JP2000213082A - Fire-resistant coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve durability by applying a coating treatment to the peripheral edge end section of a laminated sheet laminated with a surface material layer on both faces of a sheet layer with a coating material. SOLUTION: A sheet layer A made of a resin composition containing a phosphorus compound and neutralized thermal expansible graphite 20-300 pts.wt. in total and an inorganic filler 20-500 pts.wt. against a thermoplastic resin and/or a rubber material 100 pts.wt. and having the weight ratio 0.01-9 between the neutralized thermal expansion graphite and the phosphorus compound is extrusion-molded. A galvanized steel sheet is laminated as a surface material B layer 1 on one face of the sheet layer A. A surface material B layer 2 made of a low-density polyethylene film, an aluminum deposition film or an aluminum lamination film is laminated on the other face to form a laminated sheet C. A coating treatment is applied to its peripheral edge end section with a coating material D mainly made of butyl rubber and containing an inorganic filler 10-500 pts.wt. against a resin component 100 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a refractory coating,
More specifically, the present invention relates to a fireproof covering material that can be easily applied to columns, beams, walls, and the like.

[0002]

2. Description of the Related Art In recent years, lightweight steel frames have been used as beams, columns, etc., which are structural materials of buildings in apartment houses and detached houses. Steel frames used as structural materials for such buildings include Ministry of Construction Notification No. 2999 and J.
A fire resistance performance standard is defined by IS A 1304, and a method of coating the surface of a steel frame with a material having excellent fire resistance (fire-resistant coating material) is generally implemented in order to satisfy the standard.

[0003] As a coating material for imparting fire resistance to steel frames, Japanese Patent Application Laid-Open No. Hei 6-32664 discloses a material in which inorganic components such as vermiculite and rock wool are mixed with water glass or hydraulic cement. . However, since this coating material needs to be applied or sprayed on the steel frame at the time of construction, there is a problem that the workability is poor. Further, the thickness of the formed refractory coating layer was likely to be uneven, and when the thickness was uneven, sufficient fire resistance could not be exhibited. In addition, cracks may occur in the formed fire-resistant coating layer, and the fire resistance may be reduced.
Furthermore, when sprayed by a wet or semi-dry method, it takes a long time to cure, so that the working efficiency is poor.

Further, in order to provide fire resistance to a steel frame, a method of arranging a metal plate, an inorganic board, or the like around the steel frame has been proposed. However, in this case, a gap is generated at a portion where the ends abut. It is necessary to fill the gap with other materials,
There was a problem that extra work was required for construction.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a fired residue having a sufficient shape retention property, thereby exhibiting excellent fire resistance performance. It is an object of the present invention to provide a refractory coating material in which no gap is generated.

[0006]

The refractory coating material of the present invention comprises:
The total amount of the phosphorus compound and the neutralized heat-expandable graphite is 20 to 300 parts by weight based on 100 parts by weight of the thermoplastic resin and / or the rubber substance, and the inorganic filler 20 to 50 parts.
Weight ratio of thermally expandable graphite containing 0 parts by weight and neutralized to phosphorus compound (thermal expandable graphite / phosphorus compound)
A surface material (B) layer composed of any one of an inorganic fiber sheet, a metal plate and a resin sheet is laminated on both sides of a sheet layer (A) composed of a resin composition having a thickness of 0.01 to 9,
Further, the peripheral edge of the obtained laminated sheet (C) is coated with a coating material (D) containing 10 to 500 parts by weight of an inorganic filler based on 100 parts by weight of a resin component containing butyl rubber as a main component. It is characterized by becoming.

Hereinafter, the present invention will be described in detail. The fire-resistant covering material of the present invention is a laminated sheet (C) in which a surface material (B) layer is laminated on both surfaces of a sheet layer (A), and a peripheral edge of the laminated sheet (C) is covered with a covering material (D). The sheet layer (A) is formed of a resin composition containing a thermoplastic resin and / or a rubber substance, a phosphorus compound, neutralized heat-expandable graphite, and an inorganic filler.

The thermoplastic resin and / or rubber material is not particularly limited. For example, polyolefin resins such as polypropylene resin and polyethylene resin, poly (1-) butene resin, polypentene resin, and polystyrene resin Resin, acrylonitrile-butadiene-styrene resin, polycarbonate resin, polyphenylene ether resin, acrylic resin, polyamide resin, polyvinyl chloride resin, phenol resin, polyurethane resin, polybutene, polyisobutylene, natural rubber (N
R), isoprene rubber (IR), butadiene rubber (B
R), 1,2-polybutadiene rubber (1,2-BR),
Styrene-butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber (NBR), butyl rubber (I
IR), ethylene-propylene rubber (EPM, EPD)
M), chlorosulfonated polyethylene (CSM), acrylic rubber (ACM, ANM), epichlorohydrin rubber (CO, ECO), polyvulcanized rubber (T), silicone rubber (Q), fluoro rubber (FKM, FZ), urethane rubber (U) and the like.

Above all, halogenated resins such as chloroprene-based resins and chlorinated butyl-based resins have high flame retardancy per se, and are cross-linked by a dehalogenation reaction by heat, resulting in the combustion residue after heating. It is preferable in that the strength is improved.

The above 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. In terms of performance, safety, cost, and the like, ammonium polyphosphates are preferable. More preferred.

[0011]

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 flame retardant effect is improved by adding a small amount of the above-mentioned red phosphorus. As the red phosphorus, commercially available red phosphorus can be used, but from the viewpoint of moisture resistance, safety such as not spontaneously igniting during kneading, those obtained by coating the surface of red phosphorus particles with a resin are preferably used. .

The above ammonium polyphosphates include:
Not particularly limited, for example, ammonium polyphosphate, melamine-modified ammonium polyphosphate and the like,
Ammonium polyphosphate is preferably used in terms of flame retardancy, safety, cost and the like. Commercially available products include, for example, "AP422" and "AP462" manufactured by Hoechst; "Sumisafe P" manufactured by Sumitomo Chemical; "Terage C6" manufactured by Chisso.
0, "" Terage C70, "" Terage C80, "and the like.

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
Although expensive, it is preferable in terms of high flame retardancy.

These 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 above-mentioned heat-expandable graphite is a natural scale-like graphite, pyrolytic graphite, powder such as Kish 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 above-mentioned alkali metal compound and alkaline earth metal compound are not particularly restricted but include, for example, hydroxides, oxides, carbonates, sulfates and organic acid salts of potassium, sodium, calcium, barium, magnesium and the like. And the like.

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 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, a predetermined refractory insulation layer cannot be obtained, and when the particle size is larger than 20 mesh, there is an advantage that the degree of expansion of graphite is large,
When kneaded with a thermoplastic resin and / or a rubber substance, dispersibility deteriorates, and deterioration of physical properties cannot be avoided.

The inorganic filler is not particularly limited.
For example, metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; calcium hydroxide, magnesium hydroxide, aluminum hydroxide, hydrotalcite, and the like. Hydrous inorganic substances; Basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, barium carbonate and other metal carbonates; calcium salts such as calcium sulfate, gypsum fiber and calcium silicate; silica, diatomaceous earth, dawsonite, barium sulfate ,
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 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 powders, slag fiber , Fly ash, dehydrated sludge and the like. These may be used alone or in combination of two or more.

As the above-mentioned inorganic filler, a combination of a hydrated inorganic substance and a metal carbonate is particularly preferred. Since the above-mentioned hydrated inorganic substance and metal carbonate function as an aggregate, it is considered that they contribute to the improvement of residue strength and the increase of heat capacity.

Further, the above-mentioned hydrated inorganic substance is endothermic due to water generated by the dehydration reaction at the time of heating, and the temperature rise is reduced to obtain high heat resistance. Also, oxide remains as a heating residue. This is particularly preferable in that it works as an aggregate to improve the residue strength. Among them, magnesium hydroxide and aluminum hydroxide are different in the temperature range in which the dehydrating effect is exerted, so that when used in combination, the temperature range in which the dehydrating effect is exerted expands, and a more effective temperature rise suppression effect is obtained, so that they are used together. Is preferred.

When ammonium polyphosphate is used as the phosphorus compound, the metal carbonate is considered to promote expansion by a reaction with ammonium polyphosphate. In addition, it acts as an effective aggregate and forms a residue having high shape retention after burning.

The particle diameter of the hydrated inorganic substance and the metal carbonate is preferably 0.5 to 100 μm, more preferably 1 to 50 μm.

As a commercially available product of the above-mentioned hydrated inorganic substance, for example, aluminum hydroxide “H-4” having a particle size of 1 μm is used.
2M "(manufactured by Showa Denko KK)," H-31 "with a particle size of 18 µm
(Manufactured by Showa Denko KK).

Examples of commercially available calcium carbonate include "Whiteton SB Red" having a particle size of 1.8 μm (manufactured by Shiraishi Calcium Co., Ltd.) and "BF300" having a particle size of 8 μm (manufactured by Shiraishi Calcium Co., Ltd.). .

In the above resin composition, the compounding amount of the phosphorus compound and the neutralized heat-expandable graphite (total amount of both)
Is 20 to 500 parts by weight with respect to 100 parts by weight of the thermoplastic resin and / or rubber substance (hereinafter referred to as resin component). If the total amount of the phosphorus compound and the neutralized heat-expandable graphite is less than 20 parts by weight, sufficient thermal expansibility cannot be obtained, and if it exceeds 500 parts by weight, uniform dispersion becomes difficult. It is difficult to work with the thickness, and the working method is limited.

The weight ratio of the neutralized heat-expandable graphite to the phosphorus compound (heat-expandable graphite / phosphorus compound) is as follows:
It is 0.01-9. If the ratio of the heat-expandable graphite increases, the expanded graphite during combustion scatters and a sufficient refractory heat-insulating layer is not formed.If the ratio of the phosphorus compound increases, a sufficient refractory heat-insulating layer is not formed. Heat insulation cannot be obtained.

In the above resin composition, the compounding amount of the metal carbonate is 20 to 500 parts by weight based on 100 parts by weight of the resin component. If the amount of the metal carbonate is less than 20 parts by weight, the amount of aggregate is insufficient, so that a combustion residue with sufficient strength is not formed. It is difficult to work with the thickness, and the working method is limited.

If necessary, a liquid component such as polybutene and a tackifier such as petroleum resin may be added to the resin composition.

In order to obtain the sheet layer (A) from the above resin composition, a usual sheet forming method such as extrusion molding, calender molding, hot press molding and the like can be used.

As the surface material (B) laminated on both sides of the sheet layer (A), any one of an inorganic fiber sheet, a metal plate and a resin sheet is used. As the surface material (B), the same material may be used on both surfaces, or different materials may be used.

Examples of the inorganic fiber sheet include sheets made of glass fiber, cellulose fiber, ceramic wool fiber, rock wool fiber, etc., non-woven fabric, woven fabric and the like. Nonwoven fabrics and woven fabrics may be those obtained by laminating thin aluminum layers.

Examples of the metal plate include wire mesh, lath wire mesh, stainless steel plate, zinc alloy plated steel plate, aluminum plate, titanium plate, enamel plate, fluororesin coated steel plate, clad steel plate, copper plate, surface treated steel plate, aluminum zinc plywood , Aluminum foil, metal foil and the like.

Examples of the resin sheet include a resin sheet made of a thermoplastic resin or a rubber material such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polyvinylidene chloride, Teflon, and polyisobutylene. These resin sheets may be filled with an inorganic filler, or may be those laminated with an aluminum vapor-deposited film, aluminum foil or metal foil. Further, these resin sheets may be used alone or two or more kinds may be laminated.

As the laminated sheet (C), a laminated sheet of the sheet layer (A) and the surface material (B) layer is used. The method for laminating the sheet layer (A) and the surface material (B) layer is not particularly limited. For example, the surface material (B) layer may be laminated simultaneously with the formation of the sheet layer (A). After forming the layer (A), the surface material (B) layer may be press-bonded by hot pressing, or the sheet layer (A) and the surface material (B) layer may be laminated during the construction of the sheet layer (A). .
In addition, for the lamination of the sheet layer (A) and the surface material (B) layer, for example, an acrylic or epoxy-based adhesive may be used.

The peripheral edge of the laminated sheet (C) is coated with a coating material (D) as shown in FIG. 3, for example.
As the coating material (D), a composition comprising 10 to 500 parts by weight of an inorganic filler based on 100 parts by weight of a resin component containing butyl rubber as a main component is used. When the compounding amount of the inorganic filler is 1
When the amount is less than 0 parts by weight, the amount of aggregate is insufficient, so that a combustion residue having sufficient strength is not formed. When the amount is more than 300 parts by weight, uniform dispersion becomes difficult, so that it is difficult to construct a uniform thickness. The construction method is limited.

The form of the coating material (D) is not particularly limited, and may be sheet-like or paint-like. In the case of a sheet form, for example, there is a method in which the peripheral edge of the laminated sheet (C) is coated in a U-shaped cross section by utilizing the adhesiveness of butyl rubber. In the case of a paint form, spray coating by spraying or brushing is used. Coating method.

The coating material (D) can be obtained by molding the above resin component and inorganic filler into a sheet by a known molding device in the case of a sheet, or by kneading and stirring in the case of a paint. It is obtained by kneading and stirring using an apparatus.

As the refractory coating material of the present invention, for example, FIG.
As shown in (1), a unit composed of a laminated sheet (C) having an L-shaped cross section is used. Using these two units,
After being attached around the H-shaped steel so as to hold the H-shaped steel, as shown in FIG. 2, it is fixed by bolting, bolting or the like via a dry edge provided at one end.

In FIGS. 1 and 2, a metal plate is preferably used as the surface material (B) layer (1), and a foam is provided between the surface material (B) layer (1) and the sheet layer (A). May be arranged. As the foam, for example, a resin foam such as a phenol foam, an isocyanurate foam, and a polyethylene foam is preferable. Such foams
Combustion occurs at the time of heating to form a void, and this void serves as an expansion allowance when the sheet layer (A) expands.

Between the surface material (B) layer (2) and the H-shaped steel, a plate made of a non-combustible material, for example, a calcium silicate plate, a fiber-containing calcium silicate plate, a calcium carbonate plate, a gypsum board, a reinforcement A gypsum board, a perlite cement board, a fiber reinforced cement board, a wood chip cement board, a wood powder cement board, a slag gypsum board, a rock wool heat insulating board, a ceramic wool blanket, and the like may be arranged.

In the fire-resistant coating material of the present invention, for example, the sheet layer (A) is burned and expanded by heating in a fire to form a fire-resistant heat-insulating layer of non-combustible combustion residues, and the H-shaped steel rises to a high temperature. To prevent

[0047]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following examples.

(Examples 1 to 3, Comparative Example 1) Metallocene polyethylene ("EG8200" manufactured by Dow Chemical Co., Ltd.) or butyl rubber ("butyl rubber # 065" manufactured by Exxon Chemical Co., Ltd.), Idemitsu Petrochemical "Polybutene 100R", petroleum resin), tackifier ("Tosnex" Escolets 5320 "), ammonium polyphosphate (Clariant" AP422 ")
Or "Terage C80" manufactured by Chisso Corporation), neutralized heat-expandable graphite ("GREP-EG" manufactured by Tosoh Corporation), aluminum hydroxide ("H-31" manufactured by Showa Denko KK, particle size: 1)
8 μm) and a resin composition in which calcium carbonate (“Whiten BF-300” manufactured by Shiraishi Calcium Co., Ltd., particle size: 8 μm) is uniformly mixed.
Was extruded.

A surface material (B) is provided on one side of the sheet layer (A).
A zinc iron plate is laminated as the layer (1), and a low-density polyethylene film (150 μm thick) and an aluminum vapor-deposited film (“25 Pbright-
J ") or a laminated sheet (C) by laminating a surface material (B) layer (2) made of an aluminum laminated film (manufactured by Toyo Aluminum Co., Ltd.)
After the production, a peripheral end portion was coated with a coating material (D) to obtain a refractory coating material. In addition, as the coating material (D), butyl rubber (“Butyl rubber # 065” manufactured by Exxon Chemical Co., Ltd.)
A butyl rubber sheet or a butyl rubber paint composed of 100 parts by weight, 300 parts by weight of calcium carbonate (“Whiteton BF-300” manufactured by Shiraishi Calcium Co., particle size 8 μm), and 50 parts by weight of other fillers was used.

The fire resistance of the refractory coating material obtained above was evaluated by the following method, and the results are shown in Table 1.

(1) Expansion Ratio of Sheet Layer (A) Sheet (A) cut to a size of 100 mm × 100 mm × 3 mm was used as a test piece, and a cone calorimeter (ATLAS) "CO
NE2A ”), and 50 kW / m ² from the zinc iron plate side.
The thickness of the combustion residue obtained after heating with the irradiation heat amount and complete combustion was measured, and the expansion ratio (thickness of test specimen before heating / thickness of combustion residue) was calculated from the thickness before and after heating.

(2) Breaking strength of combustion residue The combustion residue obtained in the same manner as in (1) above was treated with a circular indenter having a diameter of 0.25 cm ² using a “finger feeling tester” manufactured by Kato Tech. A load was applied at a speed of 1 cm / sec, and the maximum point of the load that first appeared in the displacement load curve was taken as the breaking strength of the combustion residue.

(3) Joint gap at the time of construction Two units having an L-shaped cross section having the configuration shown in FIG.
After arranging as shown in FIG. 2 around an H-shaped steel column (3000 mm in length) having a cross-sectional shape of mm × 300 mm × 15 mm × 10 mm and fixing the dry edge by bolting, the H-shaped steel column in the vertical direction The gap between the butted portions (joint portions) of the units was measured, and the case where the gap was less than 2 mm was indicated by “○”, and the case where the gap was 2 mm or more was indicated by “×”.

[0054]

[Table 1]

[0055]

The fire-resistant coating material of the present invention has the above-mentioned structure, and is formed by abutting the edges by covering the peripheral edges with a sticky and flexible butyl rubber-based coating material. Even if the gap (joint) does not occur, no extra work for filling the gap is required.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing a configuration of a unit used for a fireproof covering material of the present invention.

FIG. 2 is a schematic sectional view showing a state in which the unit of FIG. 1 is constructed around an H-section steel.

FIG. 3 is a schematic sectional view showing one example of a coating material (D).

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) B32B 27/20 B32B 27/20 Z C04B 41/71 C04B 41/71 E04F 13/00 E04F 13/00 B F term (reference) ) 2E001 DE01 FA01 FA02 FA03 GA42 HB02 HB03 HB04 HB06 HB08 HD02 HD04 HD08 HD11 HE01 JA04 JA06 JA22 JA29 JB01 JB07 JC09 KA01 4F100 AA00B AA00C AA00D AA04A AA08 AA37A AB01B01A01 BA01 AB01 AB01 AB03 AB10 CA08A CA23D DB16D DG01B DG01C EH711 GB07 JA02A JB16A JJ07 JK13 JL01 JL04 YY00A 4G028 FA03

Claims (1)

[Claims] 1. A thermoplastic and / or rubber material 100
The total amount of the phosphorus compound and the neutralized heat-expandable graphite is 20 to 300 parts by weight, and the inorganic filler 20 to
A sheet layer comprising a resin composition containing 500 parts by weight and having a weight ratio (thermally expandable graphite / phosphorus compound) of the neutralized thermally expandable graphite to the phosphorus compound of 0.01 to 9 ( A surface material (B) layer composed of any one of an inorganic fiber sheet, a metal plate and a resin sheet is laminated on both surfaces of A),
Further, the peripheral edge of the obtained laminated sheet (C) is coated with a coating material (D) containing 10 to 500 parts by weight of an inorganic filler based on 100 parts by weight of a resin component containing butyl rubber as a main component. A fire-resistant coating material characterized by becoming.