KR102158327B1 - Composition for flame retardant polyurethane foam and flame retardant polyurethane foam comprising cured product thereof - Google Patents

Abstract

The present specification relates to a flame-retardant polyurethane foam comprising a flame-retardant polyurethane foam composition and a cured product thereof.

Description

Flame-retardant polyurethane foam comprising a flame-retardant polyurethane foam composition and a cured product thereof {COMPOSITION FOR FLAME RETARDANT POLYURETHANE FOAM AND FLAME RETARDANT POLYURETHANE FOAM COMPRISING CURED PRODUCT THEREOF}

The present invention relates to a flame-retardant polyurethane foam comprising a flame-retardant polyurethane foam composition and a cured product thereof.

Polyurethane foam is relatively inexpensive, easy to mold, and has high elasticity, so it is widely used throughout household goods including automobile parts. However, polyurethane foam is flammable, and once ignited, there is a problem of uncontrollable combustion.

In order to solve this problem, a method of imparting flame retardancy by laminating a sheet or panel having flame retardancy on one side of the polyurethane foam was mainly used.This is not fundamentally imparting flame retardancy to the polyurethane foam, so the flame retardant effect Is limited, the manufacturing process is complicated, and the manufacturing cost is increased. Alternatively, in order to impart flame retardancy to the polyurethane foam itself, a flame retardant composed of a halogen compound such as a bromine compound or a chlorine compound is added, which may cause human and environmental problems due to toxic gases during combustion.

Accordingly, there is a need for research on a polyurethane foam that maintains high elasticity of the polyurethane foam and improves non-halogen flame retardant properties.

KR 10-2014-0109474 A

The present specification is to provide a flame-retardant polyurethane foam comprising a flame-retardant polyurethane foam composition and a cured product thereof.

A first polyol having a glass transition temperature of -50°C or less and a viscosity at 25°C of 2,000 mPa·s or less; A second polyol containing at least three functional groups reacting with an isocyanate group, a weight average molecular weight of 5,000 g/mol or more and 30,000 g/mol or less, and a viscosity at 25° C. of 20,000 mPa·s or more and 200,000 mPa·s or less; A third polyol having a heat release capacity of 500 J/g·K or less; Isocyanate-based curing agents; Antifoam; Flame retardant; And it provides a flame-retardant polyurethane foam composition comprising expanded graphite.

In addition, an exemplary embodiment of the present invention provides a flame retardant polyurethane foam comprising a cured product of the flame retardant polyurethane foam composition.

The flame-retardant polyurethane foam according to an exemplary embodiment of the present invention can minimize the risk of ignition even if it is applied to a high-temperature device because it has a flame-retardant property of V-0 as a result of a UL-94 vertical flame-retardant test.

Since the flame-retardant polyurethane foam according to an exemplary embodiment of the present invention has excellent compression and resilience, it is possible to improve durability of the device by effectively absorbing the impact between parts when applied to the device.

The flame-retardant polyurethane foam according to an exemplary embodiment of the present invention has a low compression permanent reduction rate, and thus it is possible to minimize the occurrence of a step when applied to a device.

The flame-retardant polyurethane foam according to an exemplary embodiment of the present invention, when applied between cells of a vehicle battery, has dimensional stability against changes in the volume of the cell, excellent stress absorption against vibration and shock, excellent resilience, and high fire resistance. Can be implemented.

1 shows a schematic diagram for a UL-94 vertical flame retardant test.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

Hereinafter, the present specification will be described in more detail.

An exemplary embodiment of the present invention is a first polyol having a glass transition temperature of -50 °C or less and a viscosity at 25 °C of 2,000 mPa·s or less; A second polyol containing at least three functional groups reacting with an isocyanate group, a weight average molecular weight of 5,000 g/mol or more and 30,000 g/mol or less, and a viscosity at 25° C. of 20,000 mPa·s or more and 200,000 mPa·s or less; A third polyol having a heat release capacity of 500 J/g·K or less; Isocyanate-based curing agents; Antifoam; Flame retardant; And it provides a flame-retardant polyurethane foam composition comprising expanded graphite.

According to an exemplary embodiment of the present invention, the first polyol is a polyether-based polyol having a polyalkylene oxide unit having a glass transition temperature of -50° C. or less, and the viscosity at 25° C. is 2,000 mPa·s or less. I can. Furthermore, the first polyol may include a functional group that reacts with at least two isocyanate groups.

The first polyol may have a glass transition temperature of -50° C. or less, so that high repellency and compression recovery characteristics of the flame-retardant polyurethane foam can be realized. Further, the first polyol has a viscosity of 2,000 mPa·s or less, and thus has an advantage of improving the dispersibility and workability of raw materials when preparing the flame-retardant polyurethane foam.

According to an exemplary embodiment of the present invention, the second polyol contains at least three functional groups reacting with an isocyanate group, a weight average molecular weight of 5,000 g/mol or more and 30,000 g/mol or less, and a viscosity of 20,000 mPa at 25° C. It may be a polyether-based polyol having a s or more and 200,000 mPa s or less.

According to an exemplary embodiment of the present invention, the functional group reacting with the isocyanate group may mean a functional group having a urethane bond with an isocyanate group. Specifically, the functional group reacting with the isocyanate group may be a hydroxy group, an amine group, a thiol group, or a carboxy group.

Further, according to an exemplary embodiment of the present invention, the second polyol may have a branched chain structure. Specifically, the second polyol may be one in which a hydroxyl group is bonded to both ends, and a functional group reacting with one or more isocyanate groups is bonded to a main chain to form a side chain. Specifically, the second polyol includes a functional group that reacts with three or more isocyanate groups, and may form a network having a more dense structure than a polyol having a linear structure in which hydroxyl groups are bonded only at both ends during urethane polymerization.

The second polyol serves as a framework for the flame-retardant polyurethane foam, and satisfies a weight average molecular weight of 5,000 g/mol or more and 30,000 g/mol or less, thereby improving the compression recovery ability of the flame-retardant polyurethane foam. . Furthermore, the second polyol satisfies a viscosity of 20,000 mPa·s or more and 200,000 mPa·s or less at 25°C, enabling uniform dispersion with other materials in the flame-retardant polyurethane composition, resulting in uniform quality of flame retardancy. Polyurethane foam can be produced.

According to an exemplary embodiment of the present invention, the second polyol, a polyether-based polyol; Polyfunctional isocyanate; And it may be a polymer formed using a second polyol composition comprising a chain extender having three or more functional groups.

According to an exemplary embodiment of the present invention, the polyether-based polyol in the second polyol composition may be derived from polyalkylene oxide. Specifically, the polyether-based polyol in the second polyol composition is polyethylene glycol (PEG: polyethylene glycol); Polypropylene glycol (PPG); PEG-PPG copolymer (polyethylene glycol-polypropylene glycol copolymer); And poly (tetramethylene ether) glycol (PTMG: Poly (tetramethylene ether) glycol) may include one or more selected from the group consisting of.

According to an exemplary embodiment of the present invention, a molar ratio of the polyether-based polyol and the polyfunctional isocyanate in the second polyol composition may be 1:0.5 to 1:1. Specifically, the molar ratio of the polyether-based polyol and the polyfunctional isocyanate in the second polyol composition may be 1:0.6 to 1:0.95, or 1:0.65 to 1:0.9.

When the content of the polyfunctional isocyanate in the second polyol composition is within the above range, the viscosity when preparing the second polyol is not too high to improve blendability with other compositions, and gelation may be prevented.

According to an exemplary embodiment of the present invention, the polyfunctional isocyanate in the second polyol composition may be a difunctional isocyanate. Specifically, according to an exemplary embodiment of the present invention, the polyfunctional isocyanate in the second polyol composition may be an aromatic polyfunctional isocyanate. Specifically, the aromatic polyfunctional isocyanate is 2,4-tolylene diisocyanate (TDI: tolylene diisocyanate), 2,6-tolylene diisocyanate (TDI: tolylene diisocyanate), m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI: Methylene diphenyl diisocyanate), 2,4'-diphenylmethane diisocyanate (MDI: Methylene diphenyl diisocyanate), 2,2'-diphenylmethane diisocyanate (MDI: Methylene) diphenyl diisocyanate), xylylene diisocyanate (XDI), 3,3'-dimethyl-4,4'-biphenylene diisocyanate, and 3,3'-dimethoxy-4,4'-biphenylene diisocyanate It may be one or more selected from the group consisting of.

Further, according to an exemplary embodiment of the present invention, the polyfunctional isocyanate in the second polyol composition may be an alicyclic polyfunctional isocyanate. Specifically, the alicyclic polyfunctional isocyanate is 4,4'-methylene dicyclohexyl diisocyanate (H12-MDI: 4,4'-Methylene dicyclohexyl diisocyanate), cyclohexane-1,4-diisocyanate, isophorone Diisocyanate (IPDI: isophorone diisocyanate), dicyclohexylmethane-4,4'-diisocyanate, and hydrated xylylene diisocyanate (H6-XDI: Hydrogenated xylylene diisocyanate), and methylcyclohexane diisocyanate selected from the group consisting of There may be more than one type.

In addition, according to an exemplary embodiment of the present invention, the polyfunctional isocyanate in the second polyol composition may be an aliphatic polyfunctional isocyanate. Specifically, the aliphatic polyfunctional isocyanate is one selected from the group consisting of butane-1,4-diisocyanate, hexamethylene diisocyanate (HDI: hexamethylene diisocyanate), isopropylene diisocyanate, methylene diisocyanate, and lysine isocyanate It can be more than that.

According to an exemplary embodiment of the present invention, the molar ratio of the polyether-based polyol and the chain extender having three or more functional groups in the second polyol composition may be 1:0.1 to 1:0.45. Specifically, according to an exemplary embodiment of the present invention, the molar ratio of the polyether-based polyol and the chain extender having three or more functional groups in the second polyol composition is 1:0.2 to 1:0.4, or 1:0.25 To 1:0.35, more specifically 1:0.3.

When the content of the chain extender having three or more functional groups in the second polyol composition is within the above range, there is an advantage of realizing excellent compression recovery performance by forming an appropriate crosslink in the flame-retardant polyurethane foam.

According to an exemplary embodiment of the present invention, the chain extender having three or more functional groups in the second polyol composition may be a compound containing a functional group reacting with three or more isocyanate groups. In addition, the functional groups of the chain extender having three or more functional groups in the second polyol composition may be 3 or more and 10 or less, or 3 or more and 5 or less.

According to an exemplary embodiment of the present invention, the chain extender having three or more functional groups in the second polyol composition may include one or more of the following compounds.

According to an exemplary embodiment of the present invention, the content of the second polyol may be 5% by weight or more and 20% by weight or less based on the total polyol. Specifically, according to an exemplary embodiment of the present invention, the content of the second polyol may be 5% by weight or more and 15% by weight or less based on the total polyol.

When the content of the second polyol is within the above range, it is possible to maintain the soft properties of the flame-retardant polyurethane foam formed by using the flame-retardant polyurethane foam composition and implement excellent repelling properties, and minimize the loss of compression resilience to the flame retardancy. Durability of polyurethane foam can be secured.

In this specification, the total polyol may refer to the entire polyol-based material including the first polyol, the second polyol, and the third polyol. In addition, the total polyol may mean that which is composed of the first polyol, the second polyol, and the third polyol.

According to an exemplary embodiment of the present invention, the third polyol may be a polyol having a heat release capacity of 500 J/g·K or less and a limiting oxygen index of 21% or more. In addition, according to an exemplary embodiment of the present invention, the third polyol is a polyol having a heat dissipation capacity of 500 J/g·K or less and a limiting oxygen index of 21% or more, and a third polyol composition containing a polyfunctional isocyanate. It may be a polymer formed by.

According to an exemplary embodiment of the present invention, the third polyol has a heat release capacity of 500 J/g·K or less polycarbonate diol and a heat release capacity of 500 It may contain at least one of polydimethylsiloxane diols of J/g·K or less.

According to an exemplary embodiment of the present invention, the polyfunctional isocyanate in the third polyol composition may serve to improve compatibility with other compositions of the third polyol.

The third polyol satisfies a heat dissipation capacity of 500 J/g·K or less, or a heat dissipation capacity of 500 J/g·K or less and a limiting oxygen index value of 21% or more. The third polyol itself may have flame-retardant properties, and through this, the flame-retardant performance of the flame-retardant polyurethane foam may be improved.

According to an exemplary embodiment of the present invention, the polyfunctional isocyanate in the third polyol composition may be the same material as the polyfunctional isocyanate in the second polyol composition.

According to an exemplary embodiment of the present invention, a heat release capacity of the polymer formed by using the third polyol composition may be 500 J/g·K or less. In addition, the heat release capacity of the polymer formed by using the third polyol composition may be 500 J/g·K or less, and the limiting oxygen index may be 21% or more.

According to an exemplary embodiment of the present invention, the molar ratio of the polyol having the heat dissipation capacity of 500 J/g·K or less and the polyfunctional isocyanate in the third polyol composition may be 1:0.05 to 1:0.25. Specifically, according to an exemplary embodiment of the present invention, the molar ratio of the polyol and the polyfunctional isocyanate having the heat dissipation capacity of 500 J/g·K or less in the third polyol composition is 1:0.05 to 1:0.15, or 1 : It may be from 0.07 to 0.12. More specifically, the molar ratio of the polyol having a heat dissipation capacity of 500 J/g·K or less and the polyfunctional isocyanate in the third polyol composition may be 1:0.1.

When the content of the polyfunctional isocyanate in the third polyol composition is within the above range, the polymer formed by using the third polyol composition may have improved compatibility with other compositions.

According to an exemplary embodiment of the present invention, the content of the third polyol may be 20% by weight or more and 50% by weight or less based on the total polyol. Specifically, according to an exemplary embodiment of the present invention, the content of the third polyol may be 25% by weight or more and 40% by weight or less, or 25% by weight or more and 35% by weight based on the total polyol.

When the content of the third polyol is within the above range, compatibility with other materials in the flame-retardant polyurethane foam composition may be secured. In addition, as a result of the UL-94 vertical flame retardant test of the flame-retardant polyurethane foam, the flame retardant property of the V-0 grade can be realized, and hardening of the flame-retardant polyurethane foam can be minimized.

According to an exemplary embodiment of the present invention, the viscosity of the third polyol may be 1,000 mPa·s or more and 7,000 mPa·s or less, or 1,500 mPa·s or more and 5,000 mPa·s or less.

When the viscosity of the third polyol is within the above range, there is an advantage of securing compatibility with other components in the flame-retardant polyurethane foam composition.

According to an exemplary embodiment of the present invention, the total content of the second polyol and the third polyol may be 30% by weight or more and 60% by weight or less based on the total polyol. Specifically, according to an exemplary embodiment of the present invention, the total content of the second polyol and the third polyol is, based on the total polyol, 30% by weight or more and 50% by weight or less, or 30% by weight or more and 45% by weight or less, or 30 It may be greater than or equal to 40% by weight.

According to an exemplary embodiment of the present invention, the flame retardant may include a non-halogen type flame retardant. Specifically, the flame retardant may include a solid or liquid non-halogen type phosphorus-based flame retardant. Specifically, according to an exemplary embodiment of the present invention, the flame retardant is phosphate (phosphate); Phosphonate; Phosphinate; Phosphine oxide; And it may include one or more selected from the group consisting of phosphazene (phosphazene). Specifically, the flame retardant may be aluminum phosphate. However, the present invention is not limited thereto, and a phosphorus-based flame retardant generally used in the art may be used.

The non-halogen-type phosphorus-based flame retardant reacts with a combustible material to form a carbonized film on the surface of the polymer, which blocks oxygen required for combustion, thereby increasing the flame retardancy of the flame-retardant polyurethane foam. In addition, the non-halogen-type phosphorus-based flame retardant reacts with an oxygen element in the polymer to perform dehydration and carbonization, and radicals generated by decomposition of phosphoric acid play a role of stabilizing -OH and -H, which are active radicals generated by combustion. can do.

According to an exemplary embodiment of the present invention, the flame retardant may include a mixture of the phosphorus-based flame retardant and flame retardant melamine powder. Specifically, the flame-retardant melamine powder may be melamine cyanurate (MCA).

According to an exemplary embodiment of the present invention, the content of the flame retardant may be 21 parts by weight or more and 50 parts by weight or less based on 100 parts by weight of the total polyol. Specifically, according to an exemplary embodiment of the present invention, the content of the flame retardant may be 21 parts by weight or more and 40 parts by weight or less, or 21 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the total polyol.

When the content of the flame retardant is within the above range, the effect of lowering the heat dissipation capacity of the polyol in the flame retardant polyurethane foam composition and increasing the limiting oxygen index may be obtained. In addition, when the content of the flame retardant is within the above range, it can help to form the polymer of the flame-retardant polyurethane foam into char during combustion, and radicals generated during combustion can be effectively removed. Further, when the content of the flame retardant is within the above range, it is possible to minimize the deterioration of the compression recovery performance of the flame retardant polyurethane foam and secure flame retardancy.

According to an exemplary embodiment of the present invention, the content of the expanded graphite may be 21 parts by weight or more and 50 parts by weight or less based on 100 parts by weight of the total polyol. Specifically, the content of the expanded graphite may be 21 parts by weight or more and 40 parts by weight or less, or 21 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the total polyol.

The expanded graphite has a layered crystal structure, and when heated, expands up to 20 to 400 times its original size, thereby inducing the formation of porous carbides during combustion. Further, when the content of the expanded graphite is adjusted within the above range, flame retardancy may be improved without lowering the compression resilience of the flame-retardant polyurethane foam.

According to an exemplary embodiment of the present invention, the weight ratio of the flame retardant and the expanded graphite may be 1: 0.8 to 1: 1.2. Specifically, according to an exemplary embodiment of the present invention, the weight ratio of the flame retardant and the expanded graphite may be 1:0.9 to 1:1.1. More specifically, the weight ratio of the flame retardant and the expanded graphite may be 1:1.

When the content of the flame retardant and the expanded graphite is controlled within the above range, the flame retardant properties of the flame retardant polyurethane foam formed using the flame retardant polyurethane foam composition may be implemented as a V-0 grade.

According to an exemplary embodiment of the present invention, the foaming agent may be applied as long as it is generally used in the manufacture of urethane foam. Specifically, the foaming agent may include at least one selected from the group consisting of a silicone-based foaming agent, an organic silicon-based foaming agent, a fluorine-based foaming agent, an ionic surfactant, and a nonionic surfactant. More specifically, the foaming agent may include polydimethylsiloxane substituted with polyalkyl oxide. However, the foaming agent is not limited thereto, and a foaming agent generally used in the art may be used. By using the foaming agent, the foaming gas forms a foam structure suitable for the polyurethane foam, and when cured into the flame-retardant polyurethane foam, it is possible to form pores of uniform size and distribution by maintaining the stable dispersibility of the gas. .

According to an exemplary embodiment of the present invention, the content of the foaming agent is 0.5 parts by weight or more and 10 parts by weight or less, or 1 part by weight or more and 5 parts by weight or less, or 2 parts by weight or more and 4 parts by weight based on 100 parts by weight of the total polyol. It may be less than or equal to part.

The gas for fabrication is a gas that does not adversely affect the reaction between polyol and isocyanate, and an inert gas such as dry air and/or nitrogen gas may be used.

According to an exemplary embodiment of the present invention, the isocyanate-based curing agent may form a urethane bond with the first to third polyols to form a polyurethane network.

According to an exemplary embodiment of the present invention, the isocyanate-based curing agent is a bifunctional or trifunctional or higher isocyanate, and may be an aromatic isocyanate, an alicyclic isocyanate, and/or an aliphatic isocyanate. As the aromatic isocyanate, alicyclic isocyanate, and aliphatic isocyanate as the isocyanate-based curing agent, the same materials as the above-described aromatic isocyanate, alicyclic isocyanate and aliphatic isocyanate may be used.

According to an exemplary embodiment of the present invention, the flame-retardant polyurethane foam composition may further include an additive selected from the group consisting of a catalyst, a crosslinking agent, and a filler.

According to an exemplary embodiment of the present invention, the catalyst may be an amine-based catalyst and/or a metal catalyst. Specifically, the amine-based catalyst may be at least one selected from the group consisting of a monoamine compound, a diamine compound, a triamine compound, a polyamine compound, a cyclic amine compound, an alcohol amine compound, and an ether amine compound. In addition, the metal catalyst may be at least one selected from the group consisting of an organic tin compound, an organic bismuth compound, an organic lead compound, an organic nickel compound, and an organic zinc compound. Specifically, according to an exemplary embodiment of the present invention, the catalyst may be dibutyltin dilaurate.

According to an exemplary embodiment of the present invention, the content of the catalyst is 0.5 parts by weight or more and 10 parts by weight or less, or 1 part by weight or more and 10 parts by weight or less, or 1 part by weight or more and 5 parts by weight based on 100 parts by weight of the total polyol. It can be below.

According to an exemplary embodiment of the present invention, the crosslinking agent may be a low molecular weight compound having a number average molecular weight of 50 or more and 800 or less having 2 to 4 active hydrogen-containing groups capable of reacting with an isocyanate group. Specifically, the crosslinking agent is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, triethanolamine, and pentaerythritol It may include one or more selected from the group consisting of.

According to an exemplary embodiment of the present invention, the content of the crosslinking agent may be 1 part by weight or more and 20 parts by weight or less, or 5 parts by weight or more and 15 parts by weight or less based on 100 parts by weight of the total polyol.

An exemplary embodiment of the present invention. It provides a flame retardant polyurethane foam comprising a cured product of the flame retardant polyurethane foam composition according to the above.

An exemplary embodiment of the present invention provides a flame-retardant polyurethane foam formed by using the flame-retardant polyurethane foam composition. As a method of manufacturing a flame-retardant polyurethane foam using the flame-retardant polyurethane foam composition, a generally known method of manufacturing a polyurethane foam may be used.

According to an exemplary embodiment of the present invention, the flame-retardant polyurethane foam may have a flame-retardant property of V-0 as a result of a UL-94 vertical flame-retardant test.

1 shows a schematic diagram for a UL-94 vertical flame retardant test. Specifically, in the UL-94 vertical flame retardant test, a specimen was prepared with a thickness of 125 ± 25 mm × 13.0 ± 0.5 mm × 13 mm or less. Prepare five sets of two specimens prepared in this way as one set, and after storage at 23±2℃ and 50±5% humidity, a blue flame of methane gas of 37 MJ/㎥ calorific value (flame height 20 ㎜, Each specimen is burned twice for 10 seconds using the distance between the lower part of the specimen and the end of the burner (9.5 ㎜), and the flame disappears after the second 10 seconds of flame combustion (t2) and the duration of flame-free combustion (t3). Thus, grades are given according to the criteria shown in Table 1 below.

UL-94 V test Rating V-O V-1 V-2 Extinguishing time after the first and second burning of each specimen
(t1 or t2) ≤ 10 ≤ 30 ≤ 30 Sum of fire extinguishing times after total combustion of 5 sets
(t1+t2) ≤ 50 ≤ 250 ≤ 250 Sum of extinguishing time and smokeless combustion time after second combustion of each specimen
(t2+t3) ≤ 30 ≤ 60 ≤ 60 Spark fragments or lumps fall off,
Whether the cotton under 305 mm of specimen burns NO NO YES

According to an exemplary embodiment of the present invention, the flame-retardant polyurethane foam may have a compression set of 10% or less measured after applying compression to 50% of the initial thickness and leaving it for 70 hours at room temperature. Specifically, according to an exemplary embodiment of the present invention, the flame-retardant polyurethane foam may have a compression set of 7% or less measured after applying compression to 50% of the initial thickness and leaving it for 70 hours at room temperature.

The compression permanent reduction rate is a value measured according to the KS M ISO 1956 standard (corresponding to ISO 1856:2000). Specifically, the compression permanent reduction rate is under the test conditions of KS M ISO 1956 standard (corresponding to ISO 1856:2000), compressing the specimen to 50% of the initial thickness using a compression jig and leaving it at 23±2° C. for 70 hours Then, it is a value measured using the thickness restored by compression removal.

According to an exemplary embodiment of the present invention, the density of the flame-retardant polyurethane foam may be 0.2 g/cm 3 or more and 0.5 g/cm 3 or less.

When the density of the flame-retardant polyurethane foam is adjusted within the above range, effective compression recovery characteristics can be realized by adhesion and excellent repulsion characteristics when applied to a device.

According to an exemplary embodiment of the present invention, the thickness of the flame-retardant polyurethane foam may be 0.1 mm or more and 10 mm or less. Specifically, the thickness of the flame-retardant polyurethane foam may be 0.1 mm or more and 5 mm or less.

When the thickness of the flame-retardant polyurethane foam is adjusted within the above range, adhesion and shock absorption can be facilitated when applied to a device.

According to an exemplary embodiment of the present invention, the flame-retardant polyurethane foam may be a packing material.

In addition, according to an exemplary embodiment of the present invention, the flame-retardant polyurethane foam may be a sealing material between cells of a vehicle battery.

Hereinafter, examples will be described in detail to illustrate the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present invention to those of ordinary skill in the art.

[Production Example 1]-Preparation of the first polyol

50% by weight of polypropylene glycol having a number average molecular weight of 4,000 g/mol, a viscosity of 1,300 mPa·s, and a heat release capacity of 553 J/g·K; And after preparing a composition containing 50% by weight of polypropylene glycol having a number average molecular weight of 2,000 g/mol, a viscosity of 300 mPa·s, and a heat dissipation capacity of 553 J/g·K, it is polymerized, and the viscosity is 730 A first polyol having a mPa·s and a glass transition temperature of -71°C was prepared.

[Production Example 2]-Preparation of the second polyol

In a reactor in which nitrogen is refluxed, H12-MDI (Evonik) and glycerol were each added to 10 kg of PEG-PPG copolymer (SC2204; KPX chemical) having a number average molecular weight of 2,000 g/mol in a molar ratio to S2204 as shown in Table 2 below. Was put in. Then, the temperature was raised to 60°C, 40 ppm of catalyst (Dibutyltin dilaurate) was added, stirred for 4 hours, and then confirmed that the isocyanate peak disappeared through FT-IR, and the reaction was terminated to prepare a second polyol as shown in Table 2 below. I did.

SC2204 H12-MDI
(Molar ratio to SC2204) Glycerol
(Molar ratio to SC2204) Viscosity
(mPa·s) Mn
(g/mol) Mw
(g/mol) PDI Remark Manufacturing Example 2 One 0.9 0.3 65,000 5,770 15,000 2.6 Manufacturing Example 2-1 One 0.75 0.3 38,000 4,000 10,000 2.5 Manufacturing Example 2-2 One 0.65 0.3 38,000 3,480 8,000 2.3 Preparation Example 2-3 One 0.9 0 68,000 7,500 15,000 2.0 Linear structure Manufacturing Example 2-4 One 1.1 0.5 - - - - Gelation occurs Manufacturing Example 2-5 One 1.1 0.3 274,000 8,000 21,000 2.6 The viscosity is too high to mix

As can be seen from Table 2, in the case of Preparation Example 2-3, a polyol having a linear structure was formed without using a chain extender (glycerol) having 3 or more functional groups. In addition, in the case of Preparation Example 2-4, the content of the polyfunctional isocyanate (H12-MDI) and the content of the chain extender (glycerol) having 3 or more functional groups were too high, resulting in a gelation phenomenon, and thus the polyol could not be formed. In addition, in the case of Preparation Example 2-5, the content of the polyfunctional isocyanate (H12-MDI) was high, and the viscosity was greatly increased to form a polyol that was difficult to mix with other compositions.

[Production Example 3]-Preparation of third polyol

In the reactor in which nitrogen is refluxed, XDI (Takenate 600, Mitsui Chemical) was added to 10 kg of polycarbonate diol (T5650E; Aksai Kasai chemical) having a number average molecular weight of 500 g/mol at a molar ratio to T5650E as shown in Table 3 below. I did. Then, the temperature was raised to 60°C, 40 ppm of catalyst (Dibutyltin dilaurate) was added, and after stirring for 4 hours, it was confirmed that the isocyanate peak disappeared through FT-IR, and the reaction was terminated. As shown in Table 3 below, the heat release capacity was 400 A third polyol of J/g·K was prepared.

T5650E XDI
(Molar ratio for T5650E) Viscosity
(mPa·s) Mn
(g/mol) Mw
(g/mol) PDI Remark Manufacturing Example 3 One 0.1 3,500 1,000 2,000 2.0 Manufacturing Example 3-1 One 0.3 12,000 4,000 9,000 2.1 Poor compatibility with other ingredients

As can be seen from Table 3, in Preparation Example 3-1, the content of the polyfunctional isocyanate (XDI) was too high, and the polyol was prepared with an excessively high viscosity, which caused a phase separation phenomenon due to poor compatibility with other components. It was difficult to manufacture a flame retardant polyurethane foam. In addition, Preparation Example 3-1 had a problem in that internal hydrogen bonds were too strong, so that the self-cohesive strength was high, so that mixing with the first and second polyols was difficult.

[Examples, Comparative Examples and Reference Examples]-Preparation of flame retardant polyurethane foam

The first to third polyols were added in a weight ratio as shown in Tables 4 to 8 in a stainless steel mixing tank equipped with a stirring device capable of high-speed stirring up to 2000 rpm, and the mixture was uniformly stirred at room temperature. Then, a flame retardant and expanded graphite were added and dispersed well, and then a foaming agent and a catalyst were added in a weight ratio as shown in Tables 4 to 8 below, and stirred at high speed for about 1 hour or more to prepare a uniform composition. At this time, the inflow of moisture was suppressed as much as possible because the urethane reaction was inhibited.

Furthermore, a polyisocyanate solution was separately prepared. The prepared composition, polyisocyanate solution, and nitrogen gas were simultaneously supplied to a high-speed mixing head at a constant rate using a metering pump. At this time, nitrogen gas was supplied while matching the density and hardness. A flame-retardant polyurethane foam sheet having a density of 0.3 g/cm 3 and a thickness of 2.0 mm by mixing the three components uniformly and coating it on a polyester film and then curing it at a high temperature in the range of about 120°C to 150°C in a reaction curing machine Was prepared.

A polyurethane foam was prepared by using the flame-retardant polyurethane foam composition in the method of preparing the flame-retardant polyurethane foam sheet and the composition ratio as shown in Tables 4 to 8 below. Further, the flame retardant properties and compression set of the prepared polyurethane foam were measured.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 First polyol Manufacturing Example 1 70 60 50 40 60 60 60 Second polyol Manufacturing Example 2 10 10 10 10 5 15 10 Tertiary polyol Manufacturing Example 3 20 30 40 50 45 25 30 Flame retardant
(MCA / Al phosphate) 25 25 25 25 25 25 21 Expanded graphite
(180 μm) 25 25 25 25 25 25 21 Antifoam 2.5 2.5 2.5 2.5 2.5 2.5 2.5 catalyst 3 3 3 3 3 3 3 Isocyanate curing agent 28 28 28 28 28 28 28 density
(g/cm3) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 thickness
(Mm) 2 2 2 2 2 2 2 UL-94 vertical flame retardant test V-0 V-0 V-0 V-0 V-0 V-0 V-0 Permanent compression reduction ratio
(%) 4.8 5.2 5.8 6.5 6.9 6.6 4.8

Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 First polyol Manufacturing Example 1 60 60 60 60 60 60 60 60 Second polyol Manufacturing Example 2 10 10 10 10 10 10 0 0 Manufacturing Example 2-1 0 0 0 0 0 0 10 0 Manufacturing Example 2-2 0 0 0 0 0 0 0 10 Tertiary polyol Manufacturing Example 3 30 30 30 30 30 0 30 30 PDMS Dior 0 0 0 0 0 30 0 0 Flame retardant
(MCA / Al phosphate) 30 25 25 25 25 40 40 40 Expanded graphite
(180 μm) 30 25 25 25 25 40 40 40 Antifoam 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 catalyst 3 3 3 3 3 3 3 3 Isocyanate curing agent 28 28 28 28 28 28 28 28 density
(g/cm3) 0.3 0.25 0.4 0.3 0.25 0.3 0.3 0.3 thickness
(Mm) 2 2 2 1.6 1.6 2 2 2 UL-94 vertical flame retardant test V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Permanent compression reduction ratio
(%) 6.1 3.6 6.4 4.2 3.5 1.7 6.9 8.5

The heat dissipation capacity of PDMS diol (Polydimethylsiloxane diol) in Table 5 is 115 J/g·K.

As can be seen in Tables 4 and 5, it can be seen that the flame-retardant polyurethane foam prepared according to the Examples has a flame-retardant property of V-0 grade and at the same time exhibits a compression set reduction rate of 10% or less.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 First polyol Manufacturing Example 1 100 100 100 100 90 60 Second polyol Manufacturing Example 2 0 0 0 0 10 0 Preparation Example 2-3 0 0 0 0 0 10 Tertiary polyol Manufacturing Example 3 0 0 0 0 0 30 Flame retardant
(MCA / Al phosphate) 20 25 30 40 25 40 Expanded graphite
(180 μm) 20 25 30 40 25 40 Antifoam 2.5 2.5 2.5 2.5 2.5 2.5 catalyst 3 3 3 3 3 3 Isocyanate curing agent 28 28 28 28 28 28 density
(g/cm3) 0.3 0.3 0.3 0.3 0.3 0.3 thickness
(Mm) 2 2 2 2 2 2 UL-94 vertical flame retardant test Out of grade V-2 V-2 V-2 V-2 V-0 Permanent compression reduction ratio
(%) 11.5 12.3 15.7 22.0 4.2 12.3

According to Comparative Examples 1 to 4, it can be seen that the polyurethane foam manufactured without using the second polyol and the third polyol has very poor flame retardant properties, and has a problem that the compression set reduction ratio exceeds 10%. In addition, according to Comparative Example 5, when the third polyol is not used, it can be seen that the flame retardant properties are remarkably deteriorated. In addition, according to Comparative Example 6, when a polyol having a linear structure is used as the third polymer, it can be seen that the flame retardant property is excellent, but the compression set reduction rate exceeds 10%.

Comparative Example 7 Comparative Example 8 Comparative Example 9 First polyol Manufacturing Example 1 60 60 60 Second polyol Manufacturing Example 2 10 10 10 Tertiary polyol Polyethylene glycol
(Heat dissipation capacity: 652 J/g·K) 30 0 0 Polycaprolactone diol
(Heat dissipation capacity: 526 J/g·K) 0 30 0 Polypropylene glycol
(Heat dissipation capacity: 553 J/g·K) 0 0 30 Flame retardant
(MCA / Al phosphate) 20 25 30 Expanded graphite
(180 μm) 20 25 30 Antifoam 2.5 2.5 2.5 catalyst 3 3 3 Isocyanate curing agent 28 28 28 density
(g/cm3) 0.3 0.3 0.3 thickness
(Mm) 2 2 2 UL-94 vertical flame retardant test V-2 V-2 V-2 Permanent compression reduction ratio
(%) 4.3 1.3 15.7

According to Table 7, it can be confirmed that the polyurethane foam produced using a polyol having a heat dissipation capacity exceeding 500 J/g·K as a third polyol does not satisfy the V-0 grade as the flame retardant property is V-2. have.

Reference Example 1 Reference Example 2 Reference Example 3 Reference Example 4 First polyol Manufacturing Example 1 80 75 70 60 Second polyol Manufacturing Example 2 10 10 10 10 Tertiary polyol Manufacturing Example 3 10 15 20 30 Flame retardant
(MCA / Al phosphate) 25 25 20 30 Expanded graphite
(180 μm) 25 25 20 20 Antifoam 2.5 2.5 2.5 2.5 catalyst 3 3 3 3 Isocyanate curing agent 28 28 28 28 density
(g/cm3) 0.3 0.3 0.3 0.25 thickness
(Mm) 2 2 2 2 UL-94 vertical flame retardant test V-2 V-2 V-2 V-2 Permanent compression reduction ratio
(%) 4.3 5.5 5.5 4.7

According to Reference Examples 1 and 2, it can be seen that the content of the third polyol is less than 20% by weight based on the total polyol, so that the flame retardant property is very poor. In addition, according to Reference Examples 3 and 4, since the content of the flame retardant and/or expanded graphite is less than 21 parts by weight based on 100 parts by weight of the total polyol, the flame retardant property may be very poor.

Claims (15)

A first polyol having a glass transition temperature of -50°C or less and a viscosity of 2,000 mPa·s or less at 25°C;
A second polyol containing at least three functional groups reacting with an isocyanate group, a weight average molecular weight of 5,000 g/mol or more and 30,000 g/mol or less, and a viscosity at 25° C. of 20,000 mPa·s or more and 200,000 mPa·s or less;
A third polyol having a heat release capacity of 500 J/g·K or less;
Isocyanate-based curing agents;
Antifoam;
Flame retardant; And
Containing expanded graphite
It is a flame retardant polyurethane foam composition,
The second polyol is a polyether-based polyol; Polyfunctional isocyanate; And it is a polymer formed by using a second polyol composition comprising a chain extender having three or more functional groups,
The molar ratio of the polyether-based polyol and the polyfunctional isocyanate in the second polyol composition is 1:0.5 to 1:1,
The molar ratio of the polyether-based polyol and the chain extender having three or more functional groups in the second polyol composition is from 1:0.1 to 1:0.45, flame-retardant polyurethane foam composition. The method according to claim 1,
The content of the second polyol is a flame-retardant polyurethane foam composition that is 5% by weight or more and 20% by weight or less based on the total polyol. The method according to claim 1,
The content of the third polyol is a flame-retardant polyurethane foam composition that is 20% by weight or more and 50% by weight or less based on the total polyol. The method according to claim 1,
The total content of the second polyol and the third polyol is 30% by weight or more and 60% by weight or less based on the total polyol. The method according to claim 1,
The content of the flame retardant is 21 parts by weight or more and 50 parts by weight or less based on 100 parts by weight of the total polyol. The method according to claim 1,
The content of the expanded graphite is a flame-retardant polyurethane foam composition of 21 parts by weight or more and 50 parts by weight or less based on 100 parts by weight of the total polyol. delete delete delete The method according to claim 1,
The third polyol is a polyol having a heat dissipation capacity of 500 J/g·K or less, or a polymer formed using a polyol having a heat dissipation capacity of 500 J/g·K or less and a third polyol composition comprising a polyfunctional isocyanate. Flame retardant polyurethane foam composition. The method of claim 10,
The flame-retardant polyurethane foam composition of the third polyol composition wherein the molar ratio of the polyol having a heat dissipation capacity of 500 J/g·K or less and the polyfunctional isocyanate is 1:0.05 to 1:0.25. Flame-retardant polyurethane foam comprising a cured product of the flame-retardant polyurethane foam composition according to claim 1. The method of claim 12,
The flame-retardant polyurethane foam is a flame-retardant polyurethane foam having a flame-retardant property of V-0 as a result of a UL-94 vertical flame-retardant test. The method of claim 12,
The flame-retardant polyurethane foam is a flame-retardant polyurethane foam having a compression set of 10% or less measured after applying compression to 50% of the initial thickness and leaving it for 70 hours at room temperature. The method of claim 12,
The flame-retardant polyurethane foam has a density of 0.2 g/cm 3 or more and 0.5 g/cm 3 or less.

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