KR102629416B1 - Flame-retardant and self-extinguishing polyurethane foam pad and method thereof - Google Patents

Abstract

The present invention relates to a flame-retardant and self-extinguishing polyurethane foam pad that can be applied to electric vehicle batteries, solar power generation devices, etc., to minimize damage from fire and prevent casualties, and to a method of manufacturing the same.
The present invention is applied to electric vehicle batteries, energy storage systems (ESS) of solar power generation devices, etc. to provide polyurethane foam with excellent flame retardancy and self-extinguishing properties, excellent shock absorption and resilience, and mica sheets with excellent heat resistance, thermal conductivity and thermal stability. By combining and, in particular, implementing a new polyurethane foam and mica sheet combination that integrates polyurethane foam and mica sheet in the form of a foam pad, various damage caused by fire can be minimized and at the same time, flame retardancy and mica sheet can be actively responded to fire prevention. A self-extinguishing polyurethane foam pad and a method for manufacturing the same are provided.

Description

Flame retardant and self-extinguishing polyurethane foam pad and method of manufacturing the same {FLAME-RETARDANT AND SELF-EXTINGUISHING POLYURETHANE FOAM PAD AND METHOD THEREOF}

The present invention relates to a flame retardant and self-extinguishing polyurethane foam pad and a method of manufacturing the same. More specifically, the present invention relates to a flame retardant and self-extinguishing polyurethane foam pad and a method of manufacturing the same. More specifically, the present invention relates to a flame retardant and self-extinguishing polyurethane foam pad that can be applied to electric vehicle batteries, solar power generation devices, etc. to minimize damage from fire and prevent human casualties. It relates to fire extinguishing polyurethane foam pads and methods of manufacturing them.

Generally, batteries are used in electric vehicles to supply electrical energy to drive the vehicle.

These batteries consist of a battery pack that can create high voltage by connecting multiple unit cells or modules, and use this to generate high power.

In other words, the energy stored in the battery is transferred to the motor through an inverter and used for vehicle starting, acceleration, and engine operation at high efficiency points. When excess energy is generated in the engine, the motor is used as a generator and the excess energy is stored in the battery.

Since these batteries use a fairly large amount of current and generate a lot of heat internally, it is most important to prevent fires that may occur in the battery due to overcurrent or short circuit in electric vehicles using batteries.

Since electric vehicles usually contain various electronic equipment such as motors and batteries, the possibility of a fire occurring due to a short circuit or other reasons cannot be ruled out. The bigger problem is that a fire in such an electric vehicle is highly likely to lead to a large-scale fire and loss of life. It's there.

Taking this into consideration, research and development have recently been conducted to minimize damage caused by fire by applying flame-retardant polyurethane foam pads between cells of electric vehicle battery modules.

As an example, a technology has been proposed to minimize the risk of ignition and suppress the spread of fire as much as possible by placing polyurethane foam pads between cells of a battery module.

As another example, a product has been proposed in which sheet-type mica (Mica), which has excellent heat resistance, thermal conductivity, and thermal stability, is applied to a polyurethane foam pad disposed between cells of a battery module.

In the case of a product that combines a polyurethane foam pad and a mica sheet, the polyurethane foam pad and the mica sheet are used by adhering them with adhesive or double-sided tape. In this case, the adhesive or double-sided tape is made of highly flammable acrylic material. When a fire occurs and a flame of approximately 1,000℃ is applied, the adhesive or double-sided tape melts and burns. Eventually, the flame accelerates using the adhesive or double-sided tape as a medium, causing flames to spread across the entire area of the polyurethane foam pad. As there is a problem that it can spread and lead to a bigger fire, there is a need to prepare countermeasures.

Public Patent Publication No. 10-2022-0168657 Registered Patent Publication No. 10-2332128 Registered Patent Publication No. 10-2425374 Registered Patent Publication No. 10-2477902

Therefore, the present invention was developed with these points in mind, and can be applied to electric vehicle batteries, energy storage systems (ESS) of solar power generation devices, etc. to provide polyurethane foam with excellent flame retardancy, self-extinguishing properties, and excellent shock absorption and resilience. By combining mica sheets with excellent heat resistance, thermal conductivity, and thermal stability, and in particular by implementing a new polyurethane foam and mica sheet combination that integrates polyurethane foam and mica sheets in the form of a foam pad, various damage caused by fire can be minimized. The purpose is to provide a flame-retardant and self-extinguishing polyurethane foam pad and a method of manufacturing the same that can actively respond to fire prevention at the same time.

In order to achieve the above object, the manufacturing method of the flame retardant and self-extinguishing polyurethane foam pad provided by the present invention has the following characteristics.

The method of manufacturing the flame-retardant and self-extinguishing polyurethane foam pad includes the steps of coating the surface of a mica sheet with a polyurethane foam foam liquid foamed through a foaming process to combine the polyurethane foam and the mica sheet, and the polyurethane foam is coated. It is characterized in that it includes the step of drying the prepared mica sheet to integrally fix the polyurethane foam and the mica sheet.

In addition, in the step of drying and fixing the polyurethane foam and mica sheet, the mica sheet coated with polyurethane foam is placed in a drying furnace and dried at a temperature of 60 to 200°C.

In addition, the mica sheet is characterized in that it is manufactured by applying at least one selected from muscovite, biotite, and phlogopite.

In addition, the mica sheet is characterized in that it is manufactured in the form of a composite sheet containing glass fiber.

In addition, the step of coating and bonding polyurethane foam to the surface of the mica sheet is characterized by coating polyurethane foam on one or both surfaces of the mica sheet.

In addition, the polyurethane foam contains 30 to 90 parts by weight of a flame retardant, 1 to 20 parts by weight of expanded graphite, 5 to 30 parts by weight of filler, and ink, based on 100 parts by weight of the polyol mixture having a weight average molecular weight in the range of 100 to 5000 g/mol. 1 to 10 parts by weight, 0.1 to 10 parts by weight of crosslinking agent, 0.1 to 5 parts by weight of organometallic compound catalyst, 0.1 to 5 parts by weight of foam stabilizer, 0.1 to 5 parts by weight of phosphoric acid ester type anionic surfactant, and 20 to 50 parts by weight. Containing 10 to 70 parts by weight of an isocyanate-based curing agent having an NCO% value, wherein the polyol mixture includes at least one selected from the group consisting of polyester-based polyol, polyether-based polyol, polycaprolactone-based polyol, and mixtures thereof. The flame retardant is a mixture of phosphorus-based flame retardant and melamine-based flame retardant in a weight ratio of 1:0.1 to 0.6, and the filler is selected from the group consisting of calcium carbonate, wollastonite, potassium titanate, spicule, and mixtures thereof. and the organometallic compound-based catalyst includes at least one selected from the group consisting of potassium octylate, cobalt naphthenate, nickel acetylacetonate, and mixtures thereof, and the anti-foaming agent is It is a silicone-based foam stabilizer, and the isocyanate-based curing agent is characterized in that it contains at least one selected from the group consisting of polymeric methylene diphenyl diisocyanate (PMDI), modified methylene diphenyl diisocyanate, and mixtures thereof.

In addition, the polyol mixture has 2 functional groups, 10 to 40% by weight of polyester polyol with a weight average molecular weight in the range of 200 to 5000 g/mol, and 2 or 3 functional groups, and a weight average molecular weight of 200 to 5000 g. 10 to 40% by weight of polyether-based polyol in the range of /mol, the number of functional groups is 2, and 0 to 40% by weight of polycaprolactone-based polyol with a weight average molecular weight in the range of 100 to 2000 g/mol and the number of functional groups is 3, weight It is a mixture of 0 to 40% by weight of polycaprolactone-based polyol with an average molecular weight in the range of 100 to 2000 g/mol, and the organometallic compound-based catalyst is potassium octylate, cobalt naphthenate, and nickel acetylacetonate at a ratio of 1:0.1 to 1:0.1. It is mixed at a weight ratio of 0.5:0.1 to 0.5, and the isocyanate-based curing agent is characterized by mixing polymeric methylene diphenyl diisocyanate (PMDI) and modified methylene diphenyl diisocyanate at a weight ratio of 1:2 to 10.

In addition, the filler is characterized in that it includes 100 parts by weight of calcium carbonate, 20 to 80 parts by weight of wollastonite, 20 to 80 parts by weight of potassium titanate, and 1 to 10 parts by weight of spicules.

In addition, the spicule is a needle-shaped Spongilla lacustris spicule whose surface has been modified to be hydrophilic, and the needle-shaped Spongilla lacustris spicule whose surface has been modified to be hydrophilic is crushed Spongilla lacustris spicule. Extracting Sponzilla lacustris spicules by supporting them in a hydrochloric acid solution, adding hydrogen peroxide, heating, and sonicating; A step of soaking the extracted Spongilla lacustris spicules in a hydrochloric acid solution, washing them with phosphate-buffered saline to neutral acidity, and then drying them to obtain needle-shaped Spongilla lacustris spicules; reacting the needle-shaped Spongilla lacustris spicules and hydrogen peroxide for 6 to 20 hours to form pores on the surface of the needle-shaped Spongilla lacustris spicules; It is characterized in that it is manufactured by a manufacturing method that includes the step of modifying the surface to be hydrophilic by reacting a needle-shaped Spongilla lacustris spicule with pores formed on the surface with a basic compound.

Meanwhile, in order to achieve the above object, the flame retardant and self-extinguishing polyurethane foam pad provided by the present invention has the following characteristics.

The flame retardant and self-extinguishing polyurethane foam pad is made by coating the surface of the mica sheet with the polyurethane foam foam liquid foamed through a foaming process, combining the polyurethane foam and the mica sheet, and then combining the mica sheet coated with the polyurethane foam. It is characterized by integrally fixing polyurethane foam and mica sheets through drying treatment.

In addition, when drying and fixing the polyurethane foam and mica sheet, the mica sheet coated with polyurethane foam is placed in a drying furnace and dried at a temperature of 60 to 200°C.

In addition, the mica sheet is characterized by applying at least one selected from muscovite, biotite, and phlogopite.

In addition, the mica sheet is characterized in that it is manufactured in the form of a composite sheet containing glass fiber.

In addition, when polyurethane foam is coated and bonded to the surface of the mica sheet, the polyurethane foam is coated on one or both surfaces of the mica sheet.

In addition, the polyurethane foam contains 30 to 90 parts by weight of a flame retardant, 1 to 20 parts by weight of expanded graphite, 5 to 30 parts by weight of filler, and ink, based on 100 parts by weight of the polyol mixture having a weight average molecular weight in the range of 100 to 5000 g/mol. 1 to 10 parts by weight, 0.1 to 10 parts by weight of crosslinking agent, 0.1 to 5 parts by weight of organometallic compound catalyst, 0.1 to 5 parts by weight of foam stabilizer, 0.1 to 5 parts by weight of phosphoric acid ester type anionic surfactant, and 20 to 50 parts by weight. Containing 10 to 70 parts by weight of an isocyanate-based curing agent having an NCO% value, wherein the polyol mixture includes at least one selected from the group consisting of polyester-based polyol, polyether-based polyol, polycaprolactone-based polyol, and mixtures thereof. The flame retardant is a mixture of phosphorus-based flame retardant and melamine-based flame retardant in a weight ratio of 1:0.1 to 0.6, and the filler is selected from the group consisting of calcium carbonate, wollastonite, potassium titanate, spicule, and mixtures thereof. and the organometallic compound-based catalyst includes at least one selected from the group consisting of potassium octylate, cobalt naphthenate, nickel acetylacetonate, and mixtures thereof, and the anti-foaming agent is It is a silicone-based foam stabilizer, and the isocyanate-based curing agent is characterized in that it contains at least one selected from the group consisting of polymeric methylene diphenyl diisocyanate (PMDI), modified methylene diphenyl diisocyanate, and mixtures thereof.

In addition, the polyol mixture has 2 functional groups, 10 to 40% by weight of polyester polyol with a weight average molecular weight in the range of 200 to 5000 g/mol, and 2 or 3 functional groups, and a weight average molecular weight of 200 to 5000 g. 10 to 40% by weight of polyether-based polyol in the range of /mol, the number of functional groups is 2, and 0 to 40% by weight of polycaprolactone-based polyol with a weight average molecular weight in the range of 100 to 2000 g/mol and the number of functional groups is 3, weight It is a mixture of 0 to 40% by weight of polycaprolactone-based polyol with an average molecular weight in the range of 100 to 2000 g/mol, and the organometallic compound-based catalyst is potassium octylate, cobalt naphthenate, and nickel acetylacetonate at a ratio of 1:0.1 to 1:0.1. It is mixed at a weight ratio of 0.5:0.1 to 0.5, and the isocyanate-based curing agent is characterized by mixing polymeric methylene diphenyl diisocyanate (PMDI) and modified methylene diphenyl diisocyanate at a weight ratio of 1:2 to 10.

In addition, the filler is characterized in that it includes 100 parts by weight of calcium carbonate, 20 to 80 parts by weight of wollastonite, 20 to 80 parts by weight of potassium titanate, and 1 to 10 parts by weight of spicules.

In addition, the spicule is a needle-shaped Spongilla lacustris spicule whose surface has been modified to be hydrophilic, and the needle-shaped Spongilla lacustris spicule whose surface has been modified to be hydrophilic is crushed Spongilla lacustris spicule. Extracting Sponzilla lacustris spicules by supporting them in a hydrochloric acid solution, adding hydrogen peroxide, heating, and sonicating; A step of soaking the extracted Spongilla lacustris spicules in a hydrochloric acid solution, washing them with phosphate-buffered saline to neutral acidity, and then drying them to obtain needle-shaped Spongilla lacustris spicules; reacting the needle-shaped Spongilla lacustris spicules and hydrogen peroxide for 6 to 20 hours to form pores on the surface of the needle-shaped Spongilla lacustris spicules; It is characterized in that it is manufactured by a manufacturing method that includes the step of modifying the surface to be hydrophilic by reacting a needle-shaped Spongilla lacustris spicule with pores formed on the surface with a basic compound.

The flame retardant and self-extinguishing polyurethane foam pad provided by the present invention and its manufacturing method have the following effects.

First, polyurethane foam with excellent flame retardancy and self-extinguishing properties, excellent shock absorption and resilience, and mica sheet with excellent heat resistance, thermal conductivity and thermal stability, which are applied to electric vehicle batteries and solar power generation energy storage systems (ESS). By applying a combined type of polyurethane foam pad, there is an effect of reducing the risk caused by fire, such as preventing fire and preventing the spread of fire in the event of a fire, and minimizing various damage caused by fire.

Second, by applying a new polyurethane foam pad that integrates polyurethane foam and mica sheet or composite sheet into a foam pad, even when a flame of approximately 1,000℃ is applied in the event of a fire, only the area directly in contact with the flame is localized. By preventing the spread of fire, such as damage, damage caused by fire can be reduced as much as possible and it has the effect of actively responding to fire prevention.

Third, compared to methods using existing adhesives or double-sided tapes, the overall manufacturing process can be simplified, which has the effect of improving productivity, reducing manufacturing costs, and ensuring excellent product quality.

Fourth, since it can be manufactured to the same specifications as the pad currently applied to battery modules, it can be easily applied to both new battery modules as well as existing battery modules, such as being able to be applied as is without improving the structure or design of the battery module. It works.

Fifth, the cell structure is finely and uniformly organized, maintaining high density and high strength in the range of 0.1 to 0.5 g/cm ³ , and not only has the effect of realizing excellent shock absorption and resilience, but also has the effect of realizing excellent shock absorption and resilience, and the results of the UL-94 vertical flame retardant test V It has the effect of having excellent flame retardancy and self-extinguishing properties of -0 grade.

As a result, it can be very useful in all household items, including electronic devices such as computers and communications, sports and medical products, and cushions and dustproof materials for automobiles. Even when applied to high-temperature devices, the risk of ignition can be minimized. It has the effect of effectively absorbing shock between parts and improving the durability of the device.

Sixth, when applied between cells of an electric vehicle battery or on the plate surface of a module composed of one or more cells, it not only provides insulation effect, but also dimensional stability against changes in cell volume, vibration and shock. It has the effect of realizing excellent stress absorption, excellent resilience, and high fire resistance.

1 is a process diagram showing a method of manufacturing a flame-retardant and self-extinguishing polyurethane foam pad according to an embodiment of the present invention.
Figure 2 is a perspective view and cross-sectional view showing an example of a flame-retardant and self-extinguishing polyurethane foam pad according to an embodiment of the present invention.
Figure 3 is a perspective view and cross-sectional view showing another example of a flame-retardant and self-extinguishing polyurethane foam pad according to an embodiment of the present invention.
Figure 4 is a perspective view and cross-sectional view showing another example of a flame-retardant and self-extinguishing polyurethane foam pad according to an embodiment of the present invention.
Figure 5 is a perspective view showing the use state of a flame-retardant and self-extinguishing polyurethane foam pad according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to the attached drawings.

Figure 1 is a process diagram showing a method of manufacturing a flame-retardant and self-extinguishing polyurethane foam pad according to an embodiment of the present invention.

The method of manufacturing the flame-retardant and self-extinguishing polyurethane foam pad consists of combining polyurethane foam on the surface of a mica sheet and fixing the combined mica sheet and polyurethane foam.

First, the polyurethane foam foam liquid foamed through the foaming process is coated on the surface of the mica sheet to bond the polyurethane foam and the mica sheet.

For this purpose, polyols such as ether-based polyol, ester-based polyol, caprolactone-based polyol, and polycarbonate-based polyol, fillers such as calcium carbonate and silica, black paste, which is a dispersion containing black pigment, a catalyst, and a foaming agent, Hardening materials such as Polymeric MDI, Modified MDI, etc. are mixed and stirred to create a premix mixture (polyol, filler, black paste, catalyst, foam stabilizer, etc.), and the premix mixture is placed in a foaming machine and foamed. Make polyurethane foam foam.

Here, in the foaming machine, the base material, curing agent, and inert gas are mechanically mixed to foam.

Then, as a base material, a plate-shaped mica sheet is made.

At this time, the mica sheet can be made of muscovite, biotite, phlogopite, etc., and can be manufactured by applying at least one selected from among them.

As a preferred embodiment, the mica sheet may be manufactured in the form of a composite sheet containing glass fiber, which has excellent durability, chemical resistance, electrical insulation, fire resistance, etc.

Here, the mica sheet containing the glass fiber may be a combination of a mica sheet and glass fiber manufactured by high-temperature fusion using a binder made of silicon.

In this way, a composite sheet that combines mica sheets and glass fibers, for example, a form in which mica sheets and glass fibers are laminated and bonded in two layers, or a form in which glass fibers are mixed and bonded within a mica sheet, can exhibit flexible characteristics. It has the advantage of securing a wide range of application.

Subsequently, the polyurethane foam foam liquid from the foamer is put into a coater, and the polyurethane foam foam liquid is coated on the surface of the substrate, that is, the mica sheet, to a certain thickness through the coater.

Here, the thickness of the polyurethane foam coated on the mica sheet is preferably about 0.5 to 4.0 mm, and the mica sheet thickness at this time is also preferably about 0.1 to 2.0 mm.

For example, if the thickness of the polyurethane foam is outside the above range and is thin, it is difficult to respond to the compression and expansion of the cell, and if it is thick, the battery cell structure becomes large and requires a large space, reducing space efficiency.

In addition, if the thickness of the mica sheet is outside the above range and is thin, there are problems such as insufficient fire resistance and poor electrical insulation, and if it is thick, cracks occur in the mica sheet and productivity is reduced.

In addition, in the step of coating and bonding polyurethane foam to the surface of the mica sheet, polyurethane foam may be coated on one or both surfaces of the mica sheet.

At this time, the mica sheet coated with the polyurethane foam can be a mica sheet made of any mica among muscovite, black silver mica, or gold and silver mica, or it can be a mica sheet in the form of a composite sheet in which glass fibers are combined. there is.

Next, the mica sheet coated with the polyurethane foam is dried to integrally fix the polyurethane foam and the mica sheet.

That is, a mica sheet coated with polyurethane foam is placed in a drying furnace, and heat-treated in the drying furnace at a temperature of about 60 to 200°C for about 1 to 20 minutes to cure the polyurethane foam on the mica sheet. By doing so, it is possible to form a polyurethane foam pad integrated with polyurethane foam and mica sheet.

Next, a step is performed to prevent tacky spots by UV coating the surface of the polyurethane foam coated and cured on the surface of the mica sheet with a urethane-acrylic coating agent.

This step is to improve the quality of the product by preventing it from sticking when the polyurethane foam pad product is rolled up.

Next, the polyurethane foam and mica sheet coated with the urethane-acrylic material on the surface are subjected to UV drying to fix (cure) the urethane-acrylic material.

Meanwhile, in one embodiment of the present invention, 30 to 90 parts by weight of a flame retardant, 1 to 20 parts by weight of expanded graphite, and 5 to 30 parts by weight of a filler are added to 100 parts by weight of a polyol mixture having a weight average molecular weight in the range of 100 to 5000 g/mol. , 1 to 10 parts by weight of ink, 0.1 to 10 parts by weight of crosslinking agent, 0.1 to 5 parts by weight of organometallic compound catalyst, 0.1 to 5 parts by weight of foam stabilizer, 0.1 to 5 parts by weight of phosphoric acid ester type anionic surfactant, and 20 to 50 parts by weight. Containing 10 to 70 parts by weight of an isocyanate-based curing agent having an NCO% value in the range;

The polyol mixture includes at least one selected from the group consisting of polyester-based polyol, polyether-based polyol, polycaprolactone-based polyol, and mixtures thereof;

The flame retardant is a mixture of a phosphorus-based flame retardant and a melamine-based flame retardant in a weight ratio of 1:0.1 to 0.6;

The filler includes one or more selected from the group consisting of calcium carbonate, wollastonite, potassium titanate, spicules, and mixtures thereof;

The organometallic compound-based catalyst includes at least one member selected from the group consisting of potassium octylate, cobalt naphthenate, nickel acetylacetonate, and mixtures thereof;

The antifoam agent is a silicone-based antifoam agent;

The isocyanate-based curing agent is a flame retardant having excellent shock absorption and high strength performance, which includes at least one selected from the group consisting of polymeric methylene diphenyl diisocyanate (PMDI), modified methylene diphenyl diisocyanate, and mixtures thereof. A polyurethane foam pad made of a self-extinguishing polyurethane foam composition is provided.

According to the flame-retardant and self-extinguishing polyurethane foam pad with excellent shock absorption and high strength performance according to an embodiment of the present invention and its manufacturing method, the cell structure is fine and uniformly organized to produce a density in the range of 0.1 to 0.5 g/cm ³ It has the effect of achieving excellent shock absorption and resilience while maintaining high density and high strength. In addition, as a result of the UL-94 vertical flame retardancy test, it has excellent flame retardancy and self-extinguishing properties of V-0 grade.

As a result, it can be very useful in all household items, including electronic devices such as computers and communications, sports and medical products, and cushions and dustproof materials for automobiles. Even when applied to high-temperature devices, the risk of ignition can be minimized. It has the effect of effectively absorbing shock between parts and improving the durability of the device.

In particular, between cells of electric vehicle batteries; Or, when applied to the plate surface of a module composed of one or more cells, it provides not only insulation effect, but also dimensional stability against cell volume changes, excellent stress absorption against vibration and impact, excellent resilience, and high fire resistance. There is an effect that can be implemented.

More specifically, the flame-retardant and self-extinguishing polyurethane foam pad with excellent shock absorption and high strength performance according to an embodiment of the present invention contains a flame retardant for 100 parts by weight of a polyol mixture having a weight average molecular weight in the range of 100 to 5000 g/mol. 30 to 90 parts by weight, expanded graphite 1 to 20 parts by weight, filler 5 to 30 parts by weight, ink 1 to 10 parts by weight, crosslinking agent 0.1 to 10 parts by weight, organometallic compound catalyst 0.1 to 5 parts by weight, foam stabilizer 0.1 to 10 parts by weight It contains 5 parts by weight, 0.1 to 5 parts by weight of a phosphoric acid ester type anionic surfactant, and 10 to 70 parts by weight of an isocyanate-based curing agent having an NCO% value in the range of 20 to 50.

First, the polyol mixture having a weight average molecular weight in the range of 100 to 5000 g/mol reacts with an isocyanate-based curing agent to maintain high density and high strength while maintaining excellent shock absorption and resilience. At the same time, in order to maintain appropriate viscosity and improve workability, the weight average molecular weight of the polyol mixture may be more preferably in the range of 100 to 5000 g/mol.

The above effect can be further improved by using the polyol mixture containing at least one selected from the group consisting of polyester-based polyol, polyether-based polyol, polycaprolactone-based polyol, and mixtures thereof.

At this time, the polyester-based polyol has excellent tensile strength, thermal stability, and chemical resistance due to the strong interaction of the ester bond, and can exhibit good elasticity even at low temperatures.

More specifically, the polyester polyol can preferably be obtained by condensation of dicarboxylic acid and diol.

At this time, non-limiting examples of the dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, isophthalic acid, maleic acid, fumaric acid, At least one selected from the group consisting of itaconic acid, tetrabromophthalic acid, trimeritic acid or their ester derivatives, acid anhydrides, and mixtures thereof can be preferably used.

In addition, non-limiting examples of the diol include ethylene glycol, propylene glycol, butanediol, pentanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, trimethylolpropane, glycerin, and pentaerythritol. , quinitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, lipopylene glycol, diglycerin, dextrose, sorbitol, and mixtures thereof. there is.

A more preferable polyester-based polyol has the number of functional groups of 2 and a weight average molecular weight in the range of 200 to 5000 g/mol.

In addition, the polyether-based polyol has an -O- bond in the molecule that is easily free to rotate, so it provides flexibility to the molecule and can exhibit mechanical properties such as excellent elasticity, compression set, and elongation even at low temperatures.

More specifically, the polyether-based polyol can preferably be one obtained by polymerizing a polyfunctional alcohol or a polyfunctional amine and alkylene oxide.

At this time, non-limiting examples of the polyfunctional alcohol include ethylene glycol, diethylene glycol, glycerin, trimethanol propane, pentaerythritol, dipentaerythritol, α-methyl glucoside, xylitol, sorbitol, sugar, and mixtures thereof. One or more types selected from the group consisting of can be preferably used.

In addition, non-limiting examples of the multifunctional amine include one selected from the group consisting of ethylenediamine, diethylenetriamine, triethanolamine, ortho-toluenediamine, diphenylmethanediamine, diethanolamine, and mixtures thereof. The above can be preferably used.

In addition, the alkylene oxide compound is a compound having at least one alkylene oxide group, for example, ethylene oxide, propylene oxide (1,2-epoxypropane), butylene oxide (1,4-epoxybutane), 1, 2-epoxybutane, 2,3-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, a At least one selected from the group consisting of mylene oxide, styrene oxide, and mixtures thereof can be preferably used.

More preferably, the polyether-based polyol has 2 or 3 functional groups and a weight average molecular weight in the range of 200 to 5000 g/mol.

The polycaprolactone-based polyol functions to improve heat resistance, water resistance, and workability. In consideration of the above-mentioned improvement effect, the polycaprolactone-based polyol is preferably contained in the polyol mixture in the range of 20 to 60% by weight.

More specifically, the polycaprolactone-based polyol can preferably be one obtained by ring-opening polymerization of ε-caprolactone using a polyol initiator or a polyamine initiator.

At this time, non-limiting examples of the polyol initiator include ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,6-hexanediol, neopentyl glycol, bisphenol A, and reso. Diols such as Resin; Triols such as glycerin, 1,2,6-hexanetriol, and 1,1,1-tris(hydroxymethyl)propane; tetraols such as pentaerythritol, erythritol, and methylglucoxide; Hexaol such as sorbitol and dipentaerythritol; At least one selected from the group consisting of octanol such as sucrose and mixtures thereof can be preferably used.

Additionally, non-limiting examples of the polyamine initiator include diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, and hydrazine; One or more polyamines selected from the group consisting of trifunctional or higher polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and mixtures thereof can be preferably used.

Non-limiting examples of commercially available polycaprolactone-based polyols include Tone™ 0240, 1241, 2241, or 1231; Capa™ 2043, 2077A, 2100A, 2125, 2205, 2201, 2101A, 2123A, 2161A, 2200A, 2200D, 2200P, 2201A, 2203A, 2209, 2302A, 2303, 2304, 2 402, 2403D, 2054, 2803, 3022, 3031, 3041, 3091, 3201, 3301, 4801, 7201A, 7203, HCl060, or HCl100; Alternatively, one or more selected from the group consisting of Placcel™ 205, 208, 210, 220, 220 CPB, 230, 230 CP, 240 or 240 CP, and mixtures thereof may be preferably used.

More preferably, the polycaprolactone-based polyol has 2 or 3 functional groups and a weight average molecular weight in the range of 100 to 2000 g/mol.

More specifically, in consideration of the above-mentioned improvement effect, the polyol mixture contains 10 to 40% by weight of a polyester-based polyol having a functional group of 2 and a weight average molecular weight in the range of 200 to 5000 g/mol; 10 to 40% by weight of a polyether-based polyol having 2 or 3 functional groups and a weight average molecular weight in the range of 200 to 5000 g/mol; 0 to 40% by weight of a polycaprolactone-based polyol having a functional group of 2 and a weight average molecular weight of 100 to 2000 g/mol; and a mixture of 0 to 40% by weight of a polycaprolactone-based polyol having a functional group count of 3 and a weight average molecular weight ranging from 100 to 2000 g/mol can be more preferably used.

Hereinafter, the content of other components constituting the flame-retardant and self-extinguishing polyurethane foam pad with excellent shock absorption and high strength performance is based on 100 parts by weight of the polyol mixture having a weight average molecular weight in the range of 100 to 5000 g/mol.

The flame retardant functions to provide excellent flame retardancy and heat resistance.

The above-mentioned effect can be further improved by using a mixture of phosphorus-based flame retardant and melamine-based flame retardant in a weight ratio of 1:0.1 to 0.6.

At this time, the phosphorus-based flame retardant is a phosphorus-based flame retardant commonly used in the art, and the type is not particularly limited, but for example, phosphate-based flame retardants, phosphonate-based flame retardants, phosphinate-based flame retardants, phosphazene-based flame retardants, At least one selected from the group consisting of melamine phosphate flame retardants, ammonium polyphosphate flame retardants, ammonium phosphinate flame retardants, phosphophenanthrene flame retardants, phosphine oxide flame retardants, and mixtures thereof can be preferably used. A more preferable phosphorus-based flame retardant may be one containing diethyl-N,N-bis(2-hydroxyethyl)aminomethylphosphonate.

In addition, the melamine-based flame retardant is a melamine-based flame retardant commonly used in the art, and the type is not particularly limited, but for example, melamine phosphate, melamine pyrophosphate, and mixtures thereof. One or more types selected from the group consisting of can be preferably used.

The flame retardant is preferably contained in an amount of 30 to 90 parts by weight based on 100 parts by weight of the polyol mixture having a weight average molecular weight of 100 to 5000 g/mol. If the content of the flame retardant is too small, the improvement effect may be insufficient, and if the content of the flame retardant is too high, there is a problem that strength and compression recovery performance may be reduced.

The expanded graphite has a layered crystal structure, and when heated, it expands 20 to 400 times its original size, thereby inducing the formation of porous carbides during combustion, thereby further improving excellent flame retardancy and self-extinguishing properties.

The above effect can be further improved by using the expanded graphite with an expansion rate of 20 to 400 ml/g and a particle size of 30 to 500 mesh.

The expanded graphite is preferably contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the polyol mixture having a weight average molecular weight of 100 to 5000 g/mol. If the content of the expanded graphite is too small, there is a problem that the improvement effect described above may be insufficient, and if the content of the expanded graphite is too large, there is a problem that it can cause a decrease in strength.

The filler not only maintains excellent high density and high strength, but also increases hardness and improves elastic modulus to provide excellent shock absorption and resilience. It has the function of improving flame retardancy and self-extinguishing properties by improving thermal stability.

The filler is preferably contained in an amount of 5 to 30 parts by weight based on 100 parts by weight of the polyol mixture having a weight average molecular weight of 100 to 5000 g/mol. If the content of the filler is too small, the improvement effect may be insufficient, and if the content of the filler is too large, workability may be reduced.

The filler may preferably include one or more selected from the group consisting of calcium carbonate, wollastonite, potassium titanate, spicules, and mixtures thereof.

More preferably, the filler may include 100 parts by weight of calcium carbonate, 20 to 80 parts by weight of wollastonite, 20 to 80 parts by weight of potassium titanate, and 1 to 10 parts by weight of spicules.

At this time, the calcium carbonate provides an excellent filling effect, maintains high density and high strength, and provides excellent flame retardant performance.

Hereinafter, the content of other components constituting the filler is based on 100 parts by weight of the calcium carbonate.

The wollastonite provides an excellent filling effect and functions to maintain high density and high strength.

The wollastonite is preferably contained in the range of 20 to 80 parts by weight based on 100 parts by weight of the calcium carbonate. If the wollastonite content is too small, the improvement effect may be insufficient, and if the wollastonite content is too large, workability may be reduced.

The potassium titanate provides an excellent filling effect and functions to maintain high density and high strength.

The above effect can be further improved by using potassium titanate having a specific surface area of 0.3 to 3 m ² /g.

The potassium titanate is preferably contained in the range of 20 to 80 parts by weight based on 100 parts by weight of the calcium carbonate. If the content of potassium titanate is too small, there is a problem that the above-described improvement effect may be insufficient, and if the content of potassium titanate is too high, there is a problem that price competitiveness may be reduced.

The spicule provides an excellent filling effect, maintaining high density and high strength, as well as excellent shock absorption and resilience. It has the function of improving flame retardancy and self-extinguishing properties.

More specifically, by using the spicule, which is a needle-shaped Spongilla lacustris spicule whose surface has been modified to be hydrophilic, the above effect can be further improved.

The needle-shaped Sponzilla lacustris spicule whose surface was modified to be hydrophilic was made by supporting crushed Spongilla lacustris in a hydrochloric acid solution, adding hydrogen peroxide, heating and ultrasonic treatment to form Spongilla lacustris spicules. Extracting step; A step of soaking the extracted Spongilla lacustris spicules in a hydrochloric acid solution, washing them with phosphate-buffered saline to neutral acidity, and then drying them to obtain needle-shaped Spongilla lacustris spicules; reacting the needle-shaped Spongilla lacustris spicules and hydrogen peroxide for 6 to 20 hours to form pores on the surface of the needle-shaped Spongilla lacustris spicules; and reacting a needle-shaped Spongilla lacustris spicule with pores formed on the surface with a basic compound to modify the surface to be hydrophilic.

At this time, it is preferable that the crushed Spongilla lacustris is crushed so that the average particle size is 10 to 50 μm.

In addition, the basic compound is generally known in the art, and its type is not particularly limited, but includes calcium hydroxide (Ca(OH) ₂ ) at a concentration of 3 to 7 N and magnesium hydroxide (Mg(OH) at a concentration of 3 to 7 N. ) By using a mixture of ₂ ) in a volume ratio of 1: 1 to 3, excellent strength improvement and flame retardant performance improvement effects can be obtained.

The spicule is preferably contained in the range of 1 to 10 parts by weight based on 100 parts by weight of the calcium carbonate. If the content of the spicules is too small, the improvement effect may be insufficient, and if the content of the spicules is too large, price competitiveness may be reduced.

The ink functions to represent color.

The ink may be a conventional ink containing colored pigments or dyes such as titanium dioxide and carbon black.

The ink is preferably contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the polyol mixture having a weight average molecular weight of 100 to 5000 g/mol. If the content of the ink is too small, the improvement effect may be insufficient, and if the content of the ink is too high, the mechanical properties may be deteriorated.

The cross-linking agent functions to achieve high density and strength by strengthening intermolecular bonds.

These crosslinking agents are commonly used in the art and are not particularly limited in type, but for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol. , polyhydric alcohols such as neopentyl glycol, glycerin, trimethylolpropane, triethanolamine, and alkylene oxide adducts of bisphenol A, polyamines such as diethyltoluenediamine, chlorodiaminobenzene, ethylenediamine, and 1,6-hexanediamine, etc. and one or more types selected from the group consisting of mixtures thereof may be used.

The crosslinking agent is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyol mixture having a weight average molecular weight of 100 to 5000 g/mol. If the content of the cross-linking agent is too small, there is a problem that the improvement effect described above may be insufficient, and if the content of the cross-linking agent is too large, there is a problem that shock absorption and resilience may be reduced.

The organometallic compound-based catalyst maintains a long foam cell formation time so that the cells are finely and uniformly organized, thereby providing excellent strength, shock absorption, and resilience.

The organometallic compound-based catalyst may preferably include one or more selected from the group consisting of potassium octylate, cobalt naphthenate, nickel acetylacetonate, and mixtures thereof.

More preferably, the organometallic compound-based catalyst is a mixture of potassium octylate, cobalt naphthenate, and nickel acetylacetonate in a weight ratio of 1: 0.1 to 0.5: 0.1 to 0.5 to further improve the above effect. there is.

The organometallic compound catalyst is preferably contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyol mixture having a weight average molecular weight of 100 to 5000 g/mol. If the content of the organometallic compound catalyst is too small, the improvement effect may be insufficient, and if the content of the organometallic compound catalyst is too large, workability may be reduced.

The foam stabilizer maintains stable dispersibility of gas when cured into foam, forming pores of uniform size and distribution, thereby providing excellent strength, shock absorption, and resilience.

The foam stabilizer is a silicone-based foam stabilizer, and more specifically, one containing polysiloxane-polyalkylene oxide copolymer can be preferably used.

The foam stabilizer is preferably contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyol mixture having a weight average molecular weight of 100 to 5000 g/mol. If the content of the foam stabilizer is too small, the improvement effect may be insufficient, and if the content of the foam stabilizer is too large, workability may be reduced.

The phosphoric acid ester-type anionic surfactant not only maintains stable dispersibility of gas when cured into foam to form pores of uniform size and distribution, but also provides excellent strength, shock absorption, and shock absorption by including phosphoric acid ester on the surface of the pores. In addition to resilience, it has the function of realizing excellent flame retardancy and self-extinguishing properties.

These phosphate ester type anionic surfactants include alkyl (C8 to 12) phosphate ester, polyoxyethylene alkyl (C12 to 18) ether phosphate ester, polyoxyethylene alkyl (C8 to 12) phenyl ether phosphate ester, and polyoxyethylene alkyl. (C8 to 12) Phosphate ester of polymer of phenyl ether, polyoxyethylene phenyl phenyl ether phosphate ester, polyoxyethylene benzyl phenyl ether phosphate ester, polyoxyethylene styryl phenyl ether phosphate ester, polymer of polyoxyethylene styryl phenyl ether Phosphate esters such as phosphoric acid esters, phosphoric acid esters of polyoxyethylene polyoxypropylene block polymers, phosphatidylcholine, phosphatidylethanolimine, and condensed phosphoric acids (e.g., tripolyphosphoric acid, etc.) and salts of these phosphoric acid esters can be used.

The phosphoric acid ester type anionic surfactant is preferably contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyol mixture having a weight average molecular weight of 100 to 5000 g/mol. If the content of the phosphate ester type anionic surfactant is too small, there is a problem that the improvement effect may be insufficient, and if the content of the phosphate ester type anionic surfactant is too large, workability may be reduced. There is a problem.

The isocyanate-based curing agent having an NCO% value in the range of 20 to 50 forms a urethane bond with the polyol mixture and forms a polyurethane network, maintaining high density and high strength, while maintaining excellent shock absorption and resilience.

Non-limiting examples of the isocyanate-based curing agent include ethylene diisocyanate, toluene diisocyanate, tolylene diisocyanate, methylene diphenyl diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate, xylene diisocyanate, and polymethylene polyphenylene. Isocyanate, hydrogenated methylene diphenyl diisocyanate, hydrogenated tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, modified products thereof, and mixtures thereof. You can use the above. At this time, the modified product may be a prepolymer-type modified product, a nurate-modified product, a urea-modified product, a carbodiimide-modified product, an arophanate-modified product, or a biuret-modified product.

A more preferable isocyanate-based curing agent may be one containing at least one selected from the group consisting of polymeric methylene diphenyl diisocyanate (PMDI), modified methylene diphenyl diisocyanate, and mixtures thereof.

More preferably, the above-described effect can be further improved by using a mixture of polymeric methylene diphenyl diisocyanate (PMDI) and modified methylene diphenyl diisocyanate in a weight ratio of 1:2 to 10 as the isocyanate-based curing agent. At this time, uretonimine-modified methylene diphenyl diisocyanate can be more preferably used as the modified methylene diphenyl diisocyanate.

The isocyanate-based curing agent having an NCO% value in the range of 20 to 50 is preferably contained in an amount of 10 to 70 parts by weight based on 100 parts by weight of the polyol mixture having a weight average molecular weight of 100 to 5000 g/mol. If the content of the isocyanate-based curing agent having an NCO% value in the range of 20 to 50 is too small, there is a problem that the improvement effect may be insufficient, and the content of the isocyanate-based curing agent having an NCO% value in the range of 20 to 50 If there is too much of this, there is a problem that the hardness may become too high and the shock absorption performance may deteriorate.

The flame retardant and self-extinguishing polyurethane foam pad with excellent shock absorption and high strength performance is used between cells of an electric vehicle battery; Alternatively, it may be attached to the plate surface of a module comprised of one or more cells. This has the effect of realizing not only an insulating effect, but also dimensional stability against changes in cell volume, excellent stress absorption against vibration and impact, excellent resilience, and high fire resistance.

In addition, in another embodiment of the present invention, 30 to 90 parts by weight of flame retardant, 1 to 20 parts by weight of expanded graphite, and 5 to 30 parts by weight of filler, based on 100 parts by weight of the polyol mixture having a weight average molecular weight in the range of 100 to 5000 g/mol. parts by weight, 1 to 10 parts by weight of ink, 0.1 to 10 parts by weight of crosslinking agent, 0.1 to 5 parts by weight of organometallic compound catalyst, 0.1 to 5 parts by weight of foam stabilizer, and 0.1 to 5 parts by weight of phosphoric acid ester type anionic surfactant, preparing a premix mixture; Mixing the premix mixture with 10 to 70 parts by weight of an isocyanate-based curing agent having an NCO% value in the range of 20 to 50, and simultaneously injecting nitrogen gas using a foamer to foam the polyurethane foam; and heat-treating the polyurethane foam at a temperature of 60 to 200° C. to provide a method for manufacturing a flame-retardant and self-extinguishing polyurethane foam pad with excellent shock absorption and high strength performance.

Each component included in the flame-retardant and self-extinguishing polyurethane foam pad with excellent shock absorption and high strength performance is as described above in “Flame retardant and self-extinguishing polyurethane foam pad with excellent shock absorption and high strength performance”.

This flame-retardant and self-extinguishing polyurethane foam pad with excellent shock absorption and high strength performance is environmentally friendly and can achieve the above-described excellent effects by performing mechanical foaming using nitrogen as a foaming agent. More specifically, the foaming can be performed by foaming by injecting nitrogen gas at a pressure of 1 to 8 bar.

Additionally, non-limiting examples of the foaming machine include an automatic mixing injection type foaming machine and an automatic mixing injection foaming machine.

In addition, the heat treatment temperature is such that the flame-retardant and self-extinguishing polyurethane foam pad with excellent shock absorption and high strength performance of the present invention does not cause discoloration (yellowing) or heat deformation, improves tensile strength and tear strength, and further improves compression characteristics. It is preferably carried out in a temperature range of 60 to 200° C. to effectively promote the polyaddition reaction and promote high molecular weight of the polyurethane foam.

According to an embodiment of the present invention, a flame-retardant and self-extinguishing polyurethane foam pad with excellent shock absorption and high strength performance and a manufacturing method thereof, the cell structure is fine and uniformly organized to provide a high density in the range of 0.1 to 0.5 g/cm ³ It has the effect of realizing excellent shock absorption and resilience while maintaining high strength. In addition, as a result of the UL-94 vertical flame retardancy test, it has excellent flame retardancy and self-extinguishing properties of V-0 grade.

As a result, it can be very useful in all household items, including electronic devices such as computers and communications, sports and medical products, and cushions and dustproof materials for automobiles. Even when applied to high-temperature devices, the risk of ignition can be minimized. It has the effect of effectively absorbing shock between parts and improving the durability of the device.

In particular, between cells of electric vehicle batteries; Or, when applied to the plate surface of a module composed of one or more cells, it provides not only insulation effect, but also dimensional stability against cell volume changes, excellent stress absorption against vibration and impact, excellent resilience, and high fire resistance. There is an effect that can be implemented.

Above, the present invention has been described in detail with preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications may be made by those skilled in the art within the scope of the technical idea of the present invention. This is possible.

<Manufacturing Example 1>

Preparation of needle-shaped Sponzilla lacustris spicules with pores formed on the surface

The crushed Sponzilla lacustris was soaked in 0.1M hydrochloric acid solution for 15 minutes, then 5 ml/g of 30% (w/w) hydrogen peroxide was added and heated for 2 hours, then heated for 1 hour at 300 W and 40 kHz. After ultrasonic treatment, the process of filtration and washing with 500 ml of purified water was repeated three times to extract Sponzilla lacustris spicules.

Thereafter, the extracted Sponzilla lacustris spicules were soaked in a 0.5 M hydrochloric acid solution for 1 day, washed with phosphate-buffered saline to neutralize the acidity, washed three times with purified water, and dried at 50°C. I got my brother's Spongilla Lacustris spicule.

Afterwards, 20 ml/g of 35% (w/w) hydrogen peroxide was added to the needle-shaped Spongilla lacustris spicules and stirred and reacted for 15 hours to form pores in the needle-shaped Spongilla lacustris spicules ( pore) was formed. Afterwards, the process of filtration and washing with 500 ml of purified water was repeated three times, and then dried at 50° C. to obtain needle-shaped Spongilla lacustris spicules with pores formed on the surface.

<Manufacturing Example 2>

Preparation of needle-shaped Spongilla lacustris spicules with surfaces modified to be hydrophilic.

The crushed Sponzilla lacustris was soaked in 0.1M hydrochloric acid solution for 15 minutes, then 5 ml/g of 30% (w/w) hydrogen peroxide was added and heated for 2 hours, then heated for 1 hour at 300 W and 40 kHz. After ultrasonic treatment, the process of filtration and washing with 500 ml of purified water was repeated three times to extract Sponzilla lacustris spicules.

Thereafter, the extracted Sponzilla lacustris spicules were soaked in a 0.5 M hydrochloric acid solution for 1 day, washed with phosphate-buffered saline to neutralize the acidity, washed three times with purified water, and dried at 50°C. I got my brother's Spongilla Lacustris spicule.

Afterwards, 20 ml/g of 35% (w/w) hydrogen peroxide was added to the needle-shaped Spongilla lacustris spicules and stirred and reacted for 15 hours to form pores in the needle-shaped Spongilla lacustris spicules ( pore) was formed. Afterwards, the process of filtration and washing with 500 ml of purified water was repeated three times, and then dried at 50° C. to obtain needle-shaped Spongilla lacustris spicules with pores formed on the surface.

10 ml/g of 1N NaOH was added to the needle-shaped Spongilla lacustris spicule with pores formed on the surface and reacted at 40° C. for 1 hour. Afterwards, the process of filtration and washing with 500 ml of purified water was repeated three times, and then dried at 50° C. to obtain needle-shaped Spongilla lacustris spicules whose surfaces were modified to be hydrophilic (hydroxyl groups).

<Production Example 3>

Preparation of needle-shaped Spongilla lacustris spicules with surfaces modified to be hydrophilic.

The crushed Sponzilla lacustris was soaked in 0.1M hydrochloric acid solution for 15 minutes, then 5 ml/g of 30% (w/w) hydrogen peroxide was added and heated for 2 hours, then heated for 1 hour at 300 W and 40 kHz. After ultrasonic treatment, the process of filtration and washing with 500 ml of purified water was repeated three times to extract Sponzilla lacustris spicules.

Thereafter, the extracted Sponzilla lacustris spicules were soaked in a 0.5 M hydrochloric acid solution for 1 day, washed with phosphate-buffered saline to neutralize the acidity, washed three times with purified water, and dried at 50°C. I got my brother's Spongilla Lacustris spicule.

Afterwards, 20 ml/g of 35% (w/w) hydrogen peroxide was added to the needle-shaped Spongilla lacustris spicules and stirred and reacted for 15 hours to form pores in the needle-shaped Spongilla lacustris spicules ( pore) was formed. Afterwards, the process of filtration and washing with 500 ml of purified water was repeated three times, and then dried at 50° C. to obtain needle-shaped Spongilla lacustris spicules with pores formed on the surface.

Calcium hydroxide (Ca(OH) _{2 ) at a concentration of 5 N and magnesium hydroxide (Mg(OH) 2 )} at a concentration of 5 N were added to the needle-shaped Spongilla lacustris spicule with pores formed on the surface in a ratio of 1: 10 ml/g of basic compound mixed at a volume ratio of 1.5 was added and reacted at 40°C for 1 hour. Afterwards, the process of filtration and washing with 500 ml of purified water was repeated three times, and then dried at 50° C. to obtain needle-shaped Spongilla lacustris spicules whose surfaces were modified to be hydrophilic (hydroxyl groups).

<Examples and Comparative Examples>

A flame retardant and self-extinguishing polyurethane foam composition with excellent shock absorption and high strength performance and a comparative composition were prepared as shown in [Table 1] below. More specifically, a premix mixture is prepared by mixing a polyol mixture, flame retardant, expanded graphite, filler, ink, crosslinking agent, organometallic compound catalyst, foam stabilizer, and phosphoric acid ester type anionic surfactant; The premix mixture was mixed with an isocyanate-based curing agent, and at the same time, nitrogen gas was injected and foamed at a pressure of 5 bar using a foamer to prepare polyurethane foam. Afterwards, the polyurethane foam was heat treated at a temperature of 150°C.

The test examples below are experiments comparing the characteristics of the Examples according to the present invention and Comparative Examples 1 and 2 so that the characteristics of Examples 1 to 3 according to the present invention disclosed above can be more easily understood. It shows the results.

<Test example>

Performance evaluation was conducted on the flame-retardant and self-extinguishing polyurethane foam composition with excellent shock absorption and high strength performance prepared in the above Example and the comparative composition prepared in the Comparative Example, and the results are shown in Table 2 below.

As can be seen in Table 2, the flame retardant and self-extinguishing polyurethane foam composition with excellent shock absorption and high strength performance prepared in the examples of the present invention has high density and high density compared to the comparative composition prepared in the comparative example. It was confirmed that it had excellent shock absorption and resilience while maintaining high strength. In addition, as a result of the UL-94 vertical flame retardancy test, it was confirmed that it had excellent flame retardancy and self-extinguishing properties with a V-0 rating.

Figures 2 to 4 are perspective views and cross-sectional views showing several examples of flame-retardant and self-extinguishing polyurethane foam pads according to embodiments of the present invention.

As shown in Figures 2 to 4, the polyurethane foam pad 13 is a combination of a mica sheet 10 and a polyurethane foam 11, and is formed by combining the mica sheet 10 and polyurethane without using an adhesive. It is formed by directly combining the foam 11 using a coating method.

For this purpose, polyurethane foam 11 is coated on the surface of the mica sheet 10 to a predetermined thickness, and accordingly, the polyurethane foam pad 13 is made of the mica sheet 10 and the poly polyurethane foam pad 13 forming a two-layer laminated structure. It is made of urethane foam (11).

For example, liquid polyurethane foam 11 foamed through a foaming process is coated on the surface of the mica sheet 10 to combine the polyurethane foam 11 and the mica sheet 10, and then the mica sheet ( By drying and fixing the polyurethane foam (11) coated on 10), it is possible to make a polyurethane foam pad (13) in which the polyurethane foam (11) and the mica sheet (10) are integrally combined. .

Here, the polyurethane foam 11 can be bonded to one or both surfaces of the mica sheet 10.

In the polyurethane foam pad 13 made by combining the polyurethane foam 11 and the mica sheet 10, the thickness of the polyurethane foam is preferably about 0.5 to 4.0 mm, and the mica sheet thickness at this time is also 0.1 to 0.1 mm. A thickness of about 2.0 mm is desirable.

In addition, the polyurethane foam 11 bonded to the surface of the mica sheet 10 can be bonded to one or both surfaces of the mica sheet 10.

At this time, the mica sheet 10 may be made of muscovite, biotite, phlogopite, etc.

As a preferred embodiment, the mica sheet 10 may be in the form of a composite sheet including glass fiber 12, which has excellent durability, chemical resistance, electrical insulation, fire resistance, etc.

Here, the form of the composite sheet made of the mica sheet 10 containing the glass fiber 12 is a form in which the glass fiber 12 is laminated on one side of the mica sheet 10 to form a two-layer form, the mica sheet 10 The glass fibers 12 can be stacked on both sides to form three layers, or the glass fibers 12 can be mixed within the mica sheet 10 to form a single body.

At this time, the composite sheet can secure a wide range of applications, such as being able to exert a flexible function due to the characteristics of the glass fiber 12.

In addition, the surface of the polyurethane foam 11 coupled to the mica sheet 10 may be coated with a urethane acrylic UV coating, and in this case, the urethane acrylic UV coating is a tag formed on the surface of the polyurethane foam 11. It has the function of eliminating energy.

At this time, the urethane-acrylic UV coating agent can be dried in a UV drying furnace using a UV drying method and fixed to the polyurethane foam (11).

Figure 5 is a perspective view showing the use state of a flame-retardant and self-extinguishing polyurethane foam pad according to an embodiment of the present invention.

As shown in Figure 5, here is an example of applying the polyurethane foam pad 13 to the battery module 14 of an electric vehicle.

The battery module 14 includes a battery module case 15, a plurality of battery cells 16 installed inside the battery module case 15, and a plurality of battery cells 16 inserted between each battery cell 16. Includes a polyurethane pad (13).

In addition, by equipping the polyurethane foam pad 13 installed between the battery cells 16 with fire prevention and damage reduction functions, explosion or fire of the battery cell 16 can be prevented in advance, and Even in the event of a fire, secondary damage such as chain explosion of the battery cell 16 can be prevented.

For example, by interposing the polyurethane foam pad 13, which has excellent fire resistance even in flames of 1,000°C or higher, between each battery cell 16, not only does it suppress the occurrence of fire, but it also prevents chain explosions of the battery module 14 due to fire. Secondary damage can be prevented.

As such, in the present invention, polyurethane foam with excellent flame retardancy and self-extinguishing properties, excellent shock absorption and resilience, heat resistance, thermal conductivity and thermal stability is applied to electric vehicle batteries, solar power generation energy storage systems (ESS), etc. By providing a new type of polyurethane foam pad that combines excellent mica sheets, various types of damage caused by fire can be minimized and proactive measures can be taken to prevent fires.

10: mica sheet
11: Polyurethane foam
12: Glass fiber
13: Polyurethane foam pad
14: Battery module
15: module case
16: battery cell

Claims (18)

A step of combining the polyurethane foam and the mica sheet by coating the surface of the mica sheet with the polyurethane foam foam liquid foamed through the foaming process, and drying the mica sheet coated with the polyurethane foam to form the polyurethane foam and the mica sheet. A method of manufacturing a flame retardant and self-extinguishing polyurethane foam pad, comprising the step of integrally fixing the sheet.
In claim 1,
In the step of drying and fixing the polyurethane foam and the mica sheet, the mica sheet coated with the polyurethane foam is placed in a drying furnace and dried at a temperature of 60 to 200 ° C. Flame retardant and self-extinguishing polyurethane foam Pad manufacturing method.
In claim 1,
A method of manufacturing a flame-retardant and self-extinguishing polyurethane foam pad, characterized in that the mica sheet is manufactured by applying at least one selected from muscovite, biotite, and phlogopite.
In claim 1 or claim 3,
A method of manufacturing a flame-retardant and self-extinguishing polyurethane foam pad, characterized in that the mica sheet is manufactured in the form of a composite sheet containing glass fiber.
In claim 1,
In the step of coating and bonding polyurethane foam to the surface of the mica sheet, a method of manufacturing a flame-retardant and self-extinguishing polyurethane foam pad, characterized in that polyurethane foam is coated on one or both surfaces of the mica sheet.
In claim 1,
The polyurethane foam contains 30 to 90 parts by weight of a flame retardant, 1 to 20 parts by weight of expanded graphite, 5 to 30 parts by weight of filler, and 1 to 1 to 2 parts by weight of ink, based on 100 parts by weight of the polyol mixture having a weight average molecular weight in the range of 100 to 5000 g/mol. 10 parts by weight, 0.1 to 10 parts by weight of crosslinking agent, 0.1 to 5 parts by weight of organometallic compound catalyst, 0.1 to 5 parts by weight of foam stabilizer, 0.1 to 5 parts by weight of phosphoric acid ester type anionic surfactant, and NCO% in the range of 20 to 50. An isocyanate-based curing agent having a value of 10 to 70 parts by weight, wherein the polyol mixture includes at least one selected from the group consisting of polyester-based polyol, polyether-based polyol, polycaprolactone-based polyol, and mixtures thereof. , The flame retardant is a mixture of a phosphorus-based flame retardant and a melamine-based flame retardant in a weight ratio of 1: 0.1 to 0.6, and the filler is 1 selected from the group consisting of calcium carbonate, wollastonite, potassium titanate, spicule, and mixtures thereof. It contains more than one species, and the organometallic compound-based catalyst includes at least one selected from the group consisting of potassium octylate, cobalt naphthenate, nickel acetylacetonate, and mixtures thereof, and the foam stabilizer is a silicone-based stabilizer. flame retardant and self-extinguishing poly, wherein the isocyanate-based curing agent includes at least one selected from the group consisting of polymeric methylene diphenyl diisocyanate (PMDI), modified methylene diphenyl diisocyanate, and mixtures thereof. Manufacturing method of urethane foam pad.
In claim 6,
The polyol mixture has a functional group of 2, a weight average molecular weight of 10 to 40% by weight of a polyester polyol in the range of 200 to 5000 g/mol, a functional group of 2 or 3, and a weight average molecular weight of 200 to 5000 g/mol. 10 to 40% by weight of polyether-based polyol in the range of 10 to 40% by weight, the number of functional groups is 2, and 0 to 40% by weight of polycaprolactone-based polyol with a weight average molecular weight in the range of 100 to 2000 g/mol, and the number of functional groups is 3, and the weight average molecular weight is 3. It is a mixture of 0 to 40% by weight of polycaprolactone-based polyol in the range of 100 to 2000 g/mol, and the organometallic compound-based catalyst is potassium octylate, cobalt naphthenate, and nickel acetylacetonate in a ratio of 1:0.1 to 0.5: It is mixed at a weight ratio of 0.1 to 0.5, and the isocyanate-based curing agent is a flame retardant and magnetic curing agent characterized in that polymeric methylene diphenyl diisocyanate (PMDI) and modified methylene diphenyl diisocyanate are mixed at a weight ratio of 1: 2 to 10. Method for manufacturing fire extinguishing polyurethane foam pad.
In claim 6,
Production of a flame-retardant and self-extinguishing polyurethane foam pad, characterized in that the filler includes 100 parts by weight of calcium carbonate, 20 to 80 parts by weight of wollastonite, 20 to 80 parts by weight of potassium titanate, and 1 to 10 parts by weight of spicules. method.
In claim 8,
The spicule is a needle-shaped Sponzilla lacustris spicule whose surface has been modified to be hydrophilic, and the needle-shaped Spongilla lacustris spicule whose surface has been modified to be hydrophilic is crushed Spongilla lacustris in hydrochloric acid. Extracting Sponzilla lacustris spicules by soaking them in a solution, adding hydrogen peroxide, heating, and sonicating; A step of soaking the extracted Spongilla lacustris spicules in a hydrochloric acid solution, washing them with phosphate-buffered saline to neutral acidity, and then drying them to obtain needle-shaped Spongilla lacustris spicules; reacting the needle-shaped Spongilla lacustris spicules and hydrogen peroxide for 6 to 20 hours to form pores on the surface of the needle-shaped Spongilla lacustris spicules; Flame-retardant and self-extinguishing polyurethane, characterized in that it is manufactured by a manufacturing method comprising the step of modifying the surface to be hydrophilic by reacting a needle-shaped Spongilla lacustris spicule with pores formed on the surface with a basic compound. Manufacturing method of foam pad.
The polyurethane foam foam liquid foamed through the foaming process is coated on the surface of the mica sheet to combine the polyurethane foam and the mica sheet. Then, the mica sheet coated with the polyurethane foam is dried to combine the polyurethane foam and the mica sheet. A flame retardant and self-extinguishing polyurethane foam pad characterized by being integrally fixed.
In claim 10,
When drying and fixing the polyurethane foam and mica sheet, the mica sheet coated with polyurethane foam is placed in a drying furnace and dried at a temperature of 60 to 200 ° C. Flame retardant and self-extinguishing polyurethane foam pad.
In claim 10,
The mica sheet is a flame-retardant and self-extinguishing polyurethane foam pad, characterized in that at least one selected from muscovite, biotite, and phlogopite is applied.
In claim 10 or claim 12,
A flame-retardant and self-extinguishing polyurethane foam pad, characterized in that the mica sheet is manufactured in the form of a composite sheet containing glass fiber.
In claim 10,
A flame retardant and self-extinguishing polyurethane foam pad, characterized in that polyurethane foam is coated on one or both surfaces of the mica sheet when the polyurethane foam is coated and bonded to the surface of the mica sheet.
In claim 10,
The polyurethane foam contains 30 to 90 parts by weight of a flame retardant, 1 to 20 parts by weight of expanded graphite, 5 to 30 parts by weight of filler, and 1 to 1 to 2 parts by weight of ink, based on 100 parts by weight of the polyol mixture having a weight average molecular weight in the range of 100 to 5000 g/mol. 10 parts by weight, 0.1 to 10 parts by weight of crosslinking agent, 0.1 to 5 parts by weight of organometallic compound catalyst, 0.1 to 5 parts by weight of foam stabilizer, 0.1 to 5 parts by weight of phosphoric acid ester type anionic surfactant, and NCO% in the range of 20 to 50. An isocyanate-based curing agent having a value of 10 to 70 parts by weight, wherein the polyol mixture includes at least one selected from the group consisting of polyester-based polyol, polyether-based polyol, polycaprolactone-based polyol, and mixtures thereof. , The flame retardant is a mixture of a phosphorus-based flame retardant and a melamine-based flame retardant in a weight ratio of 1: 0.1 to 0.6, and the filler is 1 selected from the group consisting of calcium carbonate, wollastonite, potassium titanate, spicule, and mixtures thereof. It contains more than one species, and the organometallic compound-based catalyst includes at least one selected from the group consisting of potassium octylate, cobalt naphthenate, nickel acetylacetonate, and mixtures thereof, and the foam stabilizer is a silicone-based stabilizer. flame retardant and self-extinguishing poly, wherein the isocyanate-based curing agent includes at least one selected from the group consisting of polymeric methylene diphenyl diisocyanate (PMDI), modified methylene diphenyl diisocyanate, and mixtures thereof. Urethane foam pad.
In claim 15,
The polyol mixture has a functional group of 2, a weight average molecular weight of 10 to 40% by weight of a polyester polyol in the range of 200 to 5000 g/mol, a functional group of 2 or 3, and a weight average molecular weight of 200 to 5000 g/mol. 10 to 40% by weight of polyether-based polyol in the range of 10 to 40% by weight, the number of functional groups is 2, and 0 to 40% by weight of polycaprolactone-based polyol with a weight average molecular weight in the range of 100 to 2000 g/mol, and the number of functional groups is 3, and the weight average molecular weight is 3. It is a mixture of 0 to 40% by weight of polycaprolactone-based polyol in the range of 100 to 2000 g/mol, and the organometallic compound-based catalyst is potassium octylate, cobalt naphthenate, and nickel acetylacetonate in a ratio of 1:0.1 to 0.5: It is mixed at a weight ratio of 0.1 to 0.5, and the isocyanate-based curing agent is a flame retardant and magnetic curing agent characterized in that polymeric methylene diphenyl diisocyanate (PMDI) and modified methylene diphenyl diisocyanate are mixed at a weight ratio of 1: 2 to 10. Digestive polyurethane foam pad.
In claim 15,
A flame retardant and self-extinguishing polyurethane foam pad, characterized in that the filler includes 100 parts by weight of calcium carbonate, 20 to 80 parts by weight of wollastonite, 20 to 80 parts by weight of potassium titanate, and 1 to 10 parts by weight of spicules.
In claim 17,
The spicule is a needle-shaped Sponzilla lacustris spicule whose surface has been modified to be hydrophilic, and the needle-shaped Spongilla lacustris spicule whose surface has been modified to be hydrophilic is crushed Spongilla lacustris in hydrochloric acid. Extracting Sponzilla lacustris spicules by soaking them in a solution, adding hydrogen peroxide, heating, and sonicating; A step of soaking the extracted Spongilla lacustris spicules in a hydrochloric acid solution, washing them with phosphate-buffered saline to neutral acidity, and then drying them to obtain needle-shaped Spongilla lacustris spicules; reacting the needle-shaped Spongilla lacustris spicules and hydrogen peroxide for 6 to 20 hours to form pores on the surface of the needle-shaped Spongilla lacustris spicules; Flame-retardant and self-extinguishing polyurethane, characterized in that it is manufactured by a manufacturing method comprising the step of modifying the surface to be hydrophilic by reacting a needle-shaped Spongilla lacustris spicule with pores formed on the surface with a basic compound. Foam pad.