mass, it does not pass FMVSS302 of the flammability test. On the other hand, if it exceeds 13 parts by mass, it will leak in less than 9 hours in a 100 mmAq water pressure waterstop test, and it will have good waterstop at 100 mmAq water pressure. Cannot be obtained.

  Isocyanate index is 100-150, More preferably, it is 105-140, More preferably, it is 110-130. By setting the isocyanate index to 100 to 150, the polyol component and the water repellent are completely resinated, and since the isocyanate is excessive, secondary crosslinking reaction of the isocyanate (allophanate bond, burette bond, etc.) occurs. The water repellency of the foam is further increased, and the water stoppage is further improved. When the isocyanate index is less than 100, the water stopping performance is lowered. The upper limit of the isocyanate index need not be particularly limited, but if it exceeds 150, the internal heat generation temperature in the polyurethane foam becomes high when foam is foamed (particularly when foamed into a soft slab foam), and scorch is generated. Risk of ignition. The range of a preferable isocyanate index is 100 to 150, more preferably 105 to 140, and still more preferably 110 to 130. The isocyanate index is an index used in the field of polyurethane, and is a poly- mer with respect to active hydrogen groups in raw materials (for example, active hydrogen groups contained in hydroxyl groups of polyols and active hydrogen groups such as water as a blowing agent). It is a numerical value [equivalent of NCO group / equivalent of active hydrogen group × 100] representing the equivalent ratio of isocyanate groups of isocyanate as a percentage.

  In addition, additives such as foam stabilizers and pigments can be appropriately blended. Any foam stabilizer may be used as long as it is used for polyurethane foams, and examples thereof include silicone foam stabilizers, fluorine-containing compound foam stabilizers, and known surfactants. As the pigment, those according to the required color are used.

Polyurethane foam is a known foam that stirs and mixes a polyurethane foam material composed of the polyol component, isocyanate, foaming agent, catalyst, water repellent, flame retardant, and appropriate additives to react the polyol component and isocyanate to foam. Manufactured by the method. Polyurethane foam of the present invention is preferably a density 15~40kg / ^{m 3,} particularly more preferably 20 to 35 kg / ^{m 3.} By setting the density of the polyurethane foam to 15 to 40 kg / m ³ , it is possible to develop a low density, excellent water stopping performance and low flammability, so that the material cost can be reduced, and as a water sealing material Weight reduction can be achieved.

  The water sealing material of the present invention is used after being made into a thickness and shape (for example, string shape) according to the application by punching or the like. The water sealing material of the present invention has a holding time of 100 mmAq water pressure of 9 hours or more, more preferably 24 hours or more, and exhibits a very good water-stopping property. The holding time of the 100 mmAq water pressure is as follows. A sample 50 for water-stopping measurement prepared by punching a 10 mm-thick water sealing material into a U-shape with the dimensions shown in FIG. 1, and two acrylic resin plates as shown in FIG. It is a time during which water is injected into the U-shaped test sample 50 so as to be 100 mAq water pressure and held at 100 mmAq water pressure while being sandwiched between 71 and 71 in a compressed state of 50%.

  Moreover, the water sealing material of the present invention is of low flammability that passes the FMVSS 302 combustion test. The FMVSS 302 combustion test measures the average burning speed and the maximum burning speed with respect to 10 test pieces, and passes when it falls under any one of the following (1) to (3). (1) When the test piece is not ignited, or when the test piece is ignited and fires spontaneously without reaching the combustion start mark (combustion speed 0), (2) Combusting beyond the start mark of combustion, burning When natural fire extinguishes within 50.8mm from the start mark and the time until natural fire extinguishment is within 60 seconds (natural fire extinguishing (SE)), (3) burns beyond the start mark and burns at 100mm / Min or less.

  Using a polyurethane foam raw material having the composition shown in Tables 1 and 2, water seal materials made of polyurethane foams of Examples and Comparative Examples were prepared. Each component of Table 1 and Table 2 is as follows. In addition, the foamability in Table 1 and Table 2 showed (circle) when the favorable foam was obtained, and x when the foam was inferior or not obtained.

Polyol component A1: synthesized by reacting a mixture of polyether polyol (polyol component A2 described later) / isocyanate (isocyanate described later) = 2 mol / 1 mol in the presence of a metal catalyst at 80 ° C. for about 2 hours. Hydroxyl-terminated prepolymer, hydroxyl value 33 mgKOH / g, viscosity 17000 mPa · s (30 ° C.).
Polyol component A2: polyether polyol, molecular weight 3000, functional group number 3, hydroxyl value 56 mgKOH / g, product number: GP-3000, manufactured by Sanyo Chemical Industries, Ltd. Polyol component A3: polyester polyol, molecular weight 2000, functional group number 3, hydroxyl group 84 mg KOH / g, product number; F-2010 (condensation polymerization of 3-methyl-1,5-pentanediol and adipic acid on trimethylolpropane), manufactured by Kuraray Co., Ltd.

Water repellent C1: polybutadiene polyol, molecular weight 2100, functional group number 2, product number: KRASOL LBH-P2000, manufactured by Cray Valley Co., Ltd. Water repellent C2: hydrogenated polybutadiene polyol, molecular weight 3100, functional group number 2, product number: HLBH-P3000 Water repellent C3: polybutadiene polyol, molecular weight 1200, functional group number 2.3, product number; R-15HT, manufactured by Idemitsu Kosan Co., Ltd. Water repellent C4: isoprene polyol, molecular weight 2500, functional group number 2. 1, product number; Rory ip, manufactured by Idemitsu Kosan Co., Ltd. ・ Water repellent C5: hydrogenated isoprene polyol, molecular weight 2500, functional group number 2.3, product number: Epaul, manufactured by Idemitsu Kosan Co., Ltd. ・ Water repellent C6: petroleum-based liquid Resin, product number: SAS-LH, manufactured by Nippon Oil Corporation

-Foaming agent: Water-Foam stabilizer: Silicone, Part No .: SZ-1919, manufactured by Toray Dow Corning Co., Ltd.-Catalyst F1: Reactive tertiary amine, Part No .: Kao Riser No. 51, manufactured by Kao Corporation ・ Catalyst F2: stannous octylate, product number: MRH-110, manufactured by Johoku Chemical Industry Co., Ltd.

Flame retardant G1: Triaryl isopropylated product, product number: REOFOS 35, viscosity 44 mm ² / s, 25 ° C., manufactured by Ajinomoto Fine Techno Co., Ltd. Flame retardant G2: Triaryl isopropylated product, product number: REOFOS 50, viscosity 50 mm ² / s, 25 ° C., manufactured by Ajinomoto Fine Techno Co., Ltd. ・ Flame retardant G3: Triaryl phosphate, product number: REOFOS 65, viscosity 61 mm ² / s, 25 ° C., manufactured by Ajinomoto Fine Techno Co., Ltd. • Flame retardant G4 : Triaryl isopropylated product, product number: REOFOS 95, viscosity 93 mm ² / s, 25 ° C., manufactured by Ajinomoto Fine Techno Co., Ltd. • Flame retardant G5: Triaryl isopropylated product, product number: REOFOS 110, viscosity 120 mm ² / s , 25 ℃, Ajinomoto Fine Techno -Flame retardant G6: Aliphatic condensed phosphate ester, product number: DAIGUARD-880 Daihachi Kogyo Co., Ltd.-Flame retardant G7: condensed phosphate ester, product number: fyrol PNX-S ICL-IP, Inc.-Isocyanate : 2,4-TDI / 2,6-TD1 = 80/20, product number: T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.

The density (kg / m ³ , JIS K 7222), water-stopping property, and flame retardancy were measured for the water sealing materials of Examples and Comparative Examples. In the method shown in FIG. 1 and FIG. 2, the water stoppage was measured with respect to 25 mmAq water pressure, 50 mmAq water pressure, and 100 mmAq water pressure. In addition, with regard to the water stoppage at 25 mm water pressure, water was injected from above the water sealing material 50 so as to be 25 mmAq water pressure, and when water leakage did not occur for 24 hours or more, it passed (○), When it occurs, it is rejected (×), and about 50 mm water pressure waterproofing, water is passed from above the water sealing material 50 so as to be 50 mmAq water pressure, and when water leakage does not occur for more than 24 hours (○ ), When water leakage occurs in less than 24 hours (×), for water stoppage of 100 mm water pressure, water is injected from above the water sealing material 50 so that the water pressure becomes 100 mmAq water pressure. When it did not occur, it passed (◯), when water leakage did not occur for 24 hours or more, it was judged as best (◎), and when water leakage occurred in less than 9 hours, it was rejected (x). As for flame retardancy, according to the FMVSS 302 combustion test, the average burning rate and the maximum burning rate are measured for 10 test pieces, and any one of the above criteria (1) to (3) is measured. When it corresponded, it was set as a pass (○), and when it did not correspond to any, it was set as a fail (x). The measurement results are shown at the bottom of Tables 1 and 2.

  As shown in the measurement results of Table 1, each of the water-seal materials of the non-halogen type examples passed the water stoppage of 100 mmAq water pressure and passed the FMVSS 302 combustion test for flame retardancy.

On the other hand, Comparative Example 1 shown in Table 2 is an example in which a flame retardant is not used. In Comparative Example 2, the amount of the flame retardant G3 (triaryl isopropylated product, product number: REOFOS 65) is within the scope of the present invention. This was an example of less than 5 parts by mass, and both the comparative example 1 and the comparative example 2 failed the FMVSS302 combustion test, and were inferior in flame retardancy.
Comparative Example 3 is an example in which the amount of the flame retardant G3 (triaryl isopropylated product, product number: REOFOS 65) was set to 15 parts by mass exceeding the range of the present invention, and the water stoppage of 100 mmAq water pressure was rejected. .
In Comparative Example 4, the amount of the flame retardant G2 (triaryl isopropylated phosphate, product number: REOFOS 50) is 5 parts by mass less than the range of the present invention, and the flame retardant G6 (aliphatic condensed phosphate ester, product number: DAIGUARD). -880) 2 parts by mass, both 50 mmAq water pressure and 100 mmAq water pressure were not acceptable.
Comparative Example 5 is an example in which only 5 parts by mass of flame retardant G6 (aliphatic condensed phosphate ester, product number: DAIGUARD-880) is used as a flame retardant, and both the water stoppages of 50 mmAq water pressure and 100 mmAq water pressure are rejected. It became.
Comparative Example 6 is an example in which only 10 parts by mass of a flame retardant G7 (condensed phosphate ester, product number: fyrol PNX-S) was used as a flame retardant, the foaming reaction was inhibited, and a foam was not obtained.

The comparative example 7 is an example which does not contain a water repellent agent, and the water stoppage was unacceptable in all of 25 mmAq water pressure, 50 mmAq water pressure, and 100 mmAq water pressure.
Comparative Example 8 is an example in which the polyol component does not contain a prepolymer, and the polyol component is composed of 100% polyether polyol, and the water stoppage was unacceptable at all of 25 mmAq water pressure, 50 mmAq water pressure, and 100 mmAq water pressure.
Comparative Example 9 is an example in which 75 parts by mass of the prepolymer is contained in 100 parts by mass of the polyol component, and both the water stoppages at 50 mmAq water pressure and 100 mmAq water pressure were unacceptable.
The comparative example 10 is an example whose isocyanate index is 95, and the water stop property became unacceptable in all of 25 mmAq water pressure, 50 mmAq water pressure, and 100 mmAq water pressure.
Comparative Example 11 is an example in which a petroleum liquid resin was used as the water repellent, and both the water stopping properties at 50 mmAq water pressure and 100 mmAq water pressure were unacceptable.

  Thus, the water seal material of the example is a non-halogen type having excellent water stop performance and excellent flame retardancy (low combustibility), and low combustibility in automobiles and OA equipment. It is suitable as a water sealing material for a part where the above is required.

50 Water sealing material 71 Acrylic resin plate

Claims (1)

A water sealing material composed of a polyurethane foam formed from a polyurethane raw material containing a polyol component, an isocyanate, a foaming agent, a catalyst, a water repellent, and a flame retardant,
The polyol component contains 80 to 100 parts by mass of a hydroxyl group-terminated prepolymer obtained by reaction of polyether polyol and isocyanate in 100 parts by mass,
The water repellent comprises at least one selected from the group of polybutadiene polyol, hydrogenated polyol of polybutadiene, polyisoprene polyol, and hydrogenated polyol of polyisoprene,
The flame retardant is a non-halogen non-condensed phosphate ester that is liquid at room temperature, and contains 6 to 13 parts by mass of the flame retardant with respect to 100 parts by mass of the polyol component.
Isocyanate index is 100-150, The water sealing material characterized by the above-mentioned.

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