JP6769867B2 - Refractory resin composition - Google Patents

Description

(Cross-reference in related fields)
The present application claims the priority benefit of the specification of Japanese Patent Application No. 2015-035482 filed on February 25, 2015, which is incorporated herein by reference in its entirety.
(Technical field)
The present invention relates to a refractory resin composition.

In the field of building materials, fire resistance has traditionally been important. In recent years, with the expansion of applications of resin materials, resin materials imparted with fire resistance have come to be widely used as building materials.

Patent Document 1 is a fire-resistant resin composition containing an epoxy resin, a phosphorus compound, neutralized thermosetting graphite, and an inorganic filler, each of which contains 100 parts by weight of the epoxy resin. The phosphorus compound is 50 to 150 parts by weight, the neutralized thermosetting graphite is 15 to 40 parts by weight, and the inorganic filler is 30 to 500 parts by weight. The phosphorus compound is neutralized heat. A fire-resistant resin composition is disclosed, wherein the total amount of the expandable graphite and the inorganic filler is 200 to 600 parts by weight.

Patent Document 2 discloses a fire-resistant resin composition comprising 100 parts by weight of an epoxy resin, 10 to 300 parts by weight of neutralized thermosetting graphite, and 50 to 500 parts by weight of an inorganic filler. There is.

JP-A-11-1167776 Japanese Unexamined Patent Publication No. 2000-143941

In Patent Documents 1 and 2, an epoxy resin is used as a binder for the fire-resistant resin composition, and the fire-resistant resin composition is molded into a thermosetting sheet by a conventionally known molding method such as press molding. However, it has not been known whether sufficient fire resistance can be obtained even when a thermosetting resin other than the epoxy resin is used as the binder.

Further, Patent Documents 1 and 2 have described that as the blending amount of expanded graphite and the inorganic filler increases, the mechanical properties of the refractory resin composition deteriorate significantly. Further, it has not been studied that a large amount of expanded graphite and an inorganic filler can be contained when a thermally expandable sheet made of a refractory resin composition is produced by coating.

An object of the present invention is to provide a refractory resin composition exhibiting excellent refractory performance and mechanical properties, and a sheet composed of the refractory resin composition. Another object of the present invention is to provide a refractory resin composition suitable for coating and exhibiting excellent refractory performance and mechanical properties, and a sheet made of the refractory resin composition.

In order to achieve the above object, the present inventor uses a thermosetting resin other than an epoxy resin or another liquid binder suitable for coating as a binder in a fire-resistant resin composition to obtain an expanded graphite and an inorganic filler. The present invention has been completed by finding that it is possible to fill with a high compounding amount and therefore excellent fire resistance can be obtained.

According to one aspect of the present invention, it contains a binder, a phosphorus compound, a thermosetting graphite, and an inorganic filler, and the binder is a phenol resin, a melamine resin, a urea resin, an unsaturated polyester resin, an alkyd resin, a polyurethane resin, and the like. At least one thermosetting resin selected from silicone resin and thermosetting polyimide; at least one thermoplastic resin selected from acrylic resin, vinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin; rubber Fire resistance consisting of latex; or a combination thereof, in which the phosphorus compound is 50 to 500 parts by weight and the total amount of the thermosetting graphite and the inorganic filler is 50 to 1000 parts by weight per 100 parts by weight of the binder. A resin composition is provided.

According to the present invention, since the refractory resin composition has excellent fire resistance, excellent fire resistance can be provided by applying a sheet made of the refractory resin composition to a building or the like.

A schematic diagram of a method for manufacturing a refractory sheet.

The refractory resin composition of the present invention contains a binder, a phosphorus compound, a heat-expandable graphite, and an inorganic filler.

One example of the binder is at least one thermosetting material selected from phenol resin, melamine resin, urea resin (urea resin), unsaturated polyester resin, alkyd resin, polyurethane resin, silicone resin, and thermosetting polyimide. Resin is mentioned. Another example of the binder is a thermoplastic resin suitable for coating a fire resistant resin composition, for example, an acrylic resin, a vinyl acetate resin (including ethylene vinyl acetate copolymer (EVA), polyvinyl acetate (PVAc), etc.). , Polyvinyl alcohol resin, and at least one thermoplastic resin selected from polyvinyl butyral resin. Another example of a binder is rubber or latex. The above-mentioned thermosetting resin, thermoplastic resin, rubber and latex may be used alone or in combination.

A phosphorus compound, a heat-expandable graphite, and an inorganic filler are added to the binder used in the present invention. The refractory performance of the refractory resin composition of the present invention is exhibited when these three components exhibit their respective properties. Specifically, heat-expandable graphite forms an expansion-insulating heat insulating layer during heating to prevent heat transfer. The inorganic filler then increases the heat capacity. The phosphorus compound exhibits the shape-retaining ability of the expanded heat insulating layer and the inorganic filler.

The phosphorus compound is not particularly limited, and examples thereof include red phosphorus; phosphoric acid ester; metal phosphate salt; ammonium polyphosphate; melamine polyphosphate; and a compound represented by the following general formula (1).

In the formula, R ¹ and R ³ represent hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms, which are the same or different. R ² is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or carbon. It shows the number 6 to 16 aryloxy groups.

As the red phosphorus, commercially available red phosphorus can be used. From the viewpoint of moisture resistance and safety such as not spontaneously igniting during kneading, the surface of the red phosphorus particles coated with a resin is preferable.

Examples of the phosphoric acid ester include phosphoric acid aryl esters such as triphenyl phosphate, tricredil phosphate (TCP), trixylenyl phosphate, cresyldiphenyl phosphate and xylenyl diphenyl phosphate; and alkyl phosphates such as trimethyl phosphate. Examples thereof include bisphenol A-bis, resorcinol bisdiphenyl phosphate, resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate, and bisphenol-based aromatic condensed phosphate esters. Some phosphate esters such as tricredyl phosphate (TCP) and crezyl diphenyl phosphate also function as phosphate-based plasticizers that adjust the melt viscosity of the matrix. A preferred phosphate ester is tricresyl phosphate (TCP).

Examples of the metal phosphate salt include sodium phosphate, potassium phosphate, magnesium phosphate and the like.

Examples of ammonium polyphosphates include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and the like. Ammonium polyphosphate is preferable from the viewpoint of handleability and the like. Examples of commercially available products include Hoechst's "AP422" and "AP462", Sumitomo Chemical's "Sumisafe P", and Chisso's "Terage C60".

Examples of the compound represented by the general formula (1) include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonate, butylphosphonic acid, 2-methylpropylphosphonate, and t-butylphosphonate. Acids, 2,3-dimethyl-butylphosphonate, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphonic acid, methylethylphosphonate, methylpropylphosphinic acid, diethylphosphonate, dioctylphosphonate, phenylphosphonate, Examples thereof include diethylphenylphosphonic acid, diphenylphosphonic acid, and bis (4-methoxyphenyl) phosphonic acid.

The above phosphorus compounds may be used alone or in combination of two or more.

In one embodiment, the phosphorus compound is selected from the group consisting of red phosphorus; phosphate esters; metal phosphates; ammonium polyphosphates; and melamine polyphosphates, compounds represented by the following general formula (1); At least one.

In another embodiment, the phosphorus compound is at least one selected from the group consisting of phosphate esters and ammonium polyphosphates.

The heat-expandable graphite used in the present invention is a conventionally known substance, and powders such as natural scaly graphite, thermally decomposed graphite, and kiss graphite are mixed with inorganic acids such as concentrated nitric acid, nitric acid, and selenic acid, and concentrated nitric acid and perchloric acid. A graphite interlayer compound formed by treatment with a strong oxidizing agent such as acid, perchlorate, permanganate, dichromate, hydrogen peroxide, etc., and crystals that maintain the layered structure of carbon. It is a compound.

The particle size of the heat-expandable graphite used in the present invention is preferably 20 to 200 mesh. When the particle size is coarser than 200 mesh, the degree of expansion of graphite is large and a desired refractory heat insulating layer can be obtained. When the particle size is smaller than 20 mesh, the dispersibility is good when kneaded with the resin.

Examples of the inorganic filler used in the present invention include silica, slag, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, and the like. Aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawn night, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, montmorillonite, bentonite , Activated white clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica-based balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder, various metal powders, titanium acid Candidates include potassium, magnesium sulfate "MOS", lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, and dehydrated sludge. In the present invention, metal salts, oxides, or hydroxides of metals belonging to Group II or Group III of the Periodic Table have the property of foaming during combustion to form a foamed fired product, thus improving shape retention. Is particularly preferable. Specific examples thereof include calcium carbonate and magnesium carbonate.

In general, the inorganic filler acts as an aggregate, and is therefore considered to contribute to the improvement of the residual strength and the increase of the heat capacity. The above-mentioned inorganic filler may be used alone or in combination of two or more.

The particle size of the inorganic filler is preferably 0.5 to 100 μm, more preferably 1 to 50 μm. When the amount of the inorganic filler added is small, the dispersibility greatly affects the performance, so that the inorganic filler has a small particle size, but when it is 0.5 μm or more, the dispersibility is good. When the amount added is large, the viscosity of the resin composition increases and the moldability decreases as the high filling progresses, but the viscosity of the resin composition can be decreased by increasing the particle size. A large diameter is preferable, but a particle size of 100 μm or less is desirable from the viewpoint of the surface properties of the molded product and the mechanical properties of the resin composition.

Among the above-mentioned inorganic fillers, especially hydrous inorganic substances such as magnesium hydroxide and aluminum hydroxide absorb heat due to water generated by the dehydration reaction during heating, and the temperature rise is reduced to obtain high heat resistance. , And an oxide remains as a heating residue, which is particularly preferable in that it acts as an aggregate to improve the residual strength.

As the particle size of the water-containing inorganic substance becomes smaller, the bulk becomes larger and it becomes difficult to increase the filling. Therefore, in order to enhance the dehydration effect, a large particle size is preferable for high filling. Specifically, it is known that when the particle size is 18 μm, the filling limit amount is improved by about 1.5 times as compared with the particle size of 1.5 μm. Further, by combining the one having a large particle size and the one having a small particle size, higher filling is possible.

In the commercially available products of the above-mentioned inorganic filler, for example, as aluminum hydroxide, "H-42M" (manufactured by Showa Denko Co., Ltd.) having a particle size of 1 μm, “H-31” (manufactured by Showa Denko Co., Ltd.) having a particle size of 18 μm; calcium carbonate. Examples thereof include "Whiten SB Red" (manufactured by Shiraishi Calcium Co., Ltd.) having a particle size of 1.8 μm and "BF300" (manufactured by Shiraishi Calcium Co., Ltd.) having a particle size of 8 μm. Further, it is more preferable to use an inorganic filler having a large particle size and a filler having a small particle size in combination, and by combining them, higher filling becomes possible.

In the present invention, the phosphorus compound is 50 to 500 parts by weight and the total amount of the heat-expandable graphite and the inorganic filler is 50 to 1000 parts by weight per 100 parts by weight of the binder.

When the phosphorus compound is 50 parts by weight or more, the shape retention (residual hardness) of the refractory resin composition and the sheet made thereof is obtained, and when the phosphorus compound is 500 parts by weight or less, the refractory resin composition and the refractory resin composition and the like. The mechanical properties of the sheet are maintained. Preferably, the phosphorus compound is 50 to 300 parts by weight per 100 parts by weight of the binder.

When the total amount of the thermosetting graphite and the inorganic filler is 50 parts by weight or more, the residual amount (expansion ratio) of the refractory resin composition and the sheet made of the same after heating is sufficient, and sufficient fire resistance is obtained. When the amount is 1000 parts by weight or less, the mechanical properties of the refractory resin composition and the sheet made of the same are maintained.

In one embodiment, the total amount of the heat-expandable graphite and the inorganic filler is preferably 550 to 1000 parts by weight per 100 parts by weight of the binder, and the total amount of the heat-expandable graphite and the inorganic filler is 550 to 1000 parts by weight. The heat-expandable graphite is usually 10 to 500 parts by weight, preferably 30 to 300 parts by weight, per 100 parts by weight of the binder. The inorganic filler is usually 30 to 700 parts by weight, preferably 30 to 500 parts by weight, per 100 parts by weight of the binder.

In the present invention, by combining the heat-expandable graphite and the phosphorus compound, the scattering of the heat-expandable graphite during combustion is suppressed and the shape is maintained. If the amount of the heat-expandable graphite is too large, the graphite expands during combustion. Is scattered and a sufficient expansion heat insulating layer cannot be obtained during heating. On the contrary, if the amount of phosphorus compound is too large, the heat insulating layer is not sufficient and the desired effect cannot be obtained. The weight ratio of the compound is heat-expandable graphite: phosphorus compound = 9: 1 to 1: 100.

Further, from the viewpoint of shape retention during combustion, the range of thermally expandable graphite: phosphorus compound = 1: 3 to 1: 100 is excellent. Even if the composition itself is flame-retardant, if the shape-retaining property is insufficient, the brittle residue collapses and penetrates the flame. Therefore, depending on whether the shape-retaining property is sufficient or not, the refractory composition The usage form of is very different. More preferably, the heat-expandable graphite: phosphorus compound = 1: 5 to 1:60, and particularly preferably 1: 10 to 1:40.

The fire-resistant resin composition of the present invention further contains an antioxidant such as a phenol-based, amine-based, or sulfur-based agent, a metal damage inhibitor, an antistatic agent, a stabilizer, and a cross-linking agent, as long as the physical properties are not impaired. , Lubricants, softeners, pigments and the like may be added.

The fire-resistant resin composition of the present invention can be obtained by kneading each of the above components using a kneading device such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, or a roll. The resin composition can be molded into a sheet by a conventionally known molding method such as coating, press molding, extrusion molding, or calendar molding. In coating, the refractory resin composition of the present invention is applied to a base material such as aluminum, iron or stainless steel, and then dried.

The present invention also includes a sheet produced from a refractory resin composition and a method for producing a refractory sheet by coating. The present invention also includes a refractory sheet in which a base material is laminated on one side or both sides of a layer made of a refractory resin composition.

When the refractory sheet is manufactured by coating, the fiber sheet is impregnated with the refractory resin composition. For example, as shown in FIG. 1, the lower base material 3b is placed on a moving device such as a roller stand 2 and moved in the direction of the arrow, and at the same time, the upper base material 3a is moved above the lower base material 3b. The attached fiber sheet 4 is unwound and arranged. Next, the refractory resin composition 1 is dropped onto the fiber sheet 4 and impregnated into the fiber sheet 4 to form the resin sheet 5. Next, the resin sheet 5 to which the upper base material 3a is attached and the lower base material 3b are passed through a roll 6 to form a sheet, which is then cured to produce a heat-expandable refractory sheet 7.

The upper and lower base materials may be the same material or different materials, but are usually woven fabrics or non-woven fabrics, and the fibers used for the woven fabrics or non-woven fabrics are not particularly limited. .. The fibers are preferably nonflammable agents or semi-incombustible materials, and for example, glass fibers, ceramic fibers, cellulose fibers, polyester fibers, carbon fibers, graphite fibers, thermosetting resin fibers and the like are preferable.

The fiber sheet is formed by entwining fibers into a sheet shape, and a nonflammable agent or a semi-noncombustible material is preferable. Examples of the fiber include glass fiber, ceramic fiber, cellulose fiber, polyester fiber, carbon fiber, graphite fiber, thermosetting resin fiber and the like. A glass cloth formed from glass fibers is preferable.

The refractory resin composition of the present invention can be used to impart fire resistance to building materials. For example, openings such as windows (including sliding windows, hinged windows, raising and lowering windows, etc.), shoji screens, doors (that is, doors), bran, and columns; penetrations of fire protection compartments; joints; fire-resistant resin for steel-framed concrete, etc. Compositions can be placed to reduce or prevent the ingress of fire and smoke.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1
Production of Fire-Resistant Resin Composition by Pressing Phenolic resin (5010 manufactured by DIC), tricresil phosphate (Sunsotherizer manufactured by Shin Nihon Rika Co., Ltd.), heat in the blending amount (unit of each component is parts by weight) shown in Table 1. Expandable graphite (“GREEPEG” manufactured by Tosoh Co., Ltd.), aluminum hydroxide (“H-31” manufactured by Showa Denko Co., Ltd.), and calcium carbonate (“Whiteon BF-300” manufactured by Bikita Powder Co., Ltd.) are kneaded with a kneading roll. Then, a fire-resistant resin composition was obtained. The obtained fire-resistant resin composition was applied to a galvanized iron plate having a thickness of 0.5 mm and pressed at 150 ° C. for 15 minutes to cure, to obtain a sheet-like sample having a predetermined thickness used for fire resistance evaluation.
1. 1. Fire resistance evaluation (expansion magnification)
A test piece (length 100 mm, width 100 mm, thickness 2.0 mm) prepared from the obtained molded product was supplied to an electric furnace, heated at 600 ° C. for 30 minutes, and then the thickness of the test piece was measured. The thickness of the test piece after heating) / (thickness of the test piece before heating) was calculated as the expansion ratio. When the expansion ratio was 10 or more, it was considered good, and when it was less than 10, it was considered poor.
(Residual hardness)
The heated test piece whose expansion ratio was measured was supplied to a compression tester (“Finger Filling Tester” manufactured by Kato Tech Co., Ltd.), compressed with an indenter of 0.25 cm ² at a rate of 0.1 cm / sec, and fractured. The point stress was measured. When the residual hardness was 0.3 or more, it was regarded as good (Good), and when it was less than 0.3, it was regarded as poor (Poor).

Examples 2 to 15, Comparative Examples 1 to 4
Each component was melt-kneaded using a roll at the compounding components and compounding ratios shown in Table 1 to obtain a resin composition. A test piece was prepared from the obtained resin composition in the same manner as in Example 1, and the fire resistance was evaluated. The results are shown in Table 1.

As for the polyimide resin, a sample was obtained by dissolving each component in a solution dissolved in acetone (50%), volatilizing acetone, and forming a sheet.

For unsaturated polyester resin, after dissolving each component, 1 PHR (part by weight) of NOF Park Mill D40 was added and pressed at 150 ° C. under the above conditions to obtain a sample.

Samples of urea resin and melamine resin were obtained by adding 5 PHR (part by weight) of formaldehyde solution (Wako Pure Chemical Industries, Ltd.) to the formulation and press molding.

The resins used are as follows.

Acrylic resin DIC ACRYDIC A181
Polyvinyl alcohol resin Japan Vam & Poval VP-20
Polyvinyl butyral resin BH-S manufactured by Sekisui Chemical Co., Ltd.
Alkyd resin DIC Beckozol 1334-EL
Polyurethane resin Iuliano KL-422 manufactured by Arakawa Chemical Industry Co., Ltd.
Silicone resin KR-220LP manufactured by Shinetsu Silicone Co., Ltd.
Polyimide resin TECHMIGHT E2020S manufactured by Printec Co., Ltd.
Unsaturated polyester resin Showa Denko Corporation Rigolac Urea resin DIC Corporation Beccamin P138
Melamine resin DIC Super Beccamin J-820-60

Example 16
Manufacture of heat-expandable refractory sheet by coating The same refractory resin composition as in Examples 1 and 2 was formed from glass cloth from above with the base material PET non-woven fabric (Eclat 3301A manufactured by Toyobo Co., Ltd.) laid underneath. The thickness was adjusted by dropping the fiber sheet onto the obtained fiber sheet, laminating the fiber sheet from the upper surface, and passing the fiber sheet through the roll gap.

Next, this laminated sheet was placed in an oven at 150 ° C. for 30 minutes and cured to obtain a heat-expandable refractory sheet having a thickness of 1.6 mm. As a result, both the expansion ratio and the residual hardness were good as in Examples 1 and 2.

The present invention can also have the following configurations.
[1] Contains a binder, a phosphorus compound, a heat-expandable graphite, and an inorganic filler, and the binder contains a phenol resin, a melamine resin, a urea resin, an unsaturated polyester resin, an alkyd resin, a polyurethane resin, a silicone resin, and a thermosetting resin. At least one thermosetting resin selected from sex polyimide; at least one thermoplastic resin selected from acrylic resin, vinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin; rubber; latex; or their A fire-resistant resin composition comprising a combination, wherein the phosphorus compound is 50 to 500 parts by weight per 100 parts by weight of the binder, and the total amount of the thermosetting graphite and the inorganic filler is 50 to 1000 parts by weight.
[2] The phosphorus compound is at least one selected from the group consisting of red phosphorus; phosphoric acid ester; metal phosphate salt; ammonium polyphosphate; melamine polyphosphate, and a compound represented by the following general formula (1). The fire-resistant resin composition according to the above [1].

In the formula, R ¹ and R ³ represent hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms, which are the same or different. R ² is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or carbon. It shows the number 6 to 16 aryloxy groups.
[3] The fire-resistant resin composition according to the above [1], wherein the phosphorus compound is at least one selected from the group consisting of a phosphoric acid ester and ammonium polyphosphate.
[4] The above-mentioned [2] or [3], wherein the phosphoric acid ester is at least one selected from the group consisting of a phosphoric acid aryl ester, a phosphoric acid alkyl ester, and a bisphenol-based aromatic condensed phosphoric acid ester. Fire resistant resin composition.
[5] The refractory resin composition according to any one of the above [1] to [4], wherein the phosphorus compound is 50 to 300 parts by weight per 100 parts by weight of the binder.
[6] The refractory resin composition according to any one of the above [1] to [5], wherein the heat-expandable graphite is 10 to 500 parts by weight per 100 parts by weight of the binder.
[7] The refractory resin composition according to any one of the above [1] to [5], wherein the heat-expandable graphite is 30 to 300 parts by weight per 100 parts by weight of the binder.

[8] The refractory resin composition according to any one of [1] to [7], wherein the inorganic filler is 30 to 700 parts by weight per 100 parts by weight of the binder.
[9] The amount of the inorganic filler is 30 to 500 parts by weight per 100 parts by weight of the binder. The refractory resin composition according to any one of [1] to [7].
[10] The refractory resin composition according to any one of the above [1] to [9], wherein the inorganic filler is aluminum hydroxide, calcium carbonate or a mixture thereof.
[11] The fire-resistant resin composition according to any one of the above [1] to [10], wherein the expansion ratio of the fire-resistant resin composition is 10 times or more.
[12] The refractory resin composition according to any one of the above [1] to [11], wherein the residual hardness of the refractory resin composition after heating is 0.3 or more.
[13] A refractory sheet provided with a layer made of the refractory resin composition according to any one of the above [1] to [12].
[14] The fire-resistant sheet according to [13], wherein the base material is laminated on one side or both sides of the layer made of the fire-resistant resin composition.
[15] A method for producing a refractory sheet having a layer made of the refractory resin composition, which comprises applying the refractory resin composition according to any one of [1] to [12] to a substrate and drying it. ..

Claims (4)

Contains binders, phosphorus compounds, thermally expandable graphite, and inorganic fillers,
The binder thermosetting polyimide; consists or a combination thereof; acrylic resins, vinyl acetate resins, polyvinyl alcohol resins, and at least one thermoplastic resin selected from polyvinyl butyral resin
A refractory resin composition in which the phosphorus compound is 50 to 500 parts by weight and the total amount of the heat-expandable graphite and the inorganic filler is 50 to 1000 parts by weight per 100 parts by weight of the binder. A refractory sheet provided with a layer made of the refractory resin composition according to claim 1. The fire-resistant sheet according to claim 2, wherein the base material is laminated on one side or both sides of the layer made of the fire-resistant resin composition. A method for producing a fire-resistant sheet comprising a layer made of the fire-resistant resin composition, which comprises applying the fire-resistant resin composition according to claim 1 to a base material and drying it.

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