JPH11116776A - Fire resistant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. which has a flame retardance and, when burned, leaves behind a residue having a sufficient shape retention capability and hence exhibits an excellent fire resistance by compounding an epoxy resin with a phosphorus compd., a neutralized thermally expandable graphite, and an inorg. filler in a specified ratio. SOLUTION: Hundred pts.wt. epoxy resin is compounded with 50-150 pts.wt. phosphorus compd., 15-40 pts.wt. neutralized heat expandable graphite, and 30-500 pts.wt. inorg. filler, provided the sum of amts. of the phosphorus compd., the neutralized heat expandable graphite or a hydroxylated hydrocarbon compd., and the inorg. filler is 200-600 pts.wt. An esp. pref. phosphorus compd. is ammonium polyphosphate or the like. The particle size of the graphite is pref. 20-200 mesh. The filler pref. has a particle size of 0.5-100 μm, and magnesium hydroxide and aluminum hydroxide are esp. pref. as the filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a fire-resistant resin composition.

[0002]

2. Description of the Related Art Hitherto, fire resistance has been one of the important properties in the field of building materials. 2. Description of the Related Art In recent years, resin materials have been widely used as building materials along with the expansion of uses of building materials. However, resin materials further provided with fire resistance have been demanded.

[0003] As such fire resistance, not only the material itself is not easily burned, but also such a property that the flame is not transferred to the back surface of the material is required. Since the resin component and the organic component inherently have the property of burning or melting themselves, how long does not this state occur,
Another problem is how long the contained inorganic components do not fall off.

As a method for imparting such properties to a resin material, for example, Japanese Patent Application Laid-Open No. 6-25476 discloses a method in which red phosphorus or a phosphorus compound and thermally expandable graphite are added to a polyolefin resin. . However, this method provides sufficient performance for flame retardancy, but when formed into a sheet and used as a backing material for walls, etc., only brittle ash remains in the fire and fire test, However, there were problems such as falling off and the back surface temperature rising to a reference value of 260 ° C. or more.

[0005]

SUMMARY OF THE INVENTION In view of the above, it is an object of the present invention to provide a fire-resistant material which exhibits excellent fire resistance by having flame retardancy and having a sufficient shape retention ability after burning. An object of the present invention is to provide a conductive resin composition.

[0006]

The refractory resin composition according to the first aspect of the present invention (hereinafter referred to as the first aspect of the present invention) comprises an epoxy resin, a phosphorus compound, and a neutralized heat-expandable graphite. And an inorganic filler, each content of which is 50 to 150 parts by weight of a phosphorus compound, and 15 to 40 parts by weight of a neutralized thermally expandable graphite based on 100 parts by weight of the epoxy resin. And the inorganic filler are 30 to 500 parts by weight, and the total amount of the phosphorus compound, the neutralized heat-expandable graphite and the inorganic filler is 200 to 600 parts by weight.

The refractory resin composition according to the second aspect of the present invention (hereinafter referred to as the second aspect of the present invention) comprises an epoxy resin, a phosphorus compound, a hydrocarbon compound having a hydroxyl group in a molecule, and an inorganic filler. Is a refractory resin composition, wherein the content of each is 50 to 150 parts by weight of a phosphorus compound and 100 to 150 parts by weight of a hydrocarbon compound having a hydroxyl group in a molecule thereof, based on 100 parts by weight of the epoxy resin. Parts by weight and the inorganic filler are 30 to 500 parts by weight, and the total amount of the phosphorus compound, the hydrocarbon compound having a hydroxyl group in the molecule and the inorganic filler is 200 to 600 parts by weight.

The refractory resin composition according to the third aspect of the present invention (hereinafter referred to as the third aspect of the present invention) comprises an epoxy resin, a phosphorus compound, an alkali metal, an alkaline earth metal and a group IIB of the periodic table. A refractory resin composition containing any one or more carbonates of a metal belonging to the composition, wherein the content of each is based on 100 parts by weight of the epoxy resin.
The total amount of the phosphorus compound and the carbonate is 50 to 600 parts by weight, and the weight ratio of the phosphorus compound and the carbonate is 6: 4 to
4: 6.

The refractory resin composition (1) of the present invention 1 contains an epoxy resin, a phosphorus compound, neutralized heat-expandable graphite, and an inorganic filler.

The epoxy resin is not particularly limited, but is basically obtained by reacting a monomer having an epoxy group with a curing agent. Examples of the monomer having an epoxy group include difunctional glycidyl ether type, glycidyl ester type, and polyfunctional glycidyl ether type.

The above-mentioned bifunctional glycidyl ether type monomers include, for example, polyethylene glycol type, polypropylene glycol type, neopentyl glycol type, 1,6-hexanediol type, trimethylolpropane type, propylene oxide-bisphenol A type,
Monomers such as hydrogenated bisphenol A type are exemplified.

Examples of the glycidyl ester type monomer include monomers such as hexahydrophthalic anhydride type, tetrahydrophthalic anhydride type, dimer acid type, and p-oxybenzoic acid type. Examples of the polyfunctional glycidyl ether type monomer include phenol novolak type, orthocresol novolak type, DP
Monomers such as P novolak type and dicyclopentadiene / phenol type are exemplified.

The monomers having an epoxy group may be used alone or in combination of two or more.

The curing agent may be a polyaddition type or a catalyst type. Examples of the polyaddition type curing agent include polyamine, acid anhydride, polyphenol, and polymercaptan. Further, as the catalyst type curing agent,
For example, tertiary amines, imidazoles, Lewis acid complexes and the like are exemplified.

The method for curing the epoxy resin is not particularly limited, and can be performed by a known method.

The epoxy resin may be provided with flexibility, and the following methods can be given as a method of providing flexibility. Increase the molecular weight between crosslinking points. Reduce the crosslink density. Introduce a soft molecular structure. Add plasticizer. Introduce an interpenetrating network (IPN) structure. Disperse and introduce rubbery particles. Introduce microvoids.

The method is a method in which the distance between the cross-linking points is increased by reacting in advance using an epoxy monomer having a long molecular chain and / or a curing agent, thereby exhibiting flexibility. As the curing agent, for example, polypropylene diamine or the like is used. Is a method of reducing the crosslink density in a certain region and developing flexibility by reacting with an epoxy monomer and / or a curing agent having a small number of functional groups. As a curing agent, for example, as a bifunctional amine or epoxy monomer,
For example, a monofunctional epoxy or the like is used. Is a method of introducing an epoxy monomer having a soft molecular structure and / or a curing agent to develop flexibility. As the curing agent, for example, a heterocyclic diamine, and as the epoxy monomer, for example, an alkylene diglycol diglycidyl ether is used.

Is a method in which a non-reactive diluent such as DOP, tar, petroleum resin or the like is added as a plasticizer. Is a method of developing flexibility with an interpenetrating network (IPN) structure in which a resin having another soft structure is introduced into a crosslinked structure ring of an epoxy resin. Is a method of mixing and dispersing liquid or granular rubber particles in an epoxy resin matrix. Polyester ether or the like is used as the epoxy resin matrix. Is a method of developing flexibility by introducing microvoids of 1 μm or less into an epoxy resin matrix. Molecular weight 1 as epoxy resin matrix
000-5000 polyethers are added.

The phosphorus compound is not particularly limited.
For example, red phosphorus; various phosphates such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylendiphenyl phosphate; phosphorus such as sodium phosphate, potassium phosphate, and magnesium phosphate Acid metal salts; ammonium polyphosphates; and compounds represented by the following general formula (1). Among these, from the viewpoint of fire resistance, red phosphorus, ammonium polyphosphates, and compounds represented by the following general formula (1) are preferable. Further, from the viewpoints of performance, safety, cost, and the like, ammonium polyphosphate is preferred. Are more preferred.

[0020]

Embedded image

In the formula, R ¹ and R ³ are hydrogen, C ¹ -C 1
6 represents a linear or branched alkyl group or an aryl group having 6 to 16 carbon atoms. 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, Represents an aryloxy group represented by Formulas 6 to 16.

The above-mentioned red phosphorus improves the flame-retardant effect when added in a small amount. As the red phosphorus, commercially available red phosphorus can be used, but those obtained by coating the surfaces of red phosphorus particles with a resin are preferably used from the viewpoint of moisture resistance and safety such as not spontaneously igniting during kneading.

The above ammonium polyphosphates include
Not particularly limited, for example, ammonium polyphosphate, melamine-modified ammonium polyphosphate and the like,
Particularly, ammonium polyphosphate is preferably used from the viewpoints of flame retardancy, safety, cost and the like. Examples of commercially available products include “AP422” and “AP462” manufactured by Hoechst; “Sumisafe P” manufactured by Sumitomo Chemical; “Terage C60” manufactured by Chisso.

The compound represented by the above general formula (1) is not particularly restricted but includes, for example, methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methylpropyl Phosphonic acid, t-butylphosphonic acid, 2,3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctyl Examples include phosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, and bis (4-methoxyphenyl) phosphinic acid. Among them, t-butylphosphonic acid is expensive, but is preferable in terms of high flame retardancy.

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

The neutralized heat-expandable graphite is obtained by neutralizing heat-expandable graphite which is a conventionally known substance. The heat-expandable graphite is a natural scale-like graphite, pyrolytic graphite, powder such as quiche graphite,
Produced by treating with inorganic acids such as concentrated sulfuric acid, nitric acid and selenic acid and strong oxidizing agents such as concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, hydrogen peroxide, etc. Is a crystalline intercalation compound that maintains the layered structure of carbon.

The heat-expandable graphite obtained by the acid treatment as described above is further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, etc. Heat-expandable graphite is obtained.

The aliphatic lower amine is not particularly restricted but includes, for example, monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, butylamine and the like.

The alkali metal compound and alkaline earth metal compound are not particularly limited, and include, for example, hydroxides, oxides, carbonates, sulfates, organic acid salts of potassium, sodium, calcium, barium, magnesium and the like. Is mentioned.

The particle size of the neutralized heat-expandable graphite is preferably 20 to 200 mesh. Particle size is 200
If the mesh size is smaller than the mesh, the degree of expansion of the graphite is small, and a predetermined refractory and heat insulating layer cannot be obtained. If the mesh size is larger than 20 mesh, there is an advantage that the degree of expansion of the graphite is large. Deterioration of properties and deterioration of physical properties are inevitable.

Commercial products of the neutralized heat-expandable graphite include, for example, "CA-60S" manufactured by Nippon Kasei Co., Ltd. and "GREP-EG" manufactured by Tosoh Corporation.

The inorganic filler is not particularly limited.
For example, silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, carbonate Calcium, magnesium carbonate, zinc carbonate, barium carbonate, dawnite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, calcium silicate, talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite , Glass fiber, glass beads, silica balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate "MOS" (trade name), lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powder, slag fibers, fly ash, and a dewatered sludge.

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

The particle size of the inorganic filler is 0.5 to
It is preferably 100 μm, more preferably 1 to 50 μm. When the amount of the inorganic filler is small, it is preferable that the particle size is small because the dispersibility greatly affects the performance. However, when the amount is less than 0.5 μm, secondary aggregation occurs, and the dispersibility deteriorates. When the addition amount of the inorganic filler is large, as the high filling proceeds, the viscosity of the resin composition increases and the moldability decreases, but the viscosity of the resin composition can be reduced by increasing the particle size. From the viewpoint, those having a large particle diameter are preferable in the above range. If the particle size exceeds 100 μm, the surface properties of the molded article and the mechanical properties of the resin composition will decrease.

Among the above-mentioned inorganic fillers, in particular, hydrated inorganic substances such as magnesium hydroxide and aluminum hydroxide endothermic due to water generated by a dehydration reaction during heating,
The point that the temperature rise is reduced and high heat resistance is obtained, and
Oxide remains as a heating residue, which is particularly preferable in that it functions as an aggregate, thereby improving the strength of the residue. Magnesium hydroxide and aluminum hydroxide have different temperature ranges in which the dehydration effect is exhibited, so when used together, the temperature range in which the dehydration effect is exhibited expands, and a more effective temperature rise suppression effect is obtained. preferable.

When the particle size of the hydrated inorganic material is small, the bulk becomes large and it becomes difficult to achieve high packing. Therefore, in order to enhance the dehydration effect, the particle size is preferably large for high filling. Specifically, it is known that when the particle size is 18 μm, the filling limit is improved about 1.5 times as compared with the particle size of 1.5 μm. Further, by combining a material having a large particle size and a material having a small particle size, higher filling can be achieved.

It is considered that when ammonium polyphosphate is used as the phosphorus compound, the metal carbonate such as calcium carbonate and zinc carbonate promotes expansion by reaction with ammonium polyphosphate. In addition, it acts as an effective aggregate and forms a residue having high shape retention after burning.

Commercially available inorganic fillers include, for example, aluminum hydroxide having a particle size of 1 μm, “H-42M”.
“H-31” (manufactured by Showa Denko KK), particle size 18 μm (manufactured by Showa Denko KK); 1.8 μm particle size “whiten SB red” (manufactured by Shiraishi Calcium Co., Ltd.)
μm “BF300” (manufactured by Shiraishi Calcium Co., Ltd.) and the like. It is more preferable to use a combination of an inorganic filler having a large particle diameter and a filler having a small particle diameter, and the combination makes it possible to further increase the packing.

In the refractory resin composition (1), the content of the phosphorus compound is 50 to 150 parts by weight based on 100 parts by weight of the epoxy resin. The content of the phosphorus compound is
If the amount is less than 50 parts by weight, sufficient shape retention cannot be obtained.
If the amount exceeds 0 parts by weight, the mechanical properties are greatly reduced, and it cannot be used.

In the refractory resin composition (1), the content of the heat-expandable graphite subjected to the neutralization treatment is as follows:
15 to 40 parts by weight based on 00 parts by weight. If the content of the neutralized heat-expandable graphite is less than 15 parts by weight, sufficient thermal expansion properties cannot be obtained, and if it exceeds 40 parts by weight, the mechanical properties are greatly reduced and it cannot be used.

In the refractory resin composition (1), the content of the inorganic filler is 30 to 500 parts by weight based on 100 parts by weight of the epoxy resin. If the content of the neutralized inorganic filler is less than 30 parts by weight, sufficient fire resistance cannot be obtained, and if it exceeds 500 parts by weight, the mechanical properties are greatly reduced and the material cannot be used.

In the refractory resin composition (1), the total amount of the phosphorus compound, the neutralized heat-expandable graphite and the inorganic filler is 200 parts by weight based on 100 parts by weight of the epoxy resin.
６００600 parts by weight. If the total amount is less than 200 parts by weight, the amount of the residue after heating becomes insufficient and sufficient fire resistance cannot be obtained. If the total amount exceeds 600 parts by weight, the mechanical properties are greatly reduced, and the resin cannot be used.

By combining the neutralized heat-expandable graphite and the phosphorus compound, it is possible to prevent the expansible graphite from scattering at the time of combustion and to improve shape retention.
In the above-mentioned refractory resin composition (1), if the amount of the heat-expandable graphite is too large, it expands at the time of combustion and scatters graphite, so that a sufficient expanded heat-insulating layer cannot be obtained at the time of heating, and conversely, the phosphorus compound increases. Also, since a sufficient expanded heat insulating layer cannot be obtained during heating, the weight ratio of the heat-expandable graphite to the phosphorus compound is 9: 1 to 1: 1.
00 is preferred.

From the viewpoint of shape retention during combustion, the weight ratio of the neutralized thermally expandable graphite to the phosphorus compound is preferably 1: 3 to 1: 100, more preferably 1: 5. １ ： 1: 60, particularly preferably 1:10 to 1:40
It is. Even if the fire-resistant resin composition (1) itself is flame-retardant, if the shape retention is insufficient, the brittle residue collapses and penetrates the flame, so that the shape retention is sufficient. Therefore, the application form of the fire-resistant resin composition (1) is greatly different.

By setting the weight ratio of the neutralized heat-expandable graphite to the phosphorus compound in the above-mentioned range, it can be used for applications requiring a great demand for shape retention.

Next, the refractory resin composition (2) of the present invention 2
Will be described. The refractory resin composition (2) contains an epoxy resin, a phosphorus compound, a hydrocarbon compound having a hydroxyl group in a molecule, and an inorganic filler.

In the refractory resin composition (2), the same components as those of the first embodiment are used for the epoxy resin, the phosphorus compound and the inorganic filler.

The hydrocarbon compound having a hydroxyl group in the molecule preferably has 1 to 50 carbon atoms. However,
For polymers such as starch, this refers to one in which the number of carbon atoms in the monomer unit is within this range.

Among such hydrocarbon compounds, polyhydric alcohols having two or more hydroxyl groups in the molecule are particularly preferable. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, butanediol 1,4, hexanediol 1,6, monopentaerythritol, dipentaerythritol, tripentaerythritol, neopentaerythritol , Sorbitol, inositol,
Mannitol, glucose, fructose, starch,
Cellulose and the like may be mentioned, and these may be used alone or in combination of two or more.

The hydrocarbon compound is preferably [the number of hydroxyl groups in the molecule / the number of carbons in the molecule] = 0.2 to 2, more preferably pentaerythritol,
[The number of hydroxyl groups in the molecule / the number of carbon atoms in the molecule] = 0.7 to 1.5, such as sorbitol and mannitol. Among them, pentaerythritols are most preferable because of their high hydroxyl group content and high carbonization promoting effect.

If the above [the number of hydroxyl groups in the molecule / the number of carbons in the molecule] is less than 0.2, the decomposition of carbon chains is more likely to occur at the time of combustion than the dehydration condensation. It cannot be formed. When [the number of hydroxyl groups in the molecule / the number of carbons in the molecule] exceeds 2, the formation of a carbonized layer is not hindered, but the water resistance is significantly reduced.
When the water resistance decreases, for example, there are problems such as elution of the hydrocarbon compound when the molded body is cooled with water during molding, and bleed out of the hydrocarbon compound due to humidity during storage of the molded body.

In the refractory resin composition (2), the content of the phosphorus compound is 50 to 50 parts by weight of the epoxy resin for the same reason as in the refractory resin composition (1).
It is 150 parts by weight.

In the refractory resin composition (2), the content of the hydrocarbon compound having a hydroxyl group in the molecule is 10 to 150 parts by weight based on 100 parts by weight of the epoxy resin. If the content is less than 10 parts by weight, the formation of the carbonized layer is insufficient and the strength of the residue is insufficient, and if it exceeds 150 parts by weight, the mechanical properties are greatly reduced and the product cannot be used.

In the refractory resin composition (2), the content of the inorganic filler is 30 to 500 parts by weight based on 100 parts by weight of the epoxy resin. If the content is less than 30 parts by weight, sufficient fire resistance cannot be obtained, and if it exceeds 500 parts by weight, the mechanical properties are greatly reduced, and it cannot be used.

In the refractory resin composition (2), the total amount of the phosphorus compound, the hydrocarbon compound having a hydroxyl group in the molecule and the inorganic filler is 200 to 600 parts by weight based on 100 parts by weight of the epoxy resin. It is. Content is 2
If the amount is less than 00 parts by weight, the amount of the residue after heating becomes insufficient and a refractory heat-insulating layer cannot be formed. If the amount exceeds 600 parts by weight, the mechanical properties of the molded article are greatly reduced and the molded article cannot be used.

Next, the refractory resin composition (3) of the present invention 3
Will be described. The refractory resin composition (3) contains an epoxy resin, a phosphorus compound, and a carbonate of at least one of an alkali metal, an alkaline earth metal, and a metal belonging to Group IIB of the periodic table. If necessary, an inorganic filler other than the alkali metal or alkaline earth metal carbonate may be added as a filler as long as the expansion of the refractory resin composition (3) is not impaired.

In the refractory resin composition (3), the same components as those of the first embodiment are used as the epoxy resin and the phosphorus compound.

Examples of the carbonates of the above alkali metals, alkaline earth metals and metals belonging to Group IIB of the periodic table include:
Examples include calcium carbonate, strontium carbonate, zinc carbonate, magnesium carbonate, sodium carbonate and the like.

In the above refractory resin composition (3), a phosphorus compound and an alkali metal, an alkaline earth metal, a periodic table II
The total amount of any one or more of the metals belonging to Group B and the carbonate is 50 to 60 parts by weight based on 100 parts by weight of the epoxy resin.
0 parts by weight. If the total content is less than 50 parts by weight, sufficient fire resistance cannot be obtained, and if it exceeds 600 parts by weight, the mechanical properties are greatly reduced and use cannot be tolerated.

The phosphorus compound and any one of alkali metals, alkaline earth metals and metals belonging to Group IIB of the periodic table.
The weight ratio with the carbonate of at least one kind is preferably from 6: 4 to 4: 6. When the ratio of the phosphorus compound increases beyond the above range,
When the expansion ratio is increased, the residue becomes brittle, and when the ratio of carbonate exceeds the above range, the expansion ratio is suppressed.

The above-mentioned refractory resin composition may be added with a phenol-based, mamine-based, sulfur-based or the like antioxidant, a metal harm inhibitor, an antistatic agent, a stabilizer, as long as the physical properties are not impaired.
Crosslinking agents, lubricants, softeners, pigments and the like may be added.

The refractory resin composition can be obtained by melt-kneading the above-mentioned components using a known kneading apparatus such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, or a two-roll machine. The obtained resin composition can be formed into a sheet molding by a conventionally known molding method such as press molding, extrusion molding, and calendar molding.

[0063]

The refractory resin composition (1) of the present invention is characterized in that the epoxy resin, the phosphorus compound, the neutralized heat-expandable graphite, and the inorganic filler exhibit their respective properties. Demonstrate fire resistance performance. Specifically, when heated, the heat-expandable graphite forms an expandable heat-insulating layer to prevent the transfer of heat. At this time, since the epoxy resin is used, the resin component also forms a char (carbonized) layer and contributes as an expandable heat insulating layer. In addition, the inorganic filler increases the heat capacity at that time,
The phosphorus compound expresses the shape-retaining ability of the expandable heat insulating layer and the filler.

The fire-resistant resin composition (2) of the present invention 2 is characterized in that the epoxy resin, the phosphorus compound, the hydrocarbon compound having a hydroxyl group in the molecule, and the inorganic filler exhibit their respective properties. Demonstrate fire resistance performance. Specifically, although not always clear, the phosphorus compound promotes dehydration by heating, foams and acts as a carbonization catalyst. That is, the hydrocarbon compound having a hydroxyl group in the molecule forms a carbonized layer by the catalytic action of the phosphorus compound and forms a heat insulating layer having excellent shape retention. At this time, since the epoxy resin is used, the resin component also forms a char (carbonized) layer and contributes as an expandable heat insulating layer. In addition, the inorganic filler is considered to increase the heat capacity at that time.

The refractory resin composition (3) of the present invention comprises an epoxy resin, a phosphorus compound, and a carbonate of at least one of an alkali metal, an alkaline earth metal and a metal belonging to Group IIB of the periodic table. By mixing the phosphorus compound and the heat-expandable graphite, the polymetaphosphoric acid (strong acid) generated during heating and the carbonate (basic) chemically react, and degassing phenomena such as decarboxylation or deammonification occur. It is expected to be promoted. In addition, by foaming and expanding with two components of a phosphorus compound and a carbonate, and by using an epoxy resin,
A very strong combustion residue is obtained.

[0066]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Examples 1-3, Comparative Examples 1-3 Bisphenol F type epoxy monomers ("E807" manufactured by Yuka Shell Co., Ltd.) or urethane-modified bisphenol A type epoxy monomers (oil Shell E
292 ”), diamine-based curing agent (“ EK
FL052 ”), neutralized heat-expandable graphite (“ GREP-EG ”manufactured by Tosoh Corporation), ammonium polyphosphate (“ AP-422 ”manufactured by Hoechst), t-butylphosphonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) , Aluminum hydroxide ("H-31", manufactured by Showa Denko KK) and calcium carbonate ("Whiteton BF-300", manufactured by Bihoku Powder Chemical Co., Ltd.) using a kneading roll to obtain a fire-resistant resin composition. . The obtained refractory resin composition is cured by press molding at 150 ° C. for 15 minutes,
A plate sample for evaluation was obtained.

The following evaluations were performed on the plate samples for evaluation obtained above, and the results are shown in Table 1. (1) Fire resistance The above plate-shaped sample was cut into a thickness of 100 mm x 100 mm x 3 mm to prepare a test piece. With the test piece placed horizontally, a corn calorimeter (“ATLAS CO.
NE2A "), the sample was burned by applying an irradiation heat of 35 kW / cm ² for 30 minutes, and then the temperature of the back surface (the side opposite to the irradiation side) of the test piece was measured.
Those exceeding were judged as ×.

(2) Shape Retention The test piece (residue) after the above-mentioned fire resistance evaluation was subjected to 50 mm × 50
A metal plate having a size of 1 mm × 1 mm was placed, and weights of 10 g and 50 g were separately placed on the metal plate, and the state of the residue was observed. In each of 10 g and 50 g, ◎ indicates that the residue did not collapse (indentation, cracks, etc.) in the residue, ○ indicates that the collapse occurred in 50 g but did not occur in 10 g, and x indicates that the collapse occurred in 10 g. Judged.

[0070]

[Table 1]

(Examples 4 to 6, Comparative Examples 4 to 6) Bisphenol F type epoxy monomer ("E807" manufactured by Yuka Shell Co., Ltd.) or urethane-modified bisphenol A type epoxy monomer (oil Shell E
292 ”), diamine-based curing agent (“ EK
FL052 ") and monopentaerythritol (manufactured by Wako Pure Chemical Industries, Ltd.) as a hydrocarbon compound having a hydroxyl group in the molecule.
Number of hydroxyl groups in molecule / number of carbon in molecule = 0.8), D
-Sorbitol (manufactured by Wako Pure Chemical Industries, Ltd., number of hydroxyl groups in the molecule /
Number of carbons in the molecule = 1), corn starch ("PA220" manufactured by Nippon Shokuhin Kako Co., Ltd., number of hydroxyl groups in the molecule / number of carbons in the molecule = 0.5), ammonium polyphosphate ("AP-" manufactured by Hoechst) 422 "), t-butylphosphonic acid (manufactured by Wako Pure Chemical Industries, Ltd.), aluminum hydroxide (" H "manufactured by Showa Denko KK)
-31 ") and calcium carbonate (" Whiteton BF-300 "manufactured by Bihoku Powder Co., Ltd.) with a kneading roll to obtain a fire-resistant resin composition. The obtained refractory resin composition,
Press molding at 150 ° C. for 15 minutes and curing were performed to obtain a plate sample for evaluation.

With respect to the plate sample for evaluation obtained above, performance evaluation was performed in the same manner as in Example 1, and the results are shown in Table 2.

[0073]

[Table 2]

(Examples 7 to 9, Comparative Examples 7 to 9) Bisphenol F type epoxy monomers ("E807" manufactured by Yuka Shell Co., Ltd.) or urethane-modified bisphenol A type epoxy monomers (oil Shell E
292 ”), diamine-based curing agent (“ EK
FL052 "), ammonium polyphosphate (" AP-422 "manufactured by Hoechst), t-butylphosphonic acid (manufactured by Wako Pure Chemical Industries, Ltd.), calcium carbonate (" Whiteton BF-300 "manufactured by Bihoku Powder Chemical Co., Ltd.), and Strontium carbonate (manufactured by Sakai Chemical Co., Ltd.) was kneaded with a kneading roll to obtain a fire-resistant resin composition. The obtained refractory resin composition was press-molded at 150 ° C. for 15 minutes and cured to obtain a plate sample for evaluation.

With respect to the plate sample for evaluation obtained above, performance evaluation was performed in the same manner as in Example 1, and the results are shown in Table 3.

[0076]

[Table 3]

[0077] Incidentally, those evaluated as × in the evaluation of shape retention were very brittle, and collapsed only by standing the test piece in the longitudinal direction. Therefore, when the test piece was actually used as a refractory material, it fell off during combustion. It is expected that the fire resistance performance will be exhibited for a short time.

[0078]

The fire-resistant resin composition of the present invention has the above-mentioned structure, and forms an expanded heat-insulating layer at the time of heating, and exhibits remarkable fire resistance by maintaining its shape. Can be used. Further, the refractory resin composition of the present invention itself can be molded by ordinary equipment. For example, it can be molded into a sheet and used suitably for building coating applications.

Claims (4)

[Claims] 1. A fire-resistant resin composition containing an epoxy resin, a phosphorus compound, neutralized heat-expandable graphite, and an inorganic filler, each content of which is 100 parts by weight of the epoxy resin. The phosphorus compound is 50 to 150
Parts by weight, the neutralized thermally expandable graphite is 15 to 40 parts by weight, and the inorganic filler is 30 to 500 parts by weight, and the phosphorus compound, the neutralized thermally expandable graphite and the inorganic filler are included. A refractory resin composition having a total amount of 200 to 600 parts by weight. 2. A fire-resistant resin composition containing an epoxy resin, a phosphorus compound, a hydrocarbon compound having a hydroxyl group in a molecule, and an inorganic filler, wherein the content of each is:
5 parts by weight of a phosphorus compound to 100 parts by weight of the epoxy resin
0 to 150 parts by weight, 10 to 150 parts by weight of a hydrocarbon compound having a hydroxyl group in a molecule, and 30 to 5 parts by weight of an inorganic filler.
And the total amount of the phosphorus compound, the hydrocarbon compound having a hydroxyl group in the molecule and the inorganic filler is 200 parts by weight.
A refractory resin composition characterized in that the amount is from 600 to 600 parts by weight. 3. A fire-resistant resin composition containing an epoxy resin, a phosphorus compound, and a carbonate of at least one of an alkali metal, an alkaline earth metal and a metal belonging to Group IIB of the periodic table, Is the total amount of the phosphorus compound and the carbonate is 50 to 600 parts by weight, and the weight ratio of the phosphorus compound and the carbonate is 6: 4 to 4: 6. A fire-resistant resin composition, which is 6. 4. The fire-resistant resin composition according to claim 1, wherein the epoxy resin has flexibility.