KR20230016527A - A flame retardant insulation composite coated with tannic acid and the method for preparing the same - Google Patents

Abstract

According to the present specification, disclosed is a flame retardant composite insulation material which includes: a flame retardant substrate; and a flame retardant coating layer formed on the flame retardant substrate, wherein the flame retardant coating layer includes a polymer resin, a fiber coated with tannic acid (TA), and a curing agent, and the tannic acid is complexed with the polymer resin.

Description

Flame retardant composite insulation material coated with tannic acid and its manufacturing method {A FLAME RETARDANT INSULATION COMPOSITE COATED WITH TANNIC ACID AND THE METHOD FOR PREPARING THE SAME}

Disclosed herein is a flame retardant composite heat insulating material coated with tannic acid and a manufacturing method thereof.

Polymer-based composite materials are widely used in the fields of aviation, ships, automobiles, and construction because of their properties such as stiffness to weight, thermal insulation, corrosion resistance, and physical and chemical stability. However, polymeric materials easily ignite and burn even in small fire sources, and generate high heat release rates and large amounts of smoke and toxic gases, so it is urgent to develop technology to solve this problem.

In particular, polymeric materials used as a large amount of coating materials or adhesives for interior and exterior materials for construction cause serious human casualties by generating toxic gases in the event of a fire unless additional flame retardancy is imparted. Therefore, flame retardancy of polymer materials is absolutely necessary for a safe living environment.

Typically, a method of modifying the polymer itself, a method of adding a flame retardant, a method of combining with a flame retardant material, and the like are used for flame retardation of polymer materials.

Embodiments of the present invention are intended to provide a flame retardant composite material in which flame retardancy is imparted to a highly ignitable polymer material.

Embodiments of the present invention are intended to provide a flame retardant composite material that can be used as an interior/exterior building material with improved thermal and mechanical properties by uniformly dispersing fibers as a filler in a polymer matrix.

In one embodiment of the present invention, a flame retardant substrate; and a flame retardant coating layer formed on the flame retardant substrate, wherein the flame retardant coating layer includes a polymer resin, tannic acid (TA)-coated fibers, and a curing agent, wherein the tannic acid is a composite of the polymer resin and the flame retardant composite. Insulation material is provided.

In one embodiment, the flame retardant substrate may be composed of a flame retardant nanofiber matrix or foam insulation.

In one embodiment, the flame-retardant substrate may further include a filler, and the filler may include a nano-carbon structure.

In one embodiment, the curing agent may be tannic acid.

In one embodiment, the fiber may include one or more selected from the group consisting of PAN-based carbon fiber, pitch-based carbon fiber, stabilizing fiber, aramid, and FR rayon.

In one embodiment, the polymer resin is an epoxy resin, and the epoxy resin may be at least one selected from a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, and a phenol novolak-type epoxy resin.

In one embodiment, the flame retardant composite heat insulating material may include a curing agent in a molar ratio of 0.1 to 2.0 relative to the functional group of the polymer resin.

In one embodiment, the curing agent may be included in an amount of 0.05 to 300 parts by weight based on 100 parts by weight of the polymer resin.

In one embodiment, the fiber may be included in an amount of 0.1 to 20% by weight based on the total weight of the flame retardant composite heat insulating material.

In another embodiment of the present invention, forming a mixed solution by mixing a polymer resin, a fiber coated with tannic acid (TA), and a curing agent; And curing the mixed solution; provides a flame retardant composite insulation material manufacturing method comprising a.

In one embodiment, the coating may be performed by dispersing the tannic acid and fibers in a solvent.

In one embodiment, the curing agent may be mixed in a molar ratio of 0.1 to 2 relative to the functional groups of the polymer resin in the step of forming the mixed solution.

In one embodiment, the solvent may be removed from the mixed solution prior to curing.

In one embodiment, the curing step comprises primary curing for 30 minutes to 2 hours in a temperature range of 120 to 200 °C, and secondary curing for 1 to 4 hours in a temperature range of 170 to 250 °C. can include

The flame retardant coating agent according to embodiments of the present invention can be prepared by adjusting the curing degree of an epoxy resin with tannic acid without separately adding a conventional epoxy curing agent, and can impart flame retardancy to a polymer coating material.

In addition, the flame retardant composite material according to embodiments of the present invention may further increase flame retardancy and impart heat insulation to the polymer material by including nanofibers or foam insulation and fibers as a substrate.

1 schematically shows a tannic acid-coated flame retardant composite heat insulating material according to an embodiment of the present invention.
Figure 2 schematically shows the manufacturing steps of the tannic acid-coated flame retardant composite heat insulating material according to an embodiment of the present invention.
3 to 5 are flame retardant nanofiber matrices according to an embodiment of the present invention, including fibers containing tannic acid in polyurethane (FIG. 3), nano-carbon structures (graphene (FIG. 4), boron-doped carbon nanotubes (FIG. 5) ) shows a SEM image of nanofibers containing tannic acid-coated fillers.
6 shows a SEM image of nanofibers in which tannic acid is spray-coated on polyurethane nanofibers according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Embodiments of the present invention have been described with reference to the accompanying drawings, but this is described for illustrative purposes, whereby the technical spirit of the present invention and its configuration and application are not limited.

In the present specification, "functional group molar ratio" means a molar content based on the number of functional groups of a specific material.

In the present specification, "nanofiber" refers to a fiber having an average diameter of 10 micrometers or less or 50 nm or more to 3000 nm or less.

In the present specification, "carrier polymer" refers to a polymer material that improves the viscosity of a spinning solution (composition for producing fibers) when producing fibers.

flame retardant composite insulation material

In one embodiment of the present invention, a flame retardant substrate; and a flame retardant coating layer formed on the flame retardant substrate, wherein the flame retardant coating layer includes a polymer resin, tannic acid (TA)-coated fibers, and a curing agent, wherein the tannic acid is a composite of the polymer resin and the flame retardant composite. Insulation material is provided.

In an exemplary embodiment, the flame retardant substrate may have a structure dispersed inside a polymer resin matrix formed by curing a polymer resin. Specifically, the flame retardant substrate may be composed of a flame retardant nanofiber matrix or foam insulation.

In an exemplary embodiment, the flame retardant nanofiber of the flame retardant nanofiber matrix may be a fiber containing tannic acid in a polymer resin or a fiber containing a filler coated with tannic acid in a nanocarbon structure (graphene, carbon nanotube, etc.). For example, the fiber may include one or more selected from the group consisting of PAN-based carbon fiber, pitch-based carbon fiber, stabilizing fiber, aramid, and FR rayon. These fibers may act as a filler in a flame retardant composite insulation material, and the filler may improve mechanical and thermal properties as a reinforcing agent in a polymer, and at the same time form char during combustion to perform an insulation function.

An average diameter of the nanofibers may be 3 μm or less. Specifically, it may be 3 μm or less, 2 μm or less, 1 μm or less, 0.5 μm or less, 0.1 μm or less, or 0.05 μm or less. In addition, the nanofibers may be nanofibers having an average fiber diameter of 50 nm to 3000 nm. Specifically, the fiber may have an average diameter of 50 nm or more, 60 nm or more, 80 nm or more, 100 nm or more, 150 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, 350 nm or more, or 500 nm or more. In addition, the average diameter of the fiber may be 3000 nm or less, 2500 nm or less, 2000 nm or less, 1500 nm or less, 1000 nm or less, 800 nm or less, 500 nm or less, 400 nm or less, 380 nm or less, 370 nm or less, or 360 nm or less. there is.

For example, the foam insulator is polyurethane-based and may be a hard foam or a flexible foam depending on the structure of the polyol. Specifically, the foam insulation is polyurethane-based and may be a hard foam or a flexible foam depending on the structure of the polyol. Polyols used in rigid foam are polyaromatic, and include toluenediamine-based polyols, methylenediphenyldiamine-based polyols, and bisphenol-A-based polyols. The polyol used in flexible foam is a polyester (ester) type polymer compound containing an ester group (-CO-O-) as a repeating unit in the chain, and may have a hydroxyl group at the end.

In an exemplary embodiment, the flame retardant substrate may further include a filler, and the filler may include a nano-carbon structure. Specifically, the filler may be a nano-carbon structure, and may include, for example, graphene and carbon nanotubes (eg, doped carbon nanotubes and boron-doped carbon nanotubes).

In an exemplary embodiment, the curing agent may be tannic acid. Therefore, it is possible to improve the mechanical properties by adjusting the degree of curing of the material only with tannic acid without a separate curing agent.

On the other hand, the tannic acid may be extracted from wood, since tannic acid is abundant in nature, a large amount of tannic acid can be used at low cost. For example, the tannic acid may have a structure of Chemical Formula 1.

[Formula 1] - Tannic acid

Specifically, tannic acid may have flame retardant properties because graphite may be formed during combustion and also may deactivate radicals formed in a burning material. In addition, as can be seen in the chemical structure of tannic acid in Formula 1, tannic acid contains a large amount of hydroxyl groups in its molecular structure, and a large amount of hydroxyl groups form covalent bonds with epoxy epoxide groups to form polymers. In addition, hydrogen bonds can also be formed, which can increase the interaction between polymers and polymer chains, and as a result, improve stiffness.

In an exemplary embodiment, the fibers may include stabilizing fibers or truncated stabilizing fibers. Here, the stabilized fiber may be produced by heat treatment (around 300 to 400 degrees) of fibers at a lower temperature than the high temperature heat treatment (around 800 to 1500 degrees) process for producing carbon fibers. In addition, the delivered stabilization fiber means that the stabilization fiber is cut to a certain length, and at this time, depending on the mechanical / thermal properties depending on the fiber length and the amount of addition, it may be cut to a length of about 10 mm.

In an exemplary embodiment, the fiber may include one or more selected from the group consisting of PAN-based carbon fiber, pitch-based carbon fiber, stabilizing fiber, aramid, and FR rayon.

In an exemplary embodiment, the polymer resin is an epoxy resin, and the epoxy resin may be at least one selected from bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and phenol novolak-type 　 epoxy resin, but is limited thereto It is not. The epoxy resin may have two or more epoxide groups in a unit.

In an exemplary embodiment, the flame retardant composite heat insulating material may include a curing agent in a molar ratio of 0.1 to 2.0 relative to the functional group of the polymer resin. For example, the curing agent may be included in an amount of 0.5 to 2.0 mole ratio, 0.5 to 1.2 mole ratio, 0.8 to 1.2 mole ratio, or 1.0 to 1.2 mole ratio relative to the functional group of the polymer resin. When the curing agent is included in an amount of less than 0.1 mol or greater than 2 mol relative to the functional group of the polymer resin, the dispersion degree of the filler included in the flame retardant composite insulating material may decrease, and accordingly, the flame retardancy of the polymer resin may decrease.

In an exemplary embodiment, the curing agent may be included in an amount of 0.05 to 300 parts by weight based on 100 parts by weight of the polymer resin. When the curing agent is included in an amount of less than 0.05 parts by weight or 300 parts by weight based on 100 parts by weight of the polymer resin, the dispersion degree of the filler may decrease, and accordingly, the flame retardancy of the polymer resin may decrease.

In an exemplary embodiment, the fiber may be included in an amount of 0.1 to 20% by weight based on the total weight of the flame retardant composite heat insulating material. For example, it may be included in 1 to 5% by weight. When the fibers are included in an amount of 0.1% by weight or more based on the total weight of the flame retardant composite heat insulating material, the flame retardant epoxy composite material may have excellent thermal properties and mechanical properties. However, when added in excess of 20% by weight, the mechanical properties of the material may tend to deteriorate.

The flame retardant composite insulation material according to the present invention may have excellent flame retardant properties, for example, an excellent limiting oxygen index (LOI) value. The limiting oxygen index can be calculated with the following formula.

[Equation 1]

Here, O ₂ and N ₂ mean oxygen flow rate and nitrogen flow rate, respectively.

Therefore, the limiting oxygen index (LOI) of the flame retardant composite heat insulating material according to the present invention, for example, can be improved by about 30% or more compared to the reference sample that does not contain tannic acid.

Method for manufacturing flame retardant composite insulation material

In another embodiment of the present invention, forming a mixed solution by mixing a polymer resin, a fiber coated with tannic acid (TA), and a curing agent; And curing the mixed solution; provides a flame retardant composite insulation material manufacturing method comprising a.

First, a flame retardant substrate may be prepared. For example, in the case of preparing a flame retardant nanofiber matrix with a flame retardant substrate, after adding a fiber containing tannic acid to a polyurethane solution as a medium polymer or a filler coated with tannic acid to a nanocarbon structure, respectively, flame retardant nanofibers through solution blower spinning matrix can be made.

In an exemplary embodiment, spinning methods other than solution blower spinning may be used, such as electro-spinning, melt-blown, flash-spinning, electro-spraying, and the like. spraying), solution blow spinning, and electro-blowing. Any one or more spinning methods may be applied.

In an exemplary embodiment, the spinning may be electrospinning, and specifically, the electrospinning has a needle gauge of 15 to 20 gauge, a solution supply rate of 0.1 to 10 ml / h, a voltage of 15 to 30 kV, and a spinning distance of 10 to 17 cm. Electrospinning can be performed under these conditions.

In an exemplary embodiment, in the case of preparing a foam insulation material with a flame retardant substrate, in order to prepare the foam insulation material, the polyol is polyester, a product having a molecular weight of 3000, a functional group of 3, and a hydroxyl group of 56 (P-3022), Triethylene diamine (A-33) and bis-dimethyleaminoethylether (A-1) as surfactants and catalysts, stannous octoate (T-9), distilled water, and flame retardant tannic acid were added and sufficiently stirred to obtain a tannin-polyurethane pre-form solution. was manufactured. At this time, TDI as isocyanate is added to the preform liquid and stirred for 30 s to prepare a flexible polyurethane foam.

Next, a mixed solution may be formed by mixing a polymer resin, a fiber coated with tannic acid (TA), and a curing agent. For example, a flame retardant layer may be formed on the left and right surfaces of the foam insulator with the mixed solution.

In an exemplary embodiment, the coating may be performed by dispersing the tannic acid and fibers in a solvent. For example, the coating may be performed by cutting fibers into a certain size and then dispersing them in a tannic acid solvent. Specifically, the coating may be performed by ultrasonic dispersion. In addition, in the case of woven fibers, the coating may be coating a tannic acid solution on the woven fibers, and specifically, dip coating, spray coating, or ultrasonic spray coating may be used.

In an exemplary embodiment, the curing agent may be mixed in a molar ratio of 0.1 to 2 relative to the functional groups of the polymer resin in the step of forming the mixed solution, the same as the above.

In an exemplary embodiment, the solvent may be removed from the mixed solution prior to curing. If the solvent remains, the residual solvent volatilizes during curing to form defects such as air bubbles in the polymer resin, thereby deteriorating mechanical properties and flame retardant properties.

Next, the mixed solution may be cured. Through this curing step, the polymer resin is cured to form a polymer resin matrix.

In an exemplary embodiment, the curing process may be performed multiple times, for example two times. Specifically, the curing step includes the step of primary curing for 30 minutes to 2 hours in a temperature range of 120 to 200 ° C, and the step of secondary curing for 1 to 4 hours in a temperature range of 170 to 250 ° C. can do.

Next, the flame retardant coating layer prepared by curing the mixed solution may be bonded onto the flame retardant substrate. Specifically, a plurality of flame retardant substrates may be stacked and inserted between the flame retardant coating layers, and sealed (bonded) by hot pressing in a thermal compression method.

On the other hand, when it is difficult to bond by the thermocompression bonding method, it can be bonded by applying a tannic acid epoxy adhesive between the two layers of the flame retardant substrate and the flame retardant coating layer.

Hereinafter, the configuration and effects of the present invention will be described in more detail by way of examples. However, these examples are provided only for illustrative purposes to aid understanding of the present invention, and the scope and scope of the present invention are not limited by the following examples.

Example 1: Manufacturing method of flame retardant substrate (flame retardant nanofiber matrix)

In order to prepare a flame retardant base material of the flame retardant nanofiber matrix, polyurethane (Mw 150,000 g/mol) was uniformly dissolved in DMF at a concentration of 10 wt% by stirring at 100 °C for 3 hours. Then, fibers or nano-carbon structures (graphene (FIG. 3), boron-doped carbon nanotubes (FIG. 4)) each containing tannic acid were mixed with tannic acid-coated fillers in different amounts relative to the weight of polyurethane, and at room temperature for 3 hours. After preparing a uniform solution by stirring, it was used as a spinning solution. At this time, electrospinning finally prepares a flame retardant nanofiber matrix under the conditions of an applied voltage (18 kV), a feed rate of 0.5 ml/h, a TCD of 15 cm, and a needle gauge of 21 G.

Example 2: Manufacturing method of flame retardant substrate (foam insulation)

To manufacture the foam insulation, the polyol is polyester with a molecular weight of 3000, a product with 3 functional groups and 56 hydroxyl groups (P-3022), triethylene diamine (A-33) and bis-dimethyleaminoethylether as surfactants and catalysts. (A-1), and stannous octoate (T-9), distilled water, and flame retardant tannic acid were added and sufficiently stirred to prepare a tannin-polyurethane pre-foam solution. At this time, TDI as isocyanate was added to the preform liquid and stirred for 30 s to prepare a flexible polyurethane foam.

Example 3: Flame retardant coating layer (epoxy + tannic acid)

Adjust the weight of tannic acid (Sigma-Aldrich, CAS Number: 1401-55-4) extracted from wood with a molar ratio (0.5, 0.8, 1.0, 1.2) relative to the functional group of YD-128 (2 epoxide groups), an epoxy precursor prepared for the experiment. Completely dissolve tannic acid and 40 g of YD-128 in 50 ml of ethanol. Thereafter, the pressure is reduced at 80 degrees to completely remove ethanol, put into a mold, and cured at 160 degrees for 1 hour and 210 degrees for 2 hours to finally prepare a flame retardant coating layer of a flame retardant composite material.

Comparative Example 1: Conventional epoxy composite material (epoxy + curing agent)

A conventional flame retardant coating layer was prepared in the same manner as in Example 3, except that a coating material solution was formed by mixing 20 g of a hardener (polyetheramine hardener (Kukdo chemical, trade name D-230) instead of tannic acid extracted from wood.

Example 4: Flame retardant coating layer (epoxy + tannic acid + carbon fiber fabric / stabilized fiber fabric)

40 g of tannic acid (Sigma-Aldrich, CAS Number: 1401-55-4) extracted from wood and 250 ml of epoxy resin (YD-128, Kukdo Chemical) were added to 50 ml of ethanol to prepare a solution. Thereafter, the prepared carbon fiber fabric (T300, Toray) or stabilized fiber fabric (Taekwang) is impregnated so that the prepared carbon fiber fabric (T300, Toray) or stabilized fiber fabric (Taekwang) is sufficiently immersed in the mixed solution, and then hot-pressed at 130 degrees for 30 minutes to make a flame retardant carbon fiber composite material after pre-curing. Then, curing is performed in a vacuum oven at 210 degrees for 2 hours.

Here, the stabilized fiber fabric was prepared by heat-treating PAN fibers (around 300-400 degrees) at a lower temperature than the high-temperature heat treatment (around 800-1500 degrees) for producing carbon fibers. Afterwards, the fibers obtained through the oxidation reaction are usually referred to as quasi-carbon fibers or stabilized (salt-resistance) fibers, and have flame retardant and heat insulating properties as their main characteristics.

Example 5: Flame retardant coating layer (epoxy + tannic acid + cut stabilized fibers)

40 g of tannic acid (Sigma-Aldrich, CAS Number: 1401-55-4) extracted from wood, 250 ml of epoxy resin (YD-128, Kukdo Chemical), and cut safety fiber (Taekwang) were mixed with epoxy resin weight ratio 1, 3, 5, 10, 20 wt% was mixed in an ethanol solvent to form a coating material solution, and a tannic acid-coated flame retardant composite insulation material was prepared in the same manner as in Example 3. The samples included 1% by weight, 3% by weight, 5% by weight, 10% by weight and 20% by weight of the cut stabilizing fibers, respectively, based on the total weight of the flame retardant composite insulation material.

The stabilized fiber cut here was used by cutting the stabilized fiber of Example 4 to about 10 mm.

Example 6: Manufacturing of flame retardant composite insulation material

A flame retardant composite insulation material was prepared by combining the flame retardant substrates of Examples 1 and 2 and the flame retardant coating layers of Examples 3 to 5.

Referring to FIG. 2, a core material obtained by stacking a plurality of layers of a core material (flame retardant material) 10) was inserted into an outer covering material (flame retardant coating layer) 20. At this time, the bonding between the outer skin material and the core material is the same as the method of manufacturing the composite material layer, and sealing (adhesion) is performed by hot press and thermal compression. If it is difficult to heat-compress the outer cover material and the core material, the two layers are bonded using the tannic acid epoxy adhesive used for the outer cover material.

Experimental Example 1: SEM analysis of tannic acid-coated flame retardant composite insulation material

3-5 are SEM image results of observing the surface of the flame retardant nanofibers of Example 1. 3 shows a tannic acid/PU nanofiber matrix, FIG. 4 shows a tannic acid/graphene/PU nanofiber matrix, and FIG. 5 shows a tannic acid/doped CNT/PU nanofiber matrix, respectively. It can be seen that most of the fibers are spun in the form of stable nanofibers having a uniform diameter distribution without a bead shape. Most of the morphologies of the spun nanowebs were stable, and the average diameter of the nanofibers ranged from 255 to 404 nm.

Experimental Example 2: Analysis of flame retardant properties

Experimental and comparative examples were tested for limited oxygen index (LOI) by making specimens of 100 mm × 6 mm × 4 mm.

After standing the specimen vertically in the limiting oxygen index equipment (Fire Testing Technology, UK), set high-purity nitrogen and oxygen and wait until the flow rate of oxygen concentration becomes constant. Apply a flame to the upper part of the sample and remove it once every 5 seconds to see if it can be ignited for 30 seconds. If ignition occurred within 30 seconds, time was measured from the point of ignition, and the oxygen concentration that did not last for 180 seconds was defined as the limiting oxygen index of the material. In addition, in order to evaluate the flame retardant performance of the nanofibers, a Cone calorimeter (iCone ^TM Calorimeter) manufactured by Fire Testing Technology (FTT, UK) was used according to the E1354 standard.

The measured values of the limiting oxygen index (LOI), PHRR (heat release rate), THR (total heat release rate), and HRC (heat release rate) are shown in Table 1 below.

Sample TA content Fiber content (wt%) Filler content (wt%) LOI PHRR (W/g) THR (kJ/g) HRC (J/gk) Comparative Example 1 TD0 - 18 Example 1 TD1.2 - graphene One 22.6 272.26 23.20 377.6 - 3 22.7 249.94 22.28 372 - 5 23.2 235.23 21.72 356.8 - Boron-doped CNT One 27.5 259.1 22.4 257 - 3 27.6 254 21.7 256 - 5 28.6 240 20.6 240 Example 3 TD1.2 - 25.9 Example 4 TD1.2 carbon fiber fabric 34.1 TD1.2 Stabilized fiber fabric 35.8 Example 5 TD1.2 cleaved stabilizing fibers One 26.7 3 28.2 5 30.5 10 32.7 20 33.3

Through the flame retardant characteristic analysis experiment, it was confirmed that the limiting oxygen index (LOI) of the composite material according to one embodiment of the present invention had a significantly improved value compared to the reference sample (Comparative Example 1).

In this way, through exemplary embodiments of the present invention, it is possible to easily and quickly prepare a flame retardant epoxy composite material having improved flame retardancy as well as excellent mechanical properties by uniformly dispersing the nano-carbon structures in the matrix.

Claims (14)

flame retardant materials; And a flame retardant coating layer formed on the flame retardant substrate,
The flame retardant coating layer includes a polymer resin, fibers coated with tannic acid (TA), and a curing agent,
The tannic acid is a composite flame retardant insulating material that is complexed with the polymer resin. According to claim 1,
The flame retardant substrate is composed of a flame retardant nanofiber matrix or foam insulation, flame retardant composite insulation material. According to claim 1,
The flame retardant substrate further comprises a filler,
The filler is a flame retardant composite heat insulating material containing a nano-carbon structure. According to claim 1,
The curing agent is tannic acid, flame retardant composite insulation material. According to claim 1,
The fiber is a flame retardant composite insulation material comprising at least one selected from the group consisting of PAN-based carbon fiber, pitch-based carbon fiber, stabilized fiber, aramid, and FR rayon. According to claim 1,
The polymer resin is an epoxy resin, and the epoxy resin is at least one selected from bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and phenol novolac-type epoxy resin. According to claim 1,
The flame retardant composite heat insulating material comprises a curing agent in a molar ratio of 0.1 to 2.0 relative to the functional group of the polymer resin, the flame retardant composite heat insulating material. According to claim 1,
The curing agent is included in 0.05 to 300 parts by weight based on 100 parts by weight of the polymer resin, flame retardant composite insulation material. According to claim 1,
The fiber is contained in 0.1 to 20% by weight relative to the total weight of the flame retardant composite heat insulating material, flame retardant composite heat insulating material. Forming a mixed solution by mixing a polymer resin, a fiber coated with tannic acid (TA), and a curing agent; and
Curing the mixed solution; including, flame retardant composite insulation material manufacturing method. According to claim 10,
The coating is a flame retardant composite heat insulating material manufacturing method of coating by dispersing the tannic acid and fibers in a solvent. According to claim 10,
In the mixed solution forming step, a flame retardant composite heat insulating material manufacturing method of mixing a curing agent at a molar ratio of 0.1 to 2 relative to the functional group of the polymer resin. According to claim 11,
The solvent is removed from the mixed solution prior to curing, flame retardant composite heat insulating material manufacturing method. According to claim 10,
The curing step comprises primary curing in the temperature range of 120 to 200 ° C. for 30 minutes to 2 hours, and secondary curing in the temperature range of 170 to 250 ° C. for 1 to 4 hours. Method for manufacturing composite insulation materials.

Images