KR20200027690A - Composition for flame retardant polyurethane foam and flame retardant polyurethane foam comprising cured product thereof - Google Patents

Abstract

The present invention relates to a polyurethane foam having excellent flame retardancy and compression properties, and a flame-retardant polyurethane foam composition capable of implementing the same. The polyurethane foam composition comprises polyol mixtures, isocyanate-based curing agents, surfactants, flame retardants, expanded graphite, and dispersants.

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 automobile parts and household goods. 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 a polyurethane foam was mainly used. This is not a flame retardant effect, since it is not basically imparting flame retardancy to a polyurethane foam. Is limited, there is a problem that the manufacturing process is complicated and increases the manufacturing cost. In addition, 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 has been added, which may cause human and environmental problems due to toxic gases during combustion.

Accordingly, there is a need to develop a polyurethane foam having high elasticity and excellent flame retardant properties.

KR 10-2014-0109474 A

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

However, the problem to be solved by the present invention is not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

An exemplary embodiment of the present invention includes a first polyol-based compound having a glass transition temperature of -50 ° C or less; A second polyol-based compound containing at least three functional groups that react with an isocyanate group; And a third polyol-based compound having a heat dissipation capacity of 500 J / g · K or less; Isocyanate curing agents; Antifoaming agent; Flame retardants; Expanded graphite; And it provides a flame-retardant polyurethane foam composition comprising a; dispersant comprising a titanate.

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 composition according to an exemplary embodiment of the present invention may provide a polyurethane foam having excellent flame retardancy and compression characteristics.

The flame-retardant polyurethane foam according to an exemplary embodiment of the present invention has a flame-retardant property of V-0 grade as a result of UL-94 vertical flame retardant test, so it is possible to minimize the risk of ignition even when applied to high-temperature equipment.

The flame-retardant polyurethane foam according to an exemplary embodiment of the present invention has an excellent compression and resilience, and thus, when applied to a device, can effectively absorb shock between parts to improve the durability of the device.

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

Flame-retardant polyurethane foam according to an exemplary embodiment of the present invention, when applied between cells of an automotive battery, dimensional stability to the volume change of the cell, excellent stress absorption against vibration and shock, excellent resilience and high fire resistance You can implement

The effects of the present invention are not limited to the above-described effects, and effects not mentioned will be clearly understood by those skilled in the art from the present specification and the accompanying drawings.

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

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

Throughout the present specification, the unit “parts by weight” may mean a ratio of weight between each component.

Throughout this specification, “A and / or B” means “A and B, or A or B”.

Throughout this specification, the "weight average molecular weight" and "number average molecular weight" of a compound can be calculated using the molecular weight and molecular weight distribution of that compound. Specifically, tetrahydrofuran (THF) and a compound are prepared in a 1 ml glass bottle to prepare a sample sample having a compound concentration of 1 wt%, and a standard sample (polystyrene, polystryere) and a sample sample are filtered (pore size). Is filtered through 0.45 mm), and injected into a GPC injector to compare the elution time of the sample sample with the calibration curve of the standard sample to obtain the molecular weight and molecular weight distribution of the compound. In this case, Infinity II 1260 (Agilient Co.) can be used as the measuring instrument, the flow rate can be set to 1.00 mL / min, and the column temperature can be set to 40.0 ° C.

Throughout the present specification, “Glass Temperature (Tg)” can be measured using Differential Scanning Analysis, and specifically DSC (Differential Scanning Calorimeter, DSC-STAR3, METTLER TOLEDO) Using, the sample is heated to a heating rate of 5 ° C./min in a temperature range of −60 ° C. to 150 ° C., and the experiment is conducted twice in the above section, and the middle of the DSC curve created as a point where there is a thermal change amount. The glass transition temperature can be determined by measuring the point.

Throughout the present specification, the viscosity of the compound may be a value measured with a Brookfield viscometer at a temperature of 25 ° C.

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

An exemplary embodiment of the present invention includes a first polyol-based compound having a glass transition temperature of -50 ° C or less; A second polyol-based compound containing at least three functional groups that react with an isocyanate group; And a third polyol-based compound having a heat dissipation capacity of 500 J / g · K or less; Isocyanate curing agents; Antifoaming agent; Flame retardants; Expanded graphite; And it provides a flame-retardant polyurethane foam composition comprising a; dispersant comprising a titanate.

The flame-retardant polyurethane foam composition according to an exemplary embodiment of the present invention may provide a polyurethane foam having excellent flame retardancy and compression characteristics.

According to an exemplary embodiment of the present invention, the first polyol-based compound may have a glass transition temperature of -50 ° C or less. Specifically, the glass transition temperature of the first polyol-based compound may be -80 ℃ or more -50 ℃ or less, or -75 ℃ or more -60 ℃ or less. When the glass transition temperature of the first polyol-based compound is within the above-described range, the flame-retardant polyurethane foam including a cured product of the flame-retardant polyurethane foam composition may have high rebound characteristics and compression restoration characteristics.

In addition, the first polyol-based compound may have a viscosity at 25 ° C of 2,000 mPa · s or less. Specifically, the viscosity of the first polyol-based compound at 25 ° C may be 200 mPa · s or more and 2,000 mPa · s or less. By adjusting the viscosity of the first polyol-based compound to the above-described range, there is an advantage that can increase the dispersibility and workability of the raw material when manufacturing the flame-retardant polyurethane foam.

According to an exemplary embodiment of the present invention, the first polyol-based compound has a glass transition temperature of -50 ° C or less, and is a polyether-based polyol having a polyalkylene oxide unit, and has a viscosity at 25 ° C of 2,000 mPa · s or less. May be

Further, the first polyol-based compound may include at least two functional groups that react with an isocyanate group. The functional group reacting with the isocyanate group may mean a functional group having an urethane bond with the isocyanate group. Specifically, the functional group that reacts with the isocyanate group may be a hydroxy group, an amine group, a thiol group or a carboxy group. More specifically, the first polyol-based compound has a hydroxyl group attached to both ends of the main chain, and at least one of a hydroxy group, an amine group, a thiol group, and a carboxy group may be included in the side chain of the first polyol-based compound.

According to an exemplary embodiment of the present invention, the content of the first polyol-based compound may be 60 parts by weight or more and 75 parts by weight or less with respect to 100 parts by weight of the polyol mixture. Specifically, the content of the first polyol-based compound may be 62.5 parts by weight or more and 72.5 parts by weight or less, 65 parts by weight or more, 70 parts by weight or less, or 67 parts by weight or more and 73 parts by weight or less based on 100 parts by weight of the polyol mixture. . By adjusting the content of the first polyol-based compound to the above-described range, it is possible to improve the compression and restoration properties of the polyurethane foam containing the cured product of the flame-retardant polyurethane foam composition.

In the present specification, the polyol mixture may mean the entire polyol-based material including the first polyol-based compound, the second polyol-based compound, and the third polyol-based compound. In addition, the polyol mixture may mean that the first polyol-based compound, the second polyol-based compound, and the third polyol-based compound.

According to an exemplary embodiment of the present invention, the second polyol-based compound may include at least three functional groups that react with an isocyanate group. The functional group reacting with the isocyanate group may mean a functional group having an urethane bond with the isocyanate group. Specifically, the functional group that reacts with the isocyanate group may be a hydroxy group, an amine group, a thiol group or a carboxy group.

According to an exemplary embodiment of the present invention, the second polyol-based compound may have a branched chain structure. Specifically, the second polyol-based compound may have a hydroxyl group attached to the sock end and one or more functional groups reacting with an isocyanate group attached to the main chain to form a side chain. Specifically, the second polyol-based compound may include three or more functional groups that react with an isocyanate group, thereby forming a network structure with a more compact structure when urethane is polymerized, compared to a polyol of a linear structure in which a hydroxyl group is bonded only to the sock end. .

According to an exemplary embodiment of the present invention, the weight average molecular weight of the second polyol-based compound may be 5,000 g / mol or more and 30,000 g / mol or less. Specifically, the weight average molecular weight of the second polyol-based compound is 7,000 g / mol or more and 28,000 g / mol or less, 10,000 g / mol or more, 25,000 g / mol or less, 12,000 g / mol or more, 20,000 g / mol or less, or 15,000 g It may be / mol or more and 18,000 g / mol or less. The second polyol-based compound serves as a skeleton of the flame-retardant polyurethane foam, and when the weight-average molecular weight of the second polyol-based compound is within the above-described range, the compression-recovery ability of the flame-retardant polyurethane foam can be effectively improved. .

According to an exemplary embodiment of the present invention, the second polyol-based compound may have a viscosity at 25 ° C of 20,000 mPa · s or more and 200,000 mPa · s or less. Specifically, the viscosity of the second polyol-based compound at 25 ° C is 30,000 mPa · s or more and 180,000 mPa · s or less, 35,000 mPa · s or more, 150,000 mPa · s or less, 50,000 mPa · s or more and 120,000 mPa · s or less, 60,000 mPa · s or more and 100,000 mPa · s or less, or 35,000 mPa · s or more and 70,000 mPa · s or less. When the viscosity of the second polyol-based compound is within the above-described range, uniform dispersion with other materials in the flame-retardant polyurethane composition is possible to produce a flame-retardant polyurethane foam of uniform quality.

According to an exemplary embodiment of the present invention, the second polyol-based compound includes at least three functional groups that react with an isocyanate group, and has 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. It may be a polyether-based polyol of 20,000 mPa · s or more and 200,000 mPa · s or less.

According to an exemplary embodiment of the present invention, the second polyol-based compound, a polyether-based polyol; Polyfunctional isocyanate-based compounds; And it may be a polymer of the second polyol mixture containing; chain extender comprising at least three functional groups that react with the isocyanate group.

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

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

When the content of the polyfunctional isocyanate-based compound in the second polyol mixture is within the above range, when preparing the second polyol-based compound, the viscosity may not be too high to improve the blendability with other compositions and prevent gelation. can do.

According to an exemplary embodiment of the present invention, the polyfunctional isocyanate-based compound in the second polyol mixture may include two isocyanate groups. In addition, the polyfunctional isocyanate compound in the second polyol mixture may include at least one of an aromatic polyfunctional isocyanate compound, an alicyclic polyfunctional isocyanate compound, and an aliphatic polyfunctional isocyanate compound.

Specifically, the aromatic polyfunctional isocyanate compound is 2,4-tolylene diisocyanate (TDI: tolylene diisocyanate), 2,6-tolylene diisocyanate (TDI), m-phenylenediisocyanate, p-phenylenediisocyanate , 4,4＇-diphenylmethane diisocyanate (MDI), 2,4＇-diphenylmethane diisocyanate (MDI), 2,2＇-diphenylmethane diisocyanate (MDI: Methylene diphenyl diisocyanate), xylylene diisocyanate (XDI), 3,3'-dimethyl-4,4'-biphenylenediisocyanate, and 3,3'-dimethoxy-4,4'-biphenylenedi It may contain at least one of isocyanates.

In addition, the alicyclic polyfunctional isoisonate compound 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. You can.

Further, the aliphatic polyfunctional isocyanate compound may include at least one of butane-1,4-diisocyanate, hexamethylene diisocyanate (HDI), isopropylene diisocyanate, methylene diisocyanate, and lysine isocyanate. .

According to an exemplary embodiment of the present invention, the second polyol mixture may have a molar ratio of the polyether-based polyol and the chain extender of 1: 0.1 to 1: 0.45. Specifically, the molar ratio of the polyether-based polyol and the chain extender may be 1: 0.2 to 1: 0.4, or 1: 0.25 to 1: 0.35, and more specifically 1: 0.3.

When the content of the chain extender in the second polyol mixture is within the above range, it is possible to form an appropriate crosslink in the flame-retardant polyurethane foam to realize excellent compression restoration performance.

According to an exemplary embodiment of the present invention, the chain extender in the second polyol mixture may be a compound containing three or more functional groups that react with an isocyanate group. In addition, the number of the functional water contained in the chain extender 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 in the second polyol mixture may include one or more of the following compounds.

According to an exemplary embodiment of the present invention, the content of the second polyol-based compound may be 5 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the polyol mixture. Specifically, the content of the second polyol-based compound may be 5 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the polyol mixture.

When the content of the second polyol-based compound is within the above-described range, it is possible to maintain the soft properties of the flame-retardant polyurethane foam formed using the flame-retardant polyurethane foam composition and realize excellent repelling properties. In addition, by adjusting the content of the second polyol-based compound to the above range, it is possible to secure the durability of the flame-retardant polyurethane foam by minimizing the loss of compression restoration force.

According to an exemplary embodiment of the present invention, the third polyol-based compound, a polyol having a heat dissipation capacity of 500 J / g · K or less; Or a polymer of a polyol mixture having a heat release capacity of 500 J / g · K or less and a polyfunctional isocyanate-based compound;

According to an exemplary embodiment of the present invention, as the third polyol-based compound itself, flame-retardant properties may be maintained, thereby improving flame-retardant performance of the flame-retardant polyurethane foam.

According to one embodiment of the present invention, the third polyol-based compound has a heat release capacity of 500 J / g · K or less and a polycarbonate diol and a heat release capacity. At least one of the polydimethylsiloxane diols of 500 J / g · K or less may be included.

According to an exemplary embodiment of the present invention, the polyol having a heat release capacity of 500 J / g · K or less may be a polyol having a limiting oxygen index value of 21% or more.

According to an exemplary embodiment of the present invention, the third polyol-based compound may be a polymer formed using a polyol having a heat dissipation capacity of 500 J / g · K or less and a third polyol mixture comprising a polyfunctional isocyanate-based compound. That is, the polymer may have a heat dissipation capacity of 500 J / g · K or less. In addition, the third polyol-based compound may be a polymer formed using a polyol having a heat release capacity of 500 J / g · K or less and a limiting oxygen index of 21% or more, and a third polyol mixture containing a polyfunctional isocyanate-based compound. have. That is, the polymer formed using the third polyol mixture may have a heat dissipation capacity of 500 J / g · K or less, and a limiting oxygen index of 21% or more.

According to an exemplary embodiment of the present invention, the third polyol-based compound has 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%. Satisfying the above value, it is possible to retain the flame retardant properties as the third polyol compound itself, thereby improving the flame retardant performance of the flame retardant polyurethane foam.

According to an exemplary embodiment of the present invention, the polyfunctional isocyanate-based compound in the third polyol mixture may serve to improve compatibility with other compositions of the third polyol-based compound. Further, the polyfunctional isocyanate-based compound in the third polyol mixture may be the same material as the polyfunctional isocyanate-based compound in the second polyol mixture.

According to an exemplary embodiment of the present invention, the third polyol mixture may have a molar ratio of the polyol having a heat dissipation capacity of 500 J / g · K or less and the polyfunctional isocyanate-based compound in a range from 1: 0.05 to 1: 0.25. Specifically, the molar ratio of the polyol having a heat release capacity of 500 J / g · K or less and the polyfunctional isocyanate-based compound may be 1: 0.05 to 1: 0.15, or 1: 0.07 to 0.12, and more specifically 1: 0.1. have.

When the content of the polyfunctional isocyanate-based compound in the third polyol mixture is within the above range, the polymer formed using the third polyol mixture may improve compatibility with other compositions.

According to an exemplary embodiment of the present invention, the content of the third polyol-based compound may be 15 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the polyol mixture. Specifically, the content of the third polyol-based compound may be 25 parts by weight or more and 40 parts by weight or less, or 25 parts by weight or more and 35 parts by weight with respect to 100 parts by weight of the polyol mixture.

By adjusting the content of the third polyol-based compound to the above-described range, compatibility with other materials in the flame-retardant polyurethane foam composition can be secured. In addition, when the content of the third polyol-based compound is within the above range, a UL-94 vertical flame retardant test result of the flame-retardant polyurethane foam enables to implement V-0-grade flame retardant properties, and hardening the flame-retardant polyurethane foam There is an advantage that can be minimized.

According to an exemplary embodiment of the present invention, the viscosity of the third polyol-based compound 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-based compound is within the above range, there is an advantage that can ensure 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-based compound and the third polyol-based compound may be 30 parts by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the polyol mixture. Specifically, the total content of the second polyol-based compound and the third polyol-based compound is 30 parts by weight or more and 50 parts by weight or less, or 30 parts by weight or more and 45 parts by weight or less, or 30 parts by weight based on 100 parts by weight of the polyol mixture. It may be greater than or equal to 40 parts by weight.

By adjusting the total content of the second polyol-based compound and the third polyol-based compound within the above-described range, the flame-retardant and compressive properties of the flame-retardant polyurethane foam containing the cured product of the flame-retardant polyurethane foam composition are effectively improved. You can.

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 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 phosphorus-based flame retardants 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 polymer surface, which can block the oxygen required for combustion to increase the flame retardancy of the flame retardant polyurethane foam. In addition, the non-halogen-type phosphorus-based flame retardant reacts with oxygen elements in the polymer to dehydrate and carbonize, and the radicals generated by the decomposition of phosphoric acid serve to stabilize the active radicals -OH and -H 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 with respect to 100 parts by weight of the polyol mixture. Specifically, the content of the flame retardant may be 21 parts by weight or more and 40 parts by weight or less, 21 parts by weight or more and 30 parts by weight or less, or 25 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the polyol mixture.

When the content of the flame retardant is within the above range, it is possible to obtain an effect of lowering the heat release capacity of the polyol-based compound in the flame retardant polyurethane foam composition and increasing the limiting oxygen index. In addition, when the content of the flame retardant is within the above range, it can help to form a polymer of a flame retardant polyurethane foam during combustion as a char, and can effectively remove radicals generated during combustion. Further, when the content of the flame retardant is within the above range, it is possible to secure the flame retardancy while minimizing the reduction in compression restoration performance of the flame retardant polyurethane foam.

According to an exemplary embodiment of the present invention, the dispersant may include titanate. By using a dispersant containing a titanate, the dispersibility of the flame retardant and expanded graphite in the flame retardant polyurethane foam composition can be improved. Through this, it is possible to improve the productability of the flame-retardant polyurethane foam containing the cured product of the flame-retardant polyurethane foam composition, and also improve the ductility without lowering the compressive and resilience of the flame-retardant polyurethane foam.

According to an exemplary embodiment of the present invention, the dispersant may be used by adopting a dispersant containing titanate used in the art without limitation. Specifically, the dispersant may include organic titanates. More specifically, the organic titanate may include an alkyl group having 1 to 25 carbon atoms. In the present invention, a dispersant containing isostearyl titanate may be used.

According to an exemplary embodiment of the present invention, the content of the dispersant may be 0.05 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the polyol mixture. Specifically, the content of the dispersant may be 0.5 parts by weight or more and 5 parts by weight or less, or 1 part by weight or more and 5 parts by weight or less based on 100 parts by weight of the polyol mixture. By adjusting the content of the dispersant in the above-described range, the product properties of the flame-retardant polyurethane foam can be improved, and also the ductility can be improved without lowering the compressive resilience of the flame-retardant polyurethane foam.

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 with respect to 100 parts by weight of the polyol mixture. Specifically, the content of the expanded graphite may be 21 parts by weight or more and 40 parts by weight or less, 21 parts by weight or more and 30 parts by weight or less, or 25 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the polyol mixture.

The expanded graphite has a layered crystal structure, and when heated, expands up to 20 to 400 times its original size to induce formation of porous carbides during combustion. Furthermore, when the content of the expanded graphite is adjusted within the above range, flame retardancy can be improved without lowering the compressive 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, the weight ratio of the flame retardant and the expanded graphite may be 1: 0.9 to 1: 1.1, and more specifically, 1: 1.

When the content of the flame retardant and the expanded graphite is adjusted 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 V-0 grade.

According to an exemplary embodiment of the present invention, the foam stabilizer may be applied as long as it is generally used in the production of urethane foam. Specifically, the foaming agent may include at least one of a silicone-based foaming agent, an organosilicon-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 foam stabilizer is not limited thereto, and a foam stabilizer generally used in the art may be used. By using the antifoaming agent, the foaming gas can form a foam structure suitable for polyurethane foam and maintain stable dispersion of the gas upon curing with the flame retardant polyurethane foam, thereby forming pores of uniform size and distribution. .

According to an exemplary embodiment of the present invention, the content of the foam stabilizer, 0.5 parts by weight or more and 10 parts by weight or less, 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 or more with respect to 100 parts by weight of the polyol mixture It may be:

The foaming gas is a gas that does not adversely affect the reaction between the polyol-based compound 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 polyol-based compound to the third polyol-based compound and form a polyurethane network.

According to an exemplary embodiment of the present invention, the isocyanate curing agent is a compound containing two or three or more isocyanate groups, and may include at least one of an aromatic isocyanate compound, an alicyclic isocyanate compound, and an aliphatic isocyanate compound. . The aromatic isocyanate compound, alicyclic isocyanate compound, and aliphatic isocyanate compound as the isocyanate curing agent may use the same materials as the aromatic isocyanate compound, alicyclic isocyanate compound, and aliphatic isocyanate compound in the second polyol mixture described above.

According to an exemplary embodiment of the present invention, the content of the isocyanate-based curing agent may be 20 parts by weight or more and 35 parts by weight or less with respect to 100 parts by weight of the polyol mixture. Specifically, the content of the isocyanate-based curing agent may be 25 parts by weight or more and 32.5 parts by weight or less, 27.5 parts by weight or more, 30 parts by weight or less, or 28 parts by weight or more and 32 parts by weight or less based on 100 parts by weight of the polyol mixture. By adjusting the content of the isocyanate curing agent to the above-described range, urethane bonding reaction with the first to third polyol compounds contained in the polyol mixture can be effectively performed.

According to an exemplary embodiment of the present invention, the flame retardant polyurethane foam composition may further include an additive including at least one 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 include at least one 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. Further, the metal catalyst may include at least one of a nickel-based compound, an organotin compound, an organic bismuth compound, an organic lead compound, an organic nickel compound, and an organic zinc compound.

According to an exemplary embodiment of the present invention, the content of the catalyst, 0.5 part by weight or more and 10 parts by weight or less, 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 or less with respect to 100 parts by weight of the polyol mixture You can.

According to an exemplary embodiment of the present invention, the crosslinking agent may have 2 to 4 active hydrogen-containing groups capable of reacting with an isocyanate group, and may have a low molecular weight compound having a number average molecular weight of 50 g / mol or more and 800 g / mol or less. 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 at least one 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 with respect to 100 parts by weight of the polyol mixture.

According to an exemplary embodiment of the present invention, the flame-retardant polyurethane foam composition may further include a dye. The dye may express the color of the flame-retardant polyurethane foam containing the cured product of the flame-retardant polyurethane foam composition. As the dye, what is used as a dye in the art can be used without limitation, for example, carbon black can be used.

The content of the dye may be 1 part by weight or more and 3 parts by weight or less with respect to 100 parts by weight of the polyol mixture. By adjusting the content of the dye in the above-described range, the physical properties of the flame-retardant polyurethane foam are not affected, and color can be implemented in the flame-retardant polyurethane foam.

One embodiment of the present invention. It provides a flame-retardant polyurethane foam comprising a cured product of the flame-retardant polyurethane foam composition.

One embodiment of the present invention provides a flame-retardant polyurethane foam formed using the flame-retardant polyurethane foam composition. The method of manufacturing a flame-retardant polyurethane foam using the flame-retardant polyurethane foam composition may use a method of manufacturing a generally known polyurethane foam.

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

1 shows a schematic diagram for UL-94 vertical flame retardance test. Specifically, in the UL-94 vertical flame retardant test, a specimen having a width of 125 ± 25 mm × a height of 13.0 ± 0.5 mm × a thickness of 2.0 mm is prepared. Five sets of two specimens prepared as one set were prepared, and stored at 23 ± 2 ° C., 50 ± 5% humidity, and a blue flame of methane gas having a calorific value of 37 MJ / ㎥ (flame height 20 mm, Using the distance between the lower part of the specimen and the end of the burner (9.5 mm), each specimen is burned twice for 10 seconds, and the flame disappears after the second 10 seconds (t2) and the duration of flameless combustion (t3) is measured. Then, grades are given according to the criteria as shown in Table 1 below.

UL-94 V test rating V-O V-1 V-2 Digestion time after the first or second combustion of each specimen (t1 or t2) ≤ 10 ≤ 30 ≤ 30 Sum of fire extinguishing time after 5 sets of total combustion (t1 + t2) ≤ 50 ≤ 250 ≤ 250 The sum of extinguishing time and non-combustion time after the second combustion of each specimen (t2 + t3) ≤ 30 ≤ 60 ≤ 60 Whether flame fragments or chunks fall and the cotton under the specimen 305 mm burns. NO NO YES

According to an exemplary embodiment of the present invention, the flame-retardant polyurethane foam may have a compression reduction rate of 10% or less measured after applying compression to 50% of the initial thickness and standing at room temperature for 70 hours. Specifically, according to an exemplary embodiment of the present invention, the flame-retardant polyurethane foam has a compressive permanent shrinkage of 9.5% or less, 7% or less, measured after compression at 50% of the initial thickness and standing at room temperature for 70 hours, or 6.5% or less. Therefore, the flame-retardant polyurethane foam according to an exemplary embodiment of the present invention has an advantage of excellent compression characteristics.

The compression reduction rate is a value measured according to KS M ISO 1956 standard (ISO 1856: 2000 correspondence). Specifically, the compression permanent shrinkage is KS M ISO 1956 standard (ISO 1856: 2000 correspondence), using a compression jig to compress the specimen to 50% compared to the initial thickness and left for 70 hours at 23 ± 2 ℃ 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 to the above range, effective compression restoration 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 flame-retardant polyurethane foam may have 1 or less pinholes having a diameter of 3 mm or less with respect to a surface area of 1,000 mm in width and 25,000 mm in length. Specifically, in the surface area of the flame-retardant polyurethane foam having a width of 1,000 mm and a length of 25,000 mm, one or less pinholes having a diameter of 3 mm or less may be present.

According to an exemplary embodiment of the present invention, the flame-retardant polyurethane foam may be in the form of pores therein, it can be suppressed that the pinhole is formed on the surface of the flame-retardant polyurethane foam.

Therefore, the surface of the flame-retardant polyurethane foam has the advantage of having excellent surface properties by suppressing the surface defect problem of pinhole generation.

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

Hereinafter, examples will be described in detail to specifically describe the present invention. However, the embodiments according to the present invention can be modified in various other forms, and the scope of the present invention is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present invention to those skilled in the art.

Preparation of polyol compounds

Manufacturing example  1: Preparation of the first polyol-based compound

50 parts 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 50 parts 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, followed by polymerization, and having a viscosity of 730 mPa. S, and a first polyol-based compound having a glass transition temperature of -71 ° C was prepared.

Manufacturing example  2: Preparation of second polyol-based compound

In a reactor in which nitrogen was 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, respectively, as a molar ratio to S2204 as shown in Table 2 below. It was put into the reactor. Then, the temperature was increased to 60 ° C., and 40 ppm of a catalyst (Dibutyltin dilaurate) was added. After stirring for 4 hours, the isocyanate peak disappeared through FT-IR, and the reaction was terminated to complete the second polyol-based compound as shown in Table 2 below. Was prepared.

SC2204 H12-MDI
(Molar ratio to SC2204) Glycerol
(Molar ratio to SC2204) Viscosity
(mPa · s) Mn
(g / mol) Mw
(g / mol) PDI Remark Preparation Example 2 One 0.9 0.3 65,000 5,770 15,000 2.6 Preparation Example 2-1 One 0.75 0.3 38,000 4,000 10,000 2.5 Preparation 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 Preparation Example 2-4 One 1.1 0.5 - - - - Gelation occurs Preparation Example 2-5 One 1.1 0.3 274,000 8,000 21,000 2.6 Viscosity is too high to mix

In Table 2, the molar ratio of H12-MDI and glycerol is relative to 1 mole of SC2204. As can be seen from Table 2, in the case of Preparation Example 2-3, it can be seen that a polyol having a linear structure is formed by not using a chain extender (glycerol) having three or more functional groups. In addition, in the case of Preparation Example 2-4, the content of the polyfunctional isocyanate-based compound (H12-MDI) and the content of the chain extender (glycerol) having three or more functional groups is too high to generate a gelling phenomenon to form a polyol-based compound. Did not. In addition, in the case of Preparation Example 2-5, the polyfunctional isocyanate-based compound (H12-MDI) had a high content, which greatly increased the viscosity, thereby forming a polyol that was difficult to mix with other compositions.

Manufacturing example  3: Preparation of third polyol-based compound

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 in a reactor in which nitrogen was refluxed, and then introduced into the reactor at a molar ratio of T5650E as shown in Table 3 below. Did. Then, the temperature was increased to 60 ° C., and 40 ppm of a catalyst (Dibutyltin dilaurate) was added. After stirring for 4 hours, the isocyanate peak disappeared through FT-IR, and the reaction was terminated. As shown in Table 3, the heat release capacity was 400. A third polyol-based compound having J / g · K was prepared.

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

In Table 3 above, the molar ratio of XDI is relative to 1 mole of T5650E. As can be seen from Table 3, Preparation Example 3-1 had a polyfunctional isocyanate-based compound (XDI) content that was too high, and polyol was produced with an excessively high viscosity, which was poor in compatibility with other components, resulting in phase separation. It was difficult to produce flame retardant polyurethane foam. In addition, in Production Example 3-1, there was a problem in that the internal hydrogen bond was too strong, and the self-cohesiveness was high, so that mixing with the first polyol-based compound and the second polyol-based compound was not well achieved.

Example  1: Preparation of flame retardant polyurethane foam

Prepared in Preparation Example 1 as a first polyol-based compound, prepared as prepared in Preparation Example 2 as a second polyol-based compound, and prepared as prepared in Preparation Example 3 as a third polyol-based compound .

In addition, a mixture of aluminum phosphate (Al phosphate) and flame retardant melamine cyanurate (MCA) as a flame retardant is prepared, GP-180 (Universal Camtech Co., Ltd.) having a size of 180 μm as expanded graphite is prepared, and as a foam stabilizer A polydimethylsiloxane substituted polyalkylsiloxane, L-626 (Momentive Co.) is prepared, a nickel-based catalyst LC5615 (Momentive Co.) is prepared, and H12-MDI (Kumho Mitsui Chemicals Co., Ltd.) is used as an isocyanate curing agent. ) Was prepared, and isostearyl titanate (CP317; Borica Co.) was prepared as a dispersant.

Then, 70 parts by weight of the first polyol-based compound, 10 parts by weight of the second polyol-based compound and 20 parts by weight of the third polyol-based compound were prepared to prepare a polyol mixture, and stainless steel equipped with a stirring device capable of high-speed stirring up to 2000 rpm The polyol mixture was introduced into a material mixing tank and stirred uniformly at room temperature. Then, with respect to 100 parts by weight of the polyol mixture, 25 parts by weight of a flame retardant, 25 parts by weight of expanded graphite, and 1 part by weight of a dispersant were added to disperse well, and then 2.5 parts by weight of a foam stabilizer and 3 parts by weight of a catalyst with respect to 100 parts by weight of the polyol mixture It was added and stirred at high speed for about 1 hour or more to prepare a uniform composition. At this time, the inflow of moisture was inhibited as much as possible because it inhibited the urethane reaction.

Furthermore, the prepared composition, isocyanate curing agent and nitrogen gas were simultaneously supplied to the high-speed mixing head at a constant rate using a metering pump. At this time, the isocyanate-based curing agent was added 28 parts by weight based on 100 parts by weight of the polyol mixture, nitrogen gas was supplied while adjusting the density and hardness. The three components were uniformly mixed to prepare a flame retardant polyurethane foam composition.

Then, after coating the prepared flame-retardant polyurethane foam composition on a polyester film, and cured at a high temperature in the range of about 120 ° C to 150 ° C in a reaction curing machine, the density is 0.3 g / cm 3, and the thickness is 2.0 mm. Foam sheets were prepared.

Subsequently, the produced flame-retardant polyurethane foam sheet was subjected to UL-94 vertical flame retardance test using the above-described method, compression to 50% of the initial thickness was added, and the compression permanent shrinkage measured after 70 hours at room temperature was measured. It is shown in Table 4 below.

In addition, the surface appearance state of the prepared flame-retardant polyurethane foam was evaluated as follows. For a surface area of 1,000 mm in width and 25,000 mm in length, a pinhole having a diameter of 3 mm or less was evaluated as good when there was 1 or less pinholes, and a defect was evaluated when 2 or more pinholes were present, and the results are shown in Table 4 below.

Example  2 to Example  3

A flame-retardant polyurethane foam sheet was prepared in the same manner as in Example 1, except that a flame-retardant polyurethane foam composition having a composition as shown in Table 4 was prepared.

Comparative example  1 and Comparative example  2

A flame-retardant polyurethane foam sheet was prepared in the same manner as in Example 1, except that a flame-retardant polyurethane foam composition having a composition as shown in Table 4 was prepared.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Polyol
mixture First polyol-based compound
(Parts by weight) Preparation Example 1 70 70 70 70 70 Second polyol-based compound
(Parts by weight) Preparation Example 2 10 10 10 10 10 Third polyol-based compound
(Parts by weight) Preparation Example 3 20 20 20 20 20 Polyol
mixture
100 parts by weight Flame retardant
(MCA / Al phosphate) 25 25 25 25 25 Expanded graphite
(180 μm) 25 25 25 25 25 Dispersant One 3 5 0.02 7 Antifoam 2.5 2.5 2.5 2.5 2.5 catalyst 3 3 3 3 3 Isocyanate curing agent 28 28 28 28 28 Flame retardant
Polyurethane
Form density
(g / cm 3) 0.3 0.3 0.3 0.3 0.3 thickness
(Mm) 2 2 2 2 2 UL-94 vertical flame retardant test V-0 V-0 V-0 V-0 V-0 Permanent compression reduction rate (%) 4.8 6.4 9.2 4.8 15 Surface appearance condition Good Good Good Bad Good

In Table 4, the flame retardant, expanded graphite, dispersant, foam stabilizer, catalyst and isocyanate-based curing agent content are based on 100 parts by weight of the polyol mixture (parts by weight).

Referring to Table 4, in the case of Examples 1 to 3, wherein the content of the dispersant is 0.05 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the polyol mixture, the prepared flame retardant polyurethane foam has flame retardant properties, compressive properties, and It was confirmed that the surface appearance was excellent. On the other hand, in the case of Comparative Example 1 in which the content of the dispersant is less than 0.05 parts by weight with respect to 100 parts by weight of the polyol mixture, the surface appearance of the prepared flame-retardant polyurethane foam is poor, and as the product quality is inferior, it is used as an actual product. It was confirmed that it was not suitable. In addition, in the case of Comparative Example 2 in which the content of the dispersant is more than 5 parts by weight with respect to 100 parts by weight of the polyol mixture, it was confirmed that the compression properties of the prepared flame-retardant polyurethane foam are very inferior.

Therefore, it can be seen that the flame-retardant polyurethane foam composition according to one embodiment of the present invention can provide a flame-retardant polyurethane foam having excellent compressive properties and flame-retardant properties and excellent surface appearance.

Claims (16)

A first polyol-based compound having a glass transition temperature of -50 ° C or less; A second polyol-based compound containing at least three functional groups that react with an isocyanate group; And a third polyol-based compound having a heat dissipation capacity of 500 J / g · K or less;
Isocyanate curing agents;
Antifoaming agent;
Flame retardants;
Expanded graphite; And
Dispersing agent comprising a titanate; flame-retardant polyurethane foam composition comprising a.
The method according to claim 1,
The content of the dispersant is a flame retardant polyurethane foam composition of 0.05 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the polyol mixture.
The method according to claim 1,
The content of the first polyol-based compound is 60 parts by weight or more and 75 parts by weight or less based on 100 parts by weight of the polyol mixture, and a flame retardant polyurethane foam composition.
The method according to claim 1,
The content of the second polyol-based compound is 5 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the polyol mixture, and a flame retardant polyurethane foam composition.
The method according to claim 1,
The content of the third polyol-based compound is a flame-retardant polyurethane foam composition of 15 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the polyol mixture.
The method according to claim 1,
The second polyol-based compound,
Polyether-based polyols; Polyfunctional isocyanate-based compounds; And a chain extender comprising three or more functional groups that react with isocyanate groups; a flame retardant polyurethane foam composition that is a polymer of a second polyol mixture comprising.
The method according to claim 6,
The second polyol mixture is a flame retardant polyurethane foam composition in which the molar ratio of the polyether-based polyol and the chain extender is 1: 0.1 to 1: 0.45.
The method according to claim 1,
The third polyol-based compound,
Polyols having a heat dissipation capacity of 500 J / g · K or less; or
A flame-retardant polyurethane foam composition that is a polymer of a polyol having a heat dissipating capacity of 500 J / gK or less and a third polyol mixture comprising a polyfunctional isocyanate-based compound.
The method according to claim 8,
The third polyol mixture is a flame retardant polyurethane foam composition in which the molar ratio of the polyol having a heat release capacity of 500 J / gK or less and the polyfunctional isocyanate compound is 1: 0.05 to 1: 0.25.
The method according to claim 1,
The content of the flame retardant is a flame retardant polyurethane foam composition that is 21 parts by weight or more and 50 parts by weight or less based on 100 parts by weight of the polyol mixture.
The method according to claim 1,
The content of the expanded graphite is a flame-retardant polyurethane foam composition that is 21 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the polyol mixture.
Flame-retardant polyurethane foam comprising a cured product of the flame-retardant polyurethane foam composition according to claim 1.
The method according to claim 12,
The flame-retardant polyurethane foam is a flame-retardant polyurethane foam having a flame-retardant property of V-0 grade as a result of UL-94 vertical flame retardancy test.
The method according to claim 12,
The flame-retardant polyurethane foam is a flame-retardant polyurethane foam having a compressive permanent shrinkage of 10% or less measured after applying compression at 50% of the initial thickness and standing at room temperature for 70 hours.
The method according to 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.
The method according to claim 12,
The flame-retardant polyurethane foam is a flame-retardant polyurethane foam having 1 or less pinholes having a diameter of 3 mm or less, for a surface area of 1,000 mm in width and 25,000 mm in length.

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