JP2000345638A - Fireproofing composite face bar, folded plate external wall, and fireprotection and fireproofing wall constitutive body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fireproofing composite face bar small in thickness excellent in fireproof property at either low temperature or high temperature, a folded plate external wall using the fireproofing composite face bar, and a fireprotection and fireproofing wall constitutive body. SOLUTION: This fireproofing composite face bar comprises a layered product on which a thermal-expanding fireproofing layer and an auxiliary heat insulation layer are laminated on a heating surface side and on a non-heating surface side, respectively. The thermal-expanding fireproofing layer consists of a resin composition containing a thermal-expanding inorganic compound, and its ratio of volumetric expansion is 1.1 to 100 times. The auxiliary heat insulation layer is 1.5 kcal/m.h. deg.C or under in thermal conductivity, and 10% or under in the ratio of contraction in the thickness direction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fire-resistant composite face material used for steel frames such as columns and beams (beams) and wall materials, a folded plate outer wall using the fire-resistant composite face material, and a fireproof / fireproof wall. Constitution.

[0002]

2. Description of the Related Art Along with an increase in the height of buildings, lightweight wall materials have been used as structural materials for buildings. For wall materials used as structural materials for buildings, fire resistance performance standards are set forth by the Ministry of Construction Notification No. 2999 and JIS A 1304.
It is common practice to coat the back surface of a wall material with a material having excellent fire resistance.

[0003] From the viewpoint of preventing the spread of fire, heat insulation performance at 260 ° C or lower is required for fireproof and refractory outer walls. In order to exhibit such heat insulating performance, for example, a heat expandable heat insulating material in which heat expandable graphite or vermiculite is blended is used. However, the expansion start temperature of the above-mentioned thermally expandable graphite is about 200 ° C., and when it is 300 ° C. or less, its expansion ratio is greatly reduced.
Efficiency was worse than in the case where the temperature exceeded 0 ° C., and similarly, vermiculite had poor heat insulating effect at 400 ° C. or less. Therefore, at 260 ° C. or lower, the unheated surface side of the heat-expandable heat insulating material is unexpanded or low-expanded and has a high thermal conductivity. Then, there was a problem that the thickness had to be increased.

[0004]

SUMMARY OF THE INVENTION In view of the above, the present invention provides a fire-resistant composite face material having a small thickness and excellent fire resistance at both low and high temperatures, a folded plate outer wall using the fire-resistant composite face material, Further, it is an object of the present invention to provide a fireproof / fireproof wall structure.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a fire-resistant composite face material comprising a heat-expandable fire-resistant layer laminated on a heating surface side and an auxiliary heat-insulating layer on a non-heating surface side. The layer is made of a resin composition containing a heat-expandable inorganic compound, and
The volume expansion coefficient by heating for 30 minutes under the heating condition of 50 kW / m ² is 1.1 to 100 times, and the thermal conductivity of the auxiliary heat-insulating layer is 1.5 kcal / m · h · ° C. or less. And a shrinkage rate in the thickness direction of 10% or less when heated under a heating condition of 400 ° C. for 1 hour.

Hereinafter, the present invention will be described in detail.

The refractory composite face material of the present invention comprises a laminate in which a heat-expandable refractory layer is laminated on the heating side and an auxiliary heat-insulating layer is laminated on the non-heating side. The heating surface side refers to a surface that is directly exposed to a flame during a fire or is directly heated by a high temperature.

The heat-expandable refractory layer thermally expands in the event of a fire to form a refractory heat-insulating layer, and the refractory heat-insulating layer greatly reduces the heating of the auxiliary heat-insulating layer. Materials can also be used for the auxiliary insulation layer,
The thickness of the refractory composite face material can be reduced to reduce the weight.

The heat-expandable refractory layer is formed from a resin composition containing a heat-expandable inorganic compound, and has a power of 50 kW / m ^2.
There is no particular limitation as long as the volume expansion coefficient by heating for 30 minutes under the heating condition is 1.1 to 100 times. When the volume expansion coefficient of the heat-expandable refractory layer is less than 1.1 times, the heat insulating performance is insufficient, and when it exceeds 100 times, the refractory heat-insulating layer collapses.

Examples of the above-mentioned heat-expandable inorganic compound include neutralized heat-expandable graphite, vermiculite,
Borax and the like are mentioned, and among them, neutralized heat-expandable graphite and vermiculite are preferable.

As the above-mentioned heat-expandable refractory layer, for example, 3
"Fire Barrier" manufactured by M Co. (a sheet material composed of a resin composition containing chloroprene rubber and vermiculite); "Meghicut" manufactured by Mitsui Kinzoku Co., Ltd. (a sheet material composed of a resin composition containing a polyurethane resin and thermally expandable graphite) ) Can be used.

The resin composition containing the heat-expandable inorganic compound includes a thermoplastic resin and / or a rubber substance,
A resin composition (I) comprising a phosphorus compound, neutralized thermally expandable graphite and an inorganic filler, or an epoxy resin;
It is more preferable to use the resin composition (II) comprising a phosphorus compound, neutralized heat-expandable graphite, and an inorganic filler. The resin compositions (I) and (II) form a refractory heat-insulating layer by thermal expansion to exhibit sufficient heat-insulating performance and can be molded into a sheet, so that they are excellent in handleability.

Hereinafter, the resin composition (I) will be described. The thermoplastic resin and / or rubber substance is not particularly limited, and examples thereof include polyolefin-based resins such as polypropylene-based resins, polyethylene-based resins, poly (1-) butene-based resins, and polypentene-based resins; polystyrene-based resins, acrylonitrile- Butadiene-styrene resin,
Polycarbonate resin, polyphenylene ether resin, acrylic resin, polyamide resin, polyvinyl chloride resin, phenol resin, polyurethane resin, butyl rubber, polybutene, hydrogenated petroleum resin, polychloroprene, polybutadiene, polyisobutylene, nitrile rubber And the like.

Among the above-mentioned thermoplastic resins and / or rubber substances, halogenated ones themselves have high flame retardancy and are crosslinked by a dehalogenation reaction by heat.
This is preferable in that the strength of the residue after heating is improved.

Since these resins are very flexible and have rubber-like properties, they can be highly filled with the above-mentioned inorganic filler, and the resulting resin composition is flexible and flexible. In order to obtain a more flexible and flexible resin composition, a non-vulcanized rubber or a polyethylene resin is preferably used.

Examples of the polyethylene resin include ethylene homopolymers, copolymers containing ethylene as a main component, mixtures of these (co) polymers, ethylene-vinyl acetate copolymers, ethylene-ethyl An acrylate copolymer, an ethylene-methacrylate copolymer and the like can be mentioned.

Examples of the copolymer containing ethylene as a main component include copolymers of ethylene containing ethylene portion as a main component with other α-olefins. Examples of the α-olefin include: Examples include 1-hexene, 4-methyl-1-pentene, 1-octene, 1-butene, 1-pentene and the like.

Examples of the ethylene homopolymer and the copolymer of ethylene and another α-olefin include a Ziegler-Natta catalyst, a vanadium catalyst, and a metallocene compound containing a tetravalent transition metal. Among them, polyethylene resins obtained by using a metallocene compound containing a tetravalent transition metal or the like as a polymerization catalyst are preferable.

The tetravalent transition metal contained in the metallocene compound is not particularly limited, and includes, for example, titanium, zirconium, hafnium, nickel, palladium, platinum and the like. The metallocene compound refers to a compound in which one or more cyclopentadienyl rings and one or more analogs thereof are present as ligands in the tetravalent transition metal.

Examples of the polyethylene resin obtained by using the above metallocene compound containing a tetravalent transition metal as a polymerization catalyst include, for example, "CGCT", "Affinity", "Engage" manufactured by Dow Chemical Company; and "EXTRACT" manufactured by Exxon Chemical Company. And the like.

The thermoplastic resin and / or rubber substance may be
They may be used alone or in combination of two or more. A blend of two or more resins may be used as the base resin in order to adjust the melt viscosity, flexibility, tackiness, etc. of the resin.

The thermoplastic resin and / or rubber substance may be further crosslinked or modified within a range that does not impair the fire resistance of the heat-expandable fire-resistant layer in the present invention. The timing at which the thermoplastic resin and / or rubber substance is crosslinked or modified is not particularly limited, and a previously crosslinked or modified thermoplastic resin and / or rubber substance may be used. Cross-linking and modification may be performed simultaneously when other components such as are blended. In addition, crosslinking or modification may be performed after other components are added to the thermoplastic resin and / or rubber substance, and the crosslinking or modification may be performed at any stage.

The method for crosslinking the thermoplastic resin and / or the rubber material is not particularly limited, and a crosslinking method generally used for a thermoplastic resin or a rubber material, for example, a crosslinking method using various crosslinking agents, peroxides and the like. And a crosslinking method by electron beam irradiation.

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, and ammonium polyphosphates are more preferable in terms of performance, safety, cost, and the like. preferable.

[0025]

Embedded image

Wherein R ¹ and R ³ are hydrogen, carbon number 1
It represents a 16 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,
Represents an aryl group having 6 to 16 carbon atoms or an aryloxy group having 6 to 16 carbon atoms.

The above-mentioned red phosphorus improves the flame-retardant effect by adding a small amount. 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-mentioned ammonium polyphosphates are not particularly restricted but include, for example, ammonium polyphosphate and melamine-modified ammonium polyphosphate. Of these, ammonium polyphosphate is preferably used from the viewpoint of handleability. As a commercially available product, for example, "E" manufactured by Clariant
XOLIT AP422 ”,“ EXOLIT AP46 ”
2, "Sumisafe P" manufactured by Sumitomo Chemical Co., Ltd., "Terage C60", "Terage C70", "Terage C80" manufactured by Chisso.

The compound represented by the 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 above-mentioned thermally expandable graphite is prepared by mixing powders such as natural scale graphite, pyrolytic graphite and Kish graphite with inorganic acids such as concentrated sulfuric acid, nitric acid and selenic acid, and concentrated nitric acid.
A graphite intercalation compound formed by treating with a strong oxidizing agent such as perchloric acid, perchlorate, permanganate, dichromate, hydrogen peroxide, etc., while maintaining the layered structure of carbon. It is a crystalline compound.

The heat-expandable graphite that has been subjected to the acid treatment as described above is further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, or the like, so that the heat-expandable heat-treated graphite is neutralized. Graphite.

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 the alkaline earth metal compound are not particularly limited,
For example, hydroxides, oxides, carbonates, sulfates, organic acid salts of potassium, sodium, calcium, barium, magnesium and the like can be mentioned.

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 kneading with a resin component described later, dispersibility deteriorates, and a decrease in physical properties is inevitable.

As a commercially available product of the neutralized heat-expandable graphite, for example, “Frame Cut GRE” manufactured by Tosoh Corporation
P-EG "," GRAFG "manufactured by UCAR Carbon
UARD ”and the like.

The vermiculite is not particularly limited, and includes, for example, "Vermiculite" manufactured by Kinsei Matech.

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 and the like. Among them, hydrous inorganic substances and metal carbonates are preferred.

The above-mentioned hydrated inorganic substances such as magnesium hydroxide and aluminum hydroxide endothermic due to water generated by the dehydration reaction during heating, and the temperature rise is reduced to obtain high heat resistance. Oxide remains as a residue, and it is particularly preferable in that it functions as an aggregate to improve the strength of the residue. Magnesium hydroxide and aluminum hydroxide have different temperature ranges in which the dehydrating effect is exhibited.
It is preferable to use them together because a more effective temperature rise suppression effect can be obtained.

The above metal carbonates such as calcium carbonate and zinc carbonate are considered to promote swelling by reaction with the above phosphorus compound. In particular, when ammonium polyphosphate is used as the phosphorus compound, a high swelling effect is obtained. Can be In addition, it acts as an effective aggregate and forms a residue having high shape retention after burning.

Among the above-mentioned metal carbonates, further, alkali metal carbonates such as sodium carbonate; alkaline earth metal carbonates such as magnesium carbonate, calcium carbonate and strontium carbonate; Carbonates and the like are preferred. Generally, it is considered that an inorganic filler contributes to an improvement in residue strength and an increase in heat capacity because it functions as an aggregate.

The particle size of the inorganic filler is 0.5 to
100 μm can be used. When the amount of the inorganic filler is small, the inorganic filler is preferably small in particle size because the dispersibility greatly affects the performance. However, when the inorganic filler is less than 0.5 μm, secondary aggregation occurs, and the dispersibility deteriorates. When the 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 diameter. From the viewpoint, those having a large particle size are preferred. Particle size 100μ
If it exceeds m, the surface properties of the molded article and the mechanical properties of the resin composition will decrease. More preferably, it is about 1 to 50 μm.

As the inorganic filler, for example, aluminum hydroxide “Hygilite H-particle having a particle size of 1 μm” is used.
42M "(manufactured by Showa Denko KK)," Heidilite H-31 "having a particle size of 18 m (manufactured by Showa Denko KK), and" Whiteton SB red "having a particle size of 1.8 m, which is calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.) ), And “BF300” (manufactured by Bihoku Powder Chemical Co., Ltd.) having a particle size of 8 μm.

The above-mentioned inorganic fillers may be used alone or in combination of two or more. In addition, 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. By using the inorganic filler in combination, it is possible to increase the filling while maintaining the mechanical performance of the thermally expandable refractory layer. Becomes possible.

In the resin composition (I), the total amount of the phosphorus compound and the neutralized heat-expandable graphite is 20 to 100 parts by weight of the thermoplastic resin and / or rubber substance. 200 parts by weight are preferable, and the weight ratio of the above-mentioned thermally expandable graphite to the phosphorus compound [(thermally expandable graphite) /
(Phosphorus compound)] is preferably 0.01 to 9.

The amount of the inorganic filler is from 50 to 5 based on 100 parts by weight of the thermoplastic resin and / or rubber substance.
The weight ratio of the inorganic filler to the phosphorus compound [(inorganic filler) / (phosphorus compound)] is preferably 0.1 part by weight.
6 to 1.5 is preferred.

Examples of the inorganic filler include the above-mentioned hydrated inorganic substance, alkali metal, alkaline earth metal, and periodic table.
Group IIb metal carbonates are preferred, more preferably
It is a mixture of a hydrated inorganic substance and a metal carbonate.

Hereinafter, the resin composition (II) will be described. The resin composition (II) comprises an epoxy resin, a phosphorus compound,
It consists of neutralized heat-expandable graphite and an inorganic filler.

The epoxy resin used in the resin composition (II) is not particularly limited, but is basically obtained by reacting a monomer having an epoxy group with a curing agent. The method for curing the epoxy resin is not particularly limited, and can be performed by a known method. Examples of the monomer having an epoxy group include monomers of a bifunctional glycidyl ether type, a glycidyl ester type, and a polyfunctional glycidyl ether type.

Examples of the bifunctional glycidyl ether type monomer 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 hexahydrophthalic anhydride type, tetrahydrophthalic anhydride type, dimer acid type, and p-oxybenzoic acid type monomers.

Examples of the polyfunctional glycidyl ether type monomer include phenol novolak type, orthocresol novolak type, DPP novolak type, and dicyclopentadiene phenol type monomers.

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

As the curing agent, a polyaddition type or a catalyst type is used. 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, Lewis acids, Lewis bases, and the like.

Other resins may be added to the epoxy resin. When the amount of the other resin increases, the effect of the epoxy resin is not exhibited, so that the epoxy resin 100
500 parts by weight or less based on parts by weight is preferable.

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.

Is a method in which an epoxy monomer having a long molecular chain and / or a curing agent are reacted in advance to increase the distance between cross-linking points to exhibit flexibility.
As the curing agent, for example, polypropylene diamine or the like is used. Is an epoxy monomer having a small number of functional groups and / or
Alternatively, the reaction is carried out using a curing agent to reduce the crosslink density in a certain region to exhibit flexibility.
As the curing agent, for example, a bifunctional amine is used, and as the epoxy monomer, for example, a monofunctional epoxy is used.
Is a method in which an epoxy monomer having a soft molecular structure and / or a curing agent is introduced to exhibit 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.

The method of exhibiting flexibility by an interpenetrating network (IPN) structure in which a resin having another soft structure is introduced into the crosslinked structure of the epoxy resin. Is a method of blending liquid or granular rubber particles with an epoxy resin matrix. As the epoxy resin matrix, for example, polyester ether or the like is used. Is a method of expressing flexibility by introducing microvoids of 1 μm or less into an epoxy resin matrix. As the epoxy resin matrix, for example, a molecular weight of 100
0-5000 polyethers are added.

By adjusting the rigidity and flexibility of the epoxy resin, it is possible to form a flexible sheet from a hard plate-like material, and it can be applied to various parts where fire resistance is required.

As the phosphorus compound, the neutralized heat-expandable graphite and the inorganic filler, the same components as those of the resin composition (I) are used.

In the resin composition (II), the total amount of the phosphorus compound, the neutralized thermally expandable graphite and the inorganic filler is 50 to 900 parts by weight based on 100 parts by weight of the epoxy resin. Is preferred. Further, the weight ratio of the above-mentioned thermally expandable graphite to the phosphorus compound [(thermally expandable graphite) / (phosphorus compound)] is preferably 0.01 to 9, and the weight ratio of the above-mentioned inorganic filler to the phosphorus compound [( (Inorganic filler) / (phosphorus compound)] is preferably 0.6 to 1.5.

In the resin compositions (I) and (II), the heat-expandable graphite expands by heating to form a heat-insulating layer, thereby preventing heat transmission. The inorganic filler contributes to an increase in heat capacity at that time, and the phosphorus compound has a shape retention ability of the expanded heat insulating layer.

The above-mentioned heat-expandable refractory layer preferably has an initial bulk density at 25 ° C. of 0.8 to 2 g / cm ³ .
By setting the initial bulk density at 25 ° C. in the range of 0.8 to 2 g / cm ³ , physical properties such as heat insulation and fire resistance required for the above-mentioned thermally expandable fire-resistant layer are not impaired. Excellent in properties.

If the initial bulk density of the above-mentioned thermally expandable refractory layer at 25 ° C. is less than 0.8 g / cm ³ , a sufficient amount of an expanding agent, a carbonizing agent, a nonflammable filler, etc., in the resin composition. Cannot be added, the expansion ratio after heating and the amount of residue become insufficient, and it becomes impossible to form a refractory heat insulating layer. If the initial bulk density at 25 ° C. exceeds 2 g / cm ³ , the handleability of the refractory composite face material is reduced because the weight of the resin composition becomes too large. More preferably, it is 1 to 1.8 g / cm ³ .

The heat-expandable refractory layer has a bulk density of 0.05 to 0.5 g / cm ³ when heated at 500 ° C. for 1 hour.
It is preferred that If the bulk density at the time of heating at 500 ° C. for 1 hour is less than 0.05 g / cm ³ , there are too many gaps, and the fireproof heat-insulating layer cannot maintain its shape due to collapse at the time of expansion. If it exceeds 0.5 g / cm ³ , the expansion ratio becomes insufficient, fire resistance cannot be sufficiently exhibited, and in any case, a fire-resistant heat-insulating layer cannot be formed. More preferably, 0.1 to 0.3
g / cm ³ .

In the present invention, a flame retardant, an antioxidant, a metal harm inhibitor, an antistatic agent, a stabilizer, a cross-linking agent may be added to the resin composition as long as the physical properties of the resin composition are not impaired.
Lubricants, softeners, pigments, tackifier resins and the like may be added.

The above-mentioned resin composition is melted using a known kneading apparatus such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a two-roller, a trimmer, and a planetary stirrer. It can be obtained by kneading. The obtained resin composition can be formed into a sheet-like heat-expandable refractory layer by a conventionally known method such as press molding, extrusion molding, or calendar molding.

Examples of the auxiliary heat insulating layer include a ceramic blanket, a glass wool plate, a glass mat, a rock wool plate, a gypsum board, a ceramic plate, a lightweight aerated concrete plate (ALC), a concrete plate, a cement plate, and a calcium silicate plate. , A water-containing inorganic substance-containing board, and a composite board thereof. As a commercial product,
For example, Flex Guard (Nichias "Ceramic Blanket"), Super Felton (Nichias "Glass Mat"), MG Felt (Nichias "Rock Wool"), Tiger Board (Yoshino Gypsum "Gypsum Board") And Cellston (“Calcium silicate plate” manufactured by Ask Corporation). Among these, cement boards,
A calcium silicate plate, a hydrate containing inorganic hydrate, and a gypsum board are preferred. Since they contain water of crystallization inside, they also have an endothermic effect. The auxiliary insulation layer,
They may be used alone or in combination of two or more.

The auxiliary heat-insulating layer has a thermal conductivity of 1.5 kc.
al / m · h · ° C. or less, and the shrinkage in the thickness direction by heating for 1 hour under a heating condition of 400 ° C. is 1
It is preferably 0% or less. The lower the thermal conductivity of the auxiliary heat insulating layer is, the more preferable it is, and 1.5 kcal / m · h · ° C.
If the thickness exceeds the above range, a thickness similar to that of the thermally expandable refractory layer after expansion is required to ensure sufficient heat insulation, and it is difficult to reduce the thickness of the refractory composite face material.

When the shrinkage in the thickness direction by heating for 1 hour under the heating condition of 400 ° C. exceeds 10%,
Since the shrinkage has a large effect on the heat insulating effect, it is difficult to reduce the thickness of the refractory composite face material. In addition, a general resin foam melts or burns when heated, and its volume is significantly reduced.
When heated for 1 hour under the heating condition of 00 ° C., the shrinkage ratio is 1
When it exceeds 0%, it becomes a state in which no heat insulating function is exhibited.

The above-mentioned auxiliary heat-insulating layer is made of a differential scanning calorimeter (DS).
According to C), the total endothermic amount when heated to 600 ° C. at a rate of temperature increase of 10 ° C./min is preferably 100 J / g or more. If it is 100 J / g or more, the rate of temperature rise will be slow, and the heat insulation performance will be better.

The thickness of the heat-expandable refractory layer and the auxiliary heat-insulating layer is not particularly limited.
m or less, more preferably 0.4 to 3 mm, and the thickness of the auxiliary heat insulating layer is preferably 10 mm or less, more preferably 2 to 5 mm. Within this range, the handleability is good and the indoor space is not narrowed.

When a material made of an adhesive material is used as the heat-expandable fire-resistant layer, workability in producing a fire-resistant composite face material is improved. The term "having tackiness" means having a property that enables temporary fixing to a flame-shielding layer and / or an auxiliary heat-insulating layer, which will be described later, and means having a wide range of tackiness and / or adhesion.

When the heat-expandable refractory layer has insufficient tackiness, the tackiness can be imparted, for example, by adding a tackifier to the thermoplastic resin and / or rubber substance. The tackifier is not particularly limited,
For example, tackifier resins, plasticizers, oils and fats, low-molecular high polymers, and the like can be used.

For the purpose of improving workability and strength of combustion residues, for example, lath, wire mesh, aluminum foil, aluminum glass cloth, cloth, nonwoven fabric, resin film, resin film, etc. A combustion residue reinforcing material layer made of cloth, glass cloth, or the like may be laminated. Examples of the resin film include a polyethylene film, a polypropylene film, and a polyester film.

The above-mentioned combustion residue reinforcing material layer may be laminated on the heating-side surface of the heat-expandable refractory layer, or may be laminated between the heat-expandable refractory layer and an auxiliary heat insulating layer described later. As a combustion residue reinforcing material layer, if it is not ignited by direct fire and does not burn, such as lath, wire mesh, aluminum foil, aluminum glass cloth, etc., by arranging it on the heating surface side,
The strength of the combustion residue can be reinforced more effectively.
In addition, when the resin film is disposed between the heat-expandable fire-resistant layer and the auxiliary heat-insulating layer, the combustion residue reinforcing material layer has an advantage that the heat-sealing enables the lamination with the auxiliary heat-insulating layer.
In the case of the combustion residue reinforcing material layer of the resin film, the thickness is preferably 0.25 mm or less.

In the fire-resistant composite face material of the present invention, it is preferable to further laminate a flame-shielding layer made of a non-combustible material or a quasi-non-combustible material on the heating surface side of the heat-expandable refractory layer. Examples of the non-combustible material or semi-combustible material include, for example, iron plate, stainless steel plate, galvanized steel plate, aluminum plate, other metal plate, and PVC steel plate, color steel plate, etc. Board, gypsum board, lightweight aerated concrete board (AL
C), a concrete board, a cement board, a calcium silicate board, and a composite board thereof are used. The non-combustible materials or quasi-non-combustible materials may be used alone or in combination of two or more.

The thickness of the flame-shielding layer is preferably 0.1 to 3 mm. When the thickness is less than 0.1 mm, the flame-shielding function is insufficient, and when it exceeds 3 mm, the expansion of the thermally expandable refractory layer may be hindered.

The non-combustible material or semi-combustible material is preferably a surface-processed metal plate. Examples of the surface finishing include surface treatment such as painting for measures against design, rust, corrosion, and durability, and shaping processing such as emboss shape, corrugated sheet shape, and groove shape for improving design and strength.

In the present invention, an outer wall of a folded plate can be obtained by using the metal plate subjected to the surface treatment as a noncombustible material or a quasi-noncombustible material. The method for producing the folded plate outer wall is not particularly limited, and examples thereof include the following method. First, after laminating a heat-expandable refractory layer on the back surface of a color steel plate, a bending process is performed to give an embossed, corrugated, and grooved shape, and then an auxiliary heat-insulating layer is laminated to form a folded plate outer wall. . Since the auxiliary heat-insulating layer at this time can easily follow the shape of the folded plate, a material having flexibility and good shape following properties, such as rock wool, glass mat, and ceramic blanket, can be suitably used.

The composition of the fire-resistant composite face material of the present invention is as follows.
(1) heat-expandable fire-resistant layer / auxiliary heat-insulating layer, (2) heat-expandable fire-resistant layer a / auxiliary heat-insulating layer / heat-expandable fire-resistant layer b, (3) heat-expandable fire-resistant layer / auxiliary heat-insulating layer a / auxiliary heat insulation Layer b, (4) heat-expandable fire-resistant layer a / heat-expandable fire-resistant layer b / auxiliary heat-insulating layer, (5) flame-shielding layer / heat-expandable fire-resistant layer / auxiliary heat-insulating layer, (6) combustion residue reinforcing material layer / A heat-expandable refractory layer / auxiliary heat-insulating layer.
In the above configuration, the left side represents the heating surface side, and the right side represents the non-heating surface side.

The method for producing the refractory composite face material having the above-mentioned structure is not particularly limited, and a heat-expandable refractory layer formed into a sheet in advance may be bonded to the auxiliary heat-insulating layer by self-adhesion.
You may bond together with an adhesive. It is also possible to reduce the number of steps by directly applying the resin composition constituting the heat-expandable fire-resistant layer to the auxiliary heat-insulating layer, the flame-shielding layer or the combustion residue reinforcing material layer using a coater, a laminator or the like. .

The use of the fire-resistant composite face material is not particularly limited, but it can be used in applications requiring heat insulation and fire resistance, such as in the automotive industry, the electric and electronic industries, and the building materials field. Further, depending on each application, the components of the resin composition and the mixing ratio thereof can be appropriately selected. Further, in the field of building materials, the fire-resistant composite face material of the present invention can be suitably used as a covering material for steel frames, composite wall materials, backing materials for walls such as ceilings, floors, and partition walls. However, the joint material used only for covering the joint portion is not within the scope of the present invention.

The fireproof / fireproof wall structure of the present invention has a fireproof composite face material disposed on the back surface (indoor) side of the wall material. The wall material is not particularly limited, and examples thereof include a steel plate, a stainless steel plate, an aluminum-zinc alloy plate, an aluminum plate, a calcium silicate plate, a calcium carbonate plate, a gypsum board, a pearlite cement plate, a rock wool plate, a slate plate, and an ALC.
Examples include a board, a ceramic board, a mortar, a precast concrete board, and a composite of cement and a piece of wood. As commercially available products, for example, Moen Siding (Nichiha,
Ceramic siding), Bellmatier (Matsushita Electric Works,
Ceramics siding), Asrock (extruded cement board, manufactured by Nozawa), Mace (extruded cement board, manufactured by Mitsubishi Materials), Hebel (ALC board, manufactured by Asahi Kasei Corporation), and the like.

The fire-resistant composite face material can be fixed with welding screws, nails, screws, bolts, etc., after the auxiliary heat-insulating layer is coated on the wall material side.

The above-mentioned fireproof / fireproof wall structure is 300
When the temperature is higher than 0 ° C., the heat-expandable refractory layer expands to form a refractory heat-insulating layer to prevent heat transfer, and the auxiliary heat-insulating layer prevents heat from being transmitted to the wall material. However, at a low temperature of 300 ° C. or less, the formation of the refractory heat-insulating layer due to the expansion of the heat-expandable refractory layer is insufficient, so that the auxiliary heat-insulating layer mainly prevents heat from being transmitted to the wall material. Such fire and fire wall constructions are, for example, in the automotive industry,
It can be suitably used as a wall covering material for electronic industries and buildings.

As a method of applying the above-mentioned fire-resistant and fire-resistant wall structure, in addition to a method of coating a fire-resistant composite face material which has been previously laminated on a wall material, an auxiliary heat insulating layer is coated on the back surface of the wall material, and Above is a method of coating a thermally expandable refractory layer. The method of coating the heat-expandable fire-resistant layer and the auxiliary heat-insulating layer on the back surface of the wall material is not particularly limited, and for example, a method of fixing with welding screws, nails, screws, bolts, or the like may be employed. it can. Preferably, a method is used in which the heat-expandable refractory layer and the auxiliary heat-insulating layer are fixed at once with a common welding screw or the like.

When installing the above-mentioned fire-resistant composite face material on a steel frame or a wall material, in order to prevent a flame from entering from the joint of the fire-resistant composite face material, a flame barrier layer between adjacent fire-resistant composite face materials is required. It is preferable to install them so that they overlap each other.

Further, a reinforcing member may be used from the following viewpoints. Fire-resistant coating materials such as the fire-resistant composite face material,
For example, it is necessary to satisfy a fire performance standard specified in a fire test of JIS A 1304.

The joints of the refractory composite face material and the joints of the flame barrier layer, the combustion residue reinforcing material layer, the heat-expandable fire-resistant layer, the auxiliary heat-insulating layer, and the like are mechanically weak and are not easily impacted. Also, the impact may cause deformation of the refractory composite face material. Even in the event of an actual fire, if a building member falls, the fire-resistant composite surface material is easily deformed from the joints, etc., so heat enters from the deformed part, causing the aggregate to deform or break. Become. Therefore, it is preferable to improve the mechanical strength and impact resistance by disposing a reinforcing member at the joint.

[0090]

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.

Resin Composition Constituting Heat-Expandable Fire-Resistant Layer Resin compositions A to G having the amounts shown in Table 1 were sheeted to prepare a heat-expandable fire-resistant layer having a predetermined thickness. In addition, the resin composition A
C to G were kneaded with a kneading roll and then formed into a sheet having a predetermined thickness by hot pressing. After kneading a mixture of an epoxy monomer and a curing agent with a kneading roll, the resin compositions DF were cured by a hot press at 100 ° C. for 1 hour to form a sheet having a predetermined thickness.

[0092]

[Table 1]

In Table 1, the following components and materials were used. Butyl rubber: “Butyl # 065” manufactured by Exxon Polybutene: “Polybutene # 100” manufactured by Idemitsu Petrochemical Co.
R "Hydrogenated Petroleum Resin:" Escolets #, manufactured by Tonex Corporation "
5320 "Metallocene polyethylene:" EG82 "manufactured by Dow Chemical Company
00 "Epoxy resin:" Bisphenol F-type epoxy monomer E807 "manufactured by Yuka Shell Co., Ltd. and" Diamine-based curing agent FL052 "manufactured by Yuka Shell Co., Ltd. in a weight ratio of 40:60. Thermal expandable graphite:" Frame cut "manufactured by Tosoh Corporation. GREP-
EG "Vermiculite: manufactured by Kinsei Matetsu Co., Ltd. Ammonium polyphosphate: manufactured by Clariant" EXOL "
IT AP422 "Aluminum hydroxide:" Heidilite H- manufactured by Showa Denko KK
31 "Calcium carbonate:" BF300 "manufactured by Bihoku Powder Chemical Co., Ltd. Medicicut: manufactured by Mitsui Kinzoku Paint Co., Ltd., resin sheet material composed of urethane resin and thermally expandable graphite Fire barrier: manufactured by Sumitomo 3M, resin sheet material composed of chloroprene and vermiculite

Measurement of expansion ratio of heat-expandable fire-resistant layer
A sample cut to a size of 0 mm has an inner dimension of 100 mm
After being placed on the bottom surface of a stainless steel container having a size of 100 mm and a height of 30 mm, a heat amount of 50 kW / m ² was irradiated to the heat-expandable refractory layer side for 30 minutes using an ATLAS cone calorimeter “CONE2” and burned. It was expanded (corresponding to the combustion conditions during a medium-scale fire) to form a refractory and heat-insulating layer. The expansion ratio in the thickness direction was calculated from the thickness of the obtained refractory heat-insulating layer by the following formula, and is shown in Tables 2 and 3. Expansion ratio (times) in the thickness direction = t / t ₀ , where t is the thickness after expansion, t ₀
Indicates the thickness before expansion. Since the expansion is limited only in the thickness direction by the use of the container, the expansion ratio in the thickness direction is regarded as the volume expansion rate.

(Examples 1 to 10, Comparative Examples 1 to 3) On one surface of the above-mentioned heat-expandable fire-resistant layer, a flame-shielding layer, a combustion residue reinforcing layer, a heat-expandable fire-resistant layer and an auxiliary heat-insulating layer having a predetermined thickness were laminated. Table 2
And 3 were prepared. In Examples 1, 2, 5, 6, and 10, each layer was laminated using the self-adhesiveness of the heat-expandable fire-resistant layer to obtain a fire-resistant composite face material.
In Example 3, each layer was laminated using an epoxy-based adhesive.
In Examples 4, 8 and 9, the flame-shielding layer, the combustion residue reinforcing layer and the heat-expandable fire-resistant layer were laminated using the curing of an epoxy resin, and the auxiliary heat-insulating layer was laminated using an epoxy-based adhesive. I went. The lamination of the auxiliary heat insulating layer and the iron plate was performed using an epoxy-based adhesive.

The fire-resistant composite facing material (size 1 m × 1 m) obtained in the above Examples and Comparative Examples was used as a test sample, and the test sample was subjected to a fire resistance test in accordance with JIS A 1304. The temperatures of the back surface (the auxiliary heat-insulating layer or the iron plate side) of the refractory composite face material were measured and are shown in Tables 2 and 3.

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

As described above, the fire-resistant composite face material of the present invention has excellent fire resistance even at a low temperature of 300 ° C. or lower. Accordingly, the fire-resistant composite face material of the present invention is excellent in fire resistance at both low temperature and high temperature while being thin, and is excellent in handleability and ensuring indoor space. Therefore, it can be used for various parts and uses such as steel frames such as columns and beams and wall materials. In addition, the fireproof / fireproof wall structure of the present invention also has excellent fire resistance, as well as excellent workability and room space security.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/34 C08K 3/34 C08L 21/00 C08L 21/00 63/00 63/00 C 101/00 101 / 00 (72) Inventor Hitomi Muraoka 2-1 Hyakuyama, Shimamoto-cho, Mishima-gun, Osaka Sekisui Chemical Industry Co., Ltd. (72) Inventor Kazuhiro Okada 2-1 Hyakuyama, Shimamoto-cho, Mishima-gun, Osaka Sekisui Chemical Co., Ltd. Inside

Claims (11)

[Claims] 1. A fire-resistant composite face material comprising a heat-expandable fire-resistant layer laminated on a heating surface side and an auxiliary heat-insulating layer laminated on a non-heating surface side,
The heat-expandable refractory layer is formed of a resin composition containing a heat-expandable inorganic compound, and has a volume expansion rate of 1.1 to 1.1 when heated under heating conditions of 50 kW / m ² for 30 minutes.
100 times, and the auxiliary heat-insulating layer has a thermal conductivity of 1.5
A fire-resistant composite face material having a kcal / m · h · ° C. or less and a shrinkage in a thickness direction of 10% or less when heated for 1 hour under a heating condition of 400 ° C. 2. The fire-resistant composite face material according to claim 1, wherein the heat-expandable inorganic compound is heat-expandable graphite. 3. The composite material according to claim 1, wherein the thermally expandable inorganic compound is vermiculite. 4. A resin composition (I) comprising a thermoplastic resin and / or a rubber substance, a phosphorus compound, a heat-expandable inorganic compound, and an inorganic filler. 3. The fire-resistant composite face material according to 3. 5. The refractory composite surface according to claim 1, wherein the resin composition (II) contains an epoxy resin, a phosphorus compound, a thermally expandable inorganic compound, and an inorganic filler. Wood. 6. The auxiliary heat-insulating layer comprises a differential scanning calorimeter (DS).
The refractory composite according to any one of claims 1 to 5, wherein the total endothermic amount when heated to 600 ° C at a rate of 10 ° C / min by C) is 100 J / g or more. Face material. 7. A flame-retardant layer comprising a non-combustible material or a quasi-non-combustible material is further laminated on the heat-expandable refractory layer on the heating surface side.
7. The refractory composite face material according to any one of items 6 to 6. 8. The fire-resistant composite face material according to claim 7, wherein the non-combustible material or the quasi-non-combustible material is a metal plate subjected to surface treatment. 9. The fire-resistant composite face material according to claim 1, wherein a combustion residue reinforcing material layer is laminated on the heating surface side of the heat-expandable fire-resistant layer. 10. An outer wall of a folded plate using the refractory composite face material according to claim 8. 11. A fire-resistant / fire-resistant wall structure comprising the fire-resistant composite face material according to any one of claims 1 to 9 installed on the back side of a wall material.