JP4781254B2 - Sheet made of fire resistant resin composition - Google Patents

Description

  The present invention relates to a sheet comprising a refractory resin composition.

  Conventionally, fire resistance is one of the important performances in the field of building materials. In recent years, resin materials have been widely used for building materials as the use of building materials expands. However, there is a demand for resin materials with fire resistance.

  Such fire resistance is required not only to make the material itself difficult to burn but also to prevent the flame from turning to the back of the material. Resin components and organic components inherently have the property of burning or melting themselves, so how long will it not be in such a state, how long will the contained inorganic components not fall off, etc. Is a problem.

  As a method for imparting such properties to a resin material, for example, JP-A-6-25476 discloses a method of adding red phosphorus or a phosphorus compound and thermally expandable graphite to a polyolefin resin. However, this method provides sufficient performance for flame retardancy, but when it is molded into a sheet and used as a wall lining material, only brittle ash remains in the fire and fire resistance tests, and the residue Have fallen off, and the back surface temperature has risen to a reference value of 260 ° C. or higher.

  In view of the above, an object of the present invention is to provide a sheet comprising a fire-resistant resin composition that exhibits flame resistance and exhibits excellent fire-resistance performance by having a residue having sufficient shape retention ability after combustion. There is to do.

The sheet of the fire-resistant resin composition according to the first aspect of the present invention (hereinafter referred to as the present invention) has a bifunctional amine as the curing agent (a1) and a bifunctional glycidyl ether as the epoxy monomer (a2). Epoxy resin (A) using at least one selected from the group consisting of a mold, a glycidyl ester type and a polyfunctional glycidyl ether type, a phosphorus compound (B), a heat-expandable graphite (C) subjected to neutralization treatment, And the sheet | seat which consists of a refractory resin composition containing other inorganic fillers (D), Comprising: Each content is a phosphorus compound (B) with respect to 100 weight part of this epoxy resin (A). 50 to 150 parts by weight, neutralized heat-expandable graphite (C) is 15 to 40 parts by weight, and inorganic filler (D) is 30 to 500 parts by weight. The phosphorus compound (B) and neutralization treatment The The total amount of 200-600 parts by weight der of thermally expandable graphite (C) and the inorganic filler (D) is, the inorganic filler (D) is magnesium hydroxide, hydrated inorganic such as aluminum hydroxide and / Or it is a sheet | seat which consists of a refractory resin composition which is metal carbonates, such as a calcium carbonate and a zinc carbonate .
The sheet comprising the refractory resin composition according to claim 2 of the present invention is a refractory resin composition in which the epoxy monomer (a2) is a bisphenol F type epoxy monomer or a urethane-modified bisphenol A type epoxy monomer. It is the sheet | seat which consists of.
The sheet comprising the refractory resin composition according to claim 3 of the present invention is a sheet comprising the refractory resin composition in which the water-containing inorganic substance is aluminum hydroxide and the metal carbonate is calcium carbonate. It is characterized by being.
Moreover, the sheet | seat which consists of a refractory resin composition which is invention of Claim 4 of this invention is a sheet | seat which consists of a refractory resin composition in which the particle size of the said aluminum hydroxide is larger than the particle size of the said calcium carbonate. It is characterized by being.

  The fire-resistant resin composition of the present invention has the above-described configuration, and forms an expanded heat insulating layer when heated, and further exhibits a remarkable fire-resistant performance by maintaining its shape, and thus can be used in a wide range of applications. Moreover, the fireproof resin composition itself of this invention can be shape | molded with a normal installation, for example, can be shape | molded in a sheet form and can be used conveniently for the coating | covering application etc. of a building.

  The fireproof resin composition of the present invention contains an epoxy resin, a phosphorus compound, neutralized thermally 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 bifunctional glycidyl ether type, glycidyl ester type, and polyfunctional glycidyl ether type.

  Examples of the bifunctional glycidyl ether type monomer include polyethylene glycol type, polypropylene glycol type, neopentyl glycol type, 1,6-hexanediol type, trimethylolpropane type, propylene oxide-bisphenol A type, hydrogenated bisphenol. A monomer such as type A is 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 monomers include phenol novolak type, orthocresol novolak type, DPP novolak type, dicyclopentadiene / phenol type monomer, and the like.

  The monomer having the epoxy group may be used alone or in combination of two or more.

  Examples of the curing agent include polyaddition type and catalyst type. Examples of the polyaddition type curing agent include polyamine, acid anhydride, polyphenol, and polymercaptan. Examples of the catalyst-type curing agent include tertiary amines, imidazoles, and Lewis acid complexes.

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

Flexibility may be imparted to the epoxy resin, and examples of methods for imparting flexibility include the following methods.
(1) Increase the molecular weight between cross-linking points.
(2) Reduce the crosslinking density.
(3) Introducing a soft molecular structure.
(4) A plasticizer is added.
(5) Introducing an interpenetrating network (IPN) structure.
(6) Disperse and introduce rubber-like particles.
(7) Introducing microvoids.

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

(4) is a method of adding a non-reactive diluent such as DOP, tar, petroleum resin or the like as a plasticizer.
(5) is a method of expressing flexibility with an interpenetrating network (IPN) structure in which a resin having another soft structure is introduced into the crosslinked structure ring of the epoxy resin.
(6) is a method of blending and dispersing liquid or granular rubber particles in an epoxy resin matrix. Polyester ether or the like is used as the epoxy resin matrix.
(7) is a method of expressing flexibility by introducing microvoids of 1 μm or less into the epoxy resin matrix. A polyether having a molecular weight of 1000 to 5000 is added as an epoxy resin matrix.

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

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. 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. The aryloxy group of Formula 6-16 is represented.

  The flame retardant effect of the red phosphorus is improved by adding a small amount. As red phosphorus, commercially available red phosphorus can be used, but from the viewpoint of safety such as moisture resistance and not spontaneously igniting during kneading, a material in which the surface of red phosphorus particles is coated with a resin is preferably used.

  The ammonium polyphosphates are not particularly limited and include, for example, ammonium polyphosphate, melamine-modified ammonium polyphosphate, and the like. Particularly, ammonium polyphosphate is preferably used in terms of flame retardancy, safety, cost, and the like. It is done. Examples of commercially available products include “AP422” and “AP462” manufactured by Hoechst, “Sumisafe P” manufactured by Sumitomo Chemical, and “Terrage C60” manufactured by Chisso.

  The compound represented by the general formula (1) is not particularly limited. For example, methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methylpropylphosphonic acid, t-butylphosphonic acid, 2,3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, Examples thereof include phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, and bis (4-methoxyphenyl) phosphinic acid. Of these, t-butylphosphonic acid is preferable in terms of high flame retardancy although it is expensive.

  The said phosphorus compound may be used independently and 2 or more types may be used together.

  The heat-expandable graphite subjected to the neutralization treatment is obtained by neutralizing heat-expandable graphite, which is a conventionally known substance. The above heat-expandable graphite is composed of natural scale-like graphite, pyrolytic graphite, quiche graphite and other inorganic acids such as concentrated sulfuric acid, nitric acid and selenic acid, concentrated nitric acid, perchloric acid, perchlorate and permanganic acid. It is a graphite intercalation compound produced by treatment with a strong oxidizing agent such as salt, dichromate, hydrogen peroxide, etc., and is a crystalline compound that maintains the layered structure of carbon.

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

  The aliphatic lower amine is not particularly limited, and examples thereof include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, and butylamine.

  The alkali metal compound and alkaline earth metal compound are not particularly limited, and examples thereof include hydroxides such as potassium, sodium, calcium, barium, and magnesium, oxides, carbonates, sulfates, and organic acid salts. .

  The particle size of the neutralized heat-expandable graphite is preferably 20 to 200 mesh. When the particle size is smaller than 200 mesh, the degree of expansion of graphite is small, and a predetermined fireproof heat insulating layer cannot be obtained. When the particle size is larger than 20 mesh, there is an advantage that the degree of expansion of graphite is large. In doing so, the dispersibility becomes worse, and the deterioration of physical properties is inevitable.

  As a commercial item of the said heat-expandable graphite by which the neutralization process was carried out, Nippon Kasei Co., Ltd. "CA-60S", Tosoh Corporation "GREP-EG", etc. are mentioned, for example.

  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, Calcium carbonate, 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-based balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder, various gold Powder, potassium titanate, magnesium sulfate “MOS” (trade name), lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless steel fiber, zinc borate, various magnetic powders, slag fiber, fly ash, dehydrated sludge Etc.

  In general, the inorganic filler is considered to contribute to an improvement in residual strength and an increase in heat capacity because it functions as an aggregate. The said inorganic filler may be used independently or 2 or more types may be used together.

  As a particle size of the said inorganic filler, 0.5-100 micrometers is preferable, More preferably, it is 1-50 micrometers. The inorganic filler having a small particle size is preferable because the dispersibility greatly affects the performance when the addition amount is small. However, if it is less than 0.5 μm, secondary aggregation occurs and the dispersibility is deteriorated. When the amount of the inorganic filler added is large, the viscosity of the resin composition increases and the moldability decreases as the high filling proceeds, but the viscosity of the resin composition can be decreased by increasing the particle size. In view of the above, a particle having a large particle size is preferable in the above range. When the particle size exceeds 100 μm, the surface properties of the molded body and the mechanical properties of the resin composition are lowered.

  Among the above inorganic fillers, in particular, water-containing inorganic substances such as magnesium hydroxide and aluminum hydroxide generate endotherm due to the water generated by the dehydration reaction during heating, and the temperature rise is reduced and high heat resistance is obtained. This is particularly preferable in that the oxide remains as a heating residue and this acts as an aggregate to improve the strength of the residue. Magnesium hydroxide and aluminum hydroxide differ in the temperature range where the dehydration effect is exerted. Therefore, when used together, the temperature range where the dehydration effect is exhibited widens, and a more effective temperature rise suppressing effect can be obtained. preferable.

  When the particle size of the hydrated inorganic substance is small, the bulk increases and it becomes difficult to achieve high filling. Therefore, in order to increase the dehydration effect, a large particle size is preferable. Specifically, it is known that when the particle size is 18 μm, the filling limit amount is improved by about 1.5 times compared to the particle size of 1.5 μm. Further, by combining a large particle size and a small particle size, higher packing can be achieved.

  The metal carbonates such as calcium carbonate and zinc carbonate are considered to promote expansion by reaction with ammonium polyphosphate when ammonium polyphosphate is used as the phosphorus compound. It also acts as an effective aggregate and forms a highly shape-retaining residue after combustion.

  In the commercial product of the above inorganic filler, for example, as aluminum hydroxide, “H-42M” (made by Showa Denko) having a particle size of 1 μm, “H-31” (made by Showa Denko) having a particle size of 18 μm; calcium carbonate Examples thereof include “Whiteon SB red” (manufactured by Shiraishi Calcium Co., Ltd.) having a particle diameter of 1.8 μm, “BF300” (manufactured by Shiraishi Calcium Co., Ltd.) having a particle diameter of 8 μm, and the like. In addition, it is more preferable to use a combination of an inorganic filler having a large particle size and one having a small particle size, and the combination can further increase the filling.

  In the refractory resin composition, the phosphorus compound content is 50 to 150 parts by weight with respect to 100 parts by weight of the epoxy resin. If the content of the phosphorus compound is less than 50 parts by weight, sufficient shape retention cannot be obtained, and if it exceeds 150 parts by weight, the mechanical properties are greatly deteriorated and cannot be used.

  In the above refractory resin composition, the content of the heat-expandable graphite subjected to the neutralization treatment is 15 to 40 parts by weight with respect to 100 parts by weight of the epoxy resin. If the content of the heat-expandable graphite subjected to the neutralization treatment is less than 15 parts by weight, sufficient thermal expansion cannot be obtained, and if it exceeds 40 parts by weight, the mechanical properties are greatly deteriorated and cannot be used.

  In the refractory resin composition, the content of the inorganic filler is 30 to 500 parts by weight with respect to 100 parts by weight of the epoxy resin. When the content of the inorganic filler is less than 30 parts by weight, sufficient fire resistance cannot be obtained, and when it exceeds 500 parts by weight, the mechanical properties are greatly deteriorated and cannot be used.

  In the above refractory resin composition, the total amount of the phosphorus compound, the neutralized thermally expandable graphite and the inorganic filler is 200 to 600 parts by weight with respect to 100 parts by weight of the epoxy resin. If the total amount is less than 200 parts by weight, the amount of residue after heating becomes insufficient and sufficient fire resistance cannot be obtained, and if it exceeds 600 parts by weight, the mechanical properties are greatly deteriorated and cannot be used.

  By combining the neutralized thermally expandable graphite and the phosphorus compound, scattering of the expandable graphite at the time of combustion can be suppressed, and shape retention can be improved. In the above refractory resin composition, if there is too much heat-expandable graphite, it will expand during combustion and the graphite will scatter, so that a sufficient expansion heat insulation layer will not be obtained during heating. Since a sufficient expanded heat insulating layer cannot be obtained, the weight ratio of the thermally expandable graphite and the phosphorus compound is preferably 9: 1 to 1: 100.

  Further, from the viewpoint of shape retention at the time of combustion, the weight ratio between the heat-expandable graphite subjected to the neutralization treatment and the phosphorus compound is preferably 1: 3 to 1: 100, more preferably 1: 5 to 1: 1. 60, particularly preferably 1:10 to 1:40. Even if the refractory resin composition itself is flame retardant, if the shape retention is insufficient, the brittle residue collapses and penetrates the flame, so fire resistance depends on whether the shape retention is sufficient. The application form of the functional resin composition is greatly different.

  By making the weight ratio of the heat-expandable graphite and the phosphorus compound subjected to the neutralization treatment within the above-described range, it can be used for application forms having a large demand for shape retention.

  In addition to antioxidants such as phenolic, amine-based, sulfur-based antioxidants, metal damage inhibitors, antistatic agents, stabilizers, cross-linking agents, lubricants, softening, as long as the physical properties of the refractory resin composition are not impaired. Agents, pigments and the like may be added.

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

(Function)
The fireproof resin composition of the present invention exhibits fireproof performance by the respective components of the epoxy resin, the phosphorus compound, the neutralized thermally expandable graphite, and the inorganic filler exhibiting their respective performances. Specifically, the heat-expandable graphite forms an expandable heat insulating layer during heating to prevent heat transfer. At that time, since an 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, and the phosphorus compound expresses the ability to retain the shape of the expandable heat insulating layer and the filler.

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

( Reference Example 1, Examples 1 and 2 , Comparative Examples 1 to 3)
Bisphenol F type epoxy monomer ("E807" manufactured by Yuka Shell Co., Ltd.) or urethane-modified bisphenol A type epoxy monomer ("E292" manufactured by Yuka Shell Co., Ltd.), diamine-based curing agent (oil conversion) shown in Table 1 Shell “EKFL052”), neutralized thermally expandable graphite (“GREP-EG” manufactured by Tosoh Corporation), ammonium polyphosphate (“AP-422” manufactured by Hoechst), t-butylphosphonic acid (Wako Pure) Yakuhin Co., Ltd.), aluminum hydroxide (“H-31” manufactured by Showa Denko KK), and calcium carbonate (“Baiton BF-300” manufactured by Bihoku Flour & Chemical Co., Ltd.) are kneaded with a kneading roll to produce a fireproof resin composition I got a thing. The obtained fire resistant resin composition was press-molded at 150 ° C. for 15 minutes and cured to obtain a plate sample for evaluation.

The following performance evaluation was performed on the evaluation plate-like sample obtained above, and the results are shown in Table 1.
(1) Fire resistance The said plate-shaped sample was cut | disconnected to 100 mm x 100 mm x 3 mm thickness, and the test piece was produced. Using a cone calorimeter (“CONE2A” manufactured by ATLAS) with this test piece set horizontally, it was burned by applying an irradiation heat of 35 kW / cm ² for 30 minutes, and then the back side of the test piece (on the irradiation side and The temperature on the opposite side) was measured, and 260 ° C. or lower was evaluated as ◯, and the one exceeding 260 ° C. was determined as ×.

(2) Shape retention A metal plate of 50 mm × 50 mm × 1 mm thickness is placed on the test piece (residue) after the above fire resistance evaluation, and 10 g and 50 g of weights are separately placed on the metal plate to form a residue. Was observed. Both 10 g and 50 g were crushed in the residue (recessed, cracked, etc.) ◎, 50 g was crushed but 10 g was not crushed ◯ 10 g was crushed and x was broken Judged.

  In addition, what was judged as x in the evaluation of shape retention is very brittle, it collapses just by standing the test piece in the longitudinal direction, so when actually used as a refractory material, it falls off during combustion and has fire resistance performance. It is expected to develop for a short time.

Claims (4)

Epoxy resin using bifunctional amine as curing agent (a1) and at least one selected from the group consisting of bifunctional glycidyl ether type, glycidyl ester type and polyfunctional glycidyl ether type as epoxy monomer (a2) ( A), a phosphorus compound (B), a neutralized thermally expandable graphite (C), and a sheet comprising a fireproof resin composition containing other inorganic fillers (D),
Each content is 50 to 150 parts by weight of the phosphorus compound (B), 15 to 40 parts by weight of the neutralized thermally expandable graphite (C), and 100 parts by weight of the epoxy resin (A). The inorganic filler (D) is 30 to 500 parts by weight,
The phosphorus compound (B), Ri total amount 200-600 parts by weight der neutralized thermally expandable graphite (C) and the inorganic filler (D),
The inorganic filler (D) is a sheet comprising a refractory resin composition, wherein the inorganic filler (D) is a hydrous inorganic substance such as magnesium hydroxide or aluminum hydroxide and / or a metal carbonate such as calcium carbonate or zinc carbonate .   The sheet comprising the refractory resin composition according to claim 1, wherein the epoxy monomer (a2) is a bisphenol F type epoxy monomer or a urethane-modified bisphenol A type epoxy monomer. The sheet comprising the refractory resin composition according to claim 1 , wherein the water-containing inorganic substance is aluminum hydroxide and the metal carbonate is calcium carbonate. The sheet made of the refractory resin composition according to claim 3 , wherein the particle size of the aluminum hydroxide is larger than the particle size of the calcium carbonate.