JP2002114914A - Fireproof resin composition and sheet shape of molded product therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fireproof resin composition which can display an efficient expansion ratio if it contains a thermally expansible laminar inorganic substance to make a sheet; and a fireproof sheet made from the same. SOLUTION: The fireproof resin composition comprises a thermally expansible laminar inorganic substance and is characterized in that it can provide a sheet having a rate (an orientation rate) of 60% or more, wherein the rate is a percentage occupied by the thermally expansible laminar inorganic substance which exists along a vertical cross section of the sheet and orients within the range of ±10 deg. apart from the horizontal line parallel to the sheet surface. The fireproof sheet can be made from the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fire-resistant resin composition which can be used as a fire-resistant coating material for building materials and the like, and a fire-resistant sheet-like molded article comprising the same.

[0002]

2. Description of the Related Art With the rise of buildings, lightweight steel frames and wall materials have come to be used as building materials. Steel frames and wall materials used as structural materials for buildings are required to meet fire performance standards set forth in Ministry of Construction Notification No. 2999 and JIS A 1304. In order to satisfy this criterion, a method of coating the front surface of a steel frame or the back surface of a wall material with a material having excellent fire resistance is generally performed.

As a coating material for imparting fire resistance to steel frames and the like, JP-A-6-32664 discloses a material in which inorganic components such as vermiculite and rock wool are mixed with water glass or hydraulic cement. I have. However, this has to be applied or sprayed to the steel frame at the site at the time of construction, so that the workability is a problem. In addition, the thickness of the formed refractory coating layer tends to be uneven,
When unevenness occurred, sufficient fire resistance could not be exhibited. Further, cracks may occur in the formed fire-resistant coating layer, resulting in reduced fire resistance. Furthermore, when spraying is performed by a wet or semi-dry method, a long time is required for curing, and thus there is a problem that the working efficiency is reduced.

[0004] As a coating material for imparting fire resistance to steel frames and the like, fire resistant paints are commercially available from Mitsui Kinzoku Paints Co., Ltd. and others. Such refractory paints can be used at
Since it is necessary to mix different types of paints, uneven coating easily occurs and it is difficult to impart uniform fire resistance to steel frames.

[0005] Normally, a fireproof paint forms a film-shaped insulative heat-insulating layer in the event of a fire. This insulative heat-insulating layer is liable to cause unevenness in thickness. Then, when an impact is applied to the steel frame, there is a problem that the expanded heat insulating layer collapses and sufficient fire resistance cannot be exhibited.

As a refractory coating material, further disclosed in
As disclosed in JP-A-503654, there is a form in which a material made of expandable graphite, chloroprene latex, phenolic resin, or the like is applied in a tape shape. In this form, the above-mentioned drawback of workability has been improved, and although this contains a heat-expandable inorganic substance, the expansion characteristic of the heat-expandable inorganic substance cannot be used to the maximum, and therefore, In some cases, an increase in the amount of the thermally expandable layered inorganic material is inevitable.

[0007]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, the present invention provides a sheet containing a thermally expandable layered inorganic material, and a fire-resistant resin composition exhibiting the most efficient expansion ratio and a fire-resistant resin obtained therefrom. The purpose is to provide a sheet.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, by specifying the orientation ratio of the heat-expandable layered inorganic substance to the sheet surface, sufficient fireproof performance was obtained. The present inventors have found that a refractory sheet that can be used is obtained, and completed the present invention.

That is, a first aspect of the present invention is a resin composition containing a heat-expandable layered inorganic material, wherein the heat-existing heat is present in an arbitrary vertical cross section of a sheet from the resin composition. A fire-resistant resin composition characterized in that the ratio (orientation ratio) of the expandable layered inorganic substance oriented within a range of ± 10 degrees from parallel to the sheet surface is 60% or more.

The second aspect of the present invention (the invention of claim 2)
Is a fire-resistant resin composition according to the first invention, wherein the heat-expandable layered inorganic substance is heat-expandable graphite.

The third aspect of the present invention (the third aspect of the present invention)
The fire-resistant resin composition according to the first or second invention, wherein the fire-resistant resin composition contains 20 to 350 parts by weight of a thermally expandable layered inorganic material with respect to 100 parts by weight of a resin component. It is.

A fourth aspect of the present invention (the fourth aspect of the present invention).
Is a sheet-like molded product made of the refractory resin composition according to any one of the first to third inventions.

A fifth aspect of the present invention (the invention of claim 5).
Is a sheet-like molded product according to the fourth invention, wherein the sheet-like molded product is formed by a calender molding method or a press molding method.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The fire-resistant resin composition of the present invention is a resin composition containing a heat-expandable layered inorganic material, and is present in any vertical section of a sheet from the resin composition. A fire-resistant resin composition, characterized in that the orientation ratio, which is the ratio of those in which the layered inorganic material is oriented within a range of plus or minus 10 degrees from the direction parallel to the sheet surface, is 60% or more. Here, the orientation ratio (%) is the orientation ratio (%) = (the number of thermally expandable layered inorganic substances oriented within a range of plus or minus 10 degrees from parallel to the sheet surface in a vertical cross section of the sheet / (Number of thermally expandable layered inorganic substances existing in the vertical section of the sheet) × 100.

If the orientation ratio of the heat-expandable layered inorganic material in the sheet is 60% or more, the heat-expandable layered inorganic material expands efficiently in the direction perpendicular to the sheet surface, so that a sufficient fire-resistant heat-insulating layer can be obtained. Good heat insulation can be imparted to the member coated with. On the other hand, when the orientation ratio is less than 60%, the thermally expandable layered inorganic material thermally expands in directions other than the vertical direction, and a sufficient fire-resistant heat-insulating layer cannot be obtained, and heat insulating properties deteriorate.

The fire-resistant resin composition of the present invention is not particularly limited as long as it satisfies the above-mentioned conditions when it is formed into a sheet-like molded product. For example, the resin, the heat-expandable layered inorganic material and the inorganic filler can be used. And a resin composition containing a resin composition, a resin, a thermally expandable layered inorganic material, a phosphorus compound, and an inorganic filler.

The resin of the resin composition is not particularly limited, but examples thereof include a thermoplastic resin and / or a rubber substance, or an epoxy resin.

Examples of the thermoplastic resin include polyolefin resins such as polypropylene resin, polyethylene resin, poly (1-) butene resin, polypentene resin, polystyrene resin, acrylonitrile-butadiene-styrene resin, and polycarbonate resin. Resins, polyphenylene ether resins, acrylic resins, polyamide resins, polyvinyl chloride resins, phenolic resins, polyurethane resins, etc., which may be used alone or in combination of two or more. You may. Among them, polyolefin resins are preferable, and polyethylene resins are more preferable.

Examples of the polyethylene resin include ethylene homopolymers, copolymers containing ethylene as a main component and mixtures of these (co) polymers, as well as ethylene-vinyl acetate copolymers and 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, for example, ethylene-α containing ethylene as a main component.
-Olefin copolymers and the like, and examples of the α-olefin include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.

Examples of the copolymer of the ethylene homopolymer and another α-olefin include a Ziegler-Natta catalyst,
Examples thereof include those obtained by polymerizing a vanadium catalyst and a metallocene compound containing a tetravalent transition metal as a polymerization catalyst. Among them, a polyethylene resin obtained using a metallocene compound containing a tetravalent transition metal as a polymerization catalyst is 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. A compound in which one or more cyclopentadiene rings and analogs thereof are present as one or more ligands.

Examples of the polyethylene resin obtained by using the above metallocene compound containing a tetravalent transition metal as a polymerization catalyst include, for example, “CGC” manufactured by Dow Chemical Company.
T "," Affinity "," Engage ", and commercial products such as" EXACT "(trade name, manufactured by Exxon Chemical Co., Ltd.).

As the rubber material, 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 (EPR, 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. Two or more of them may be used in combination in order to adjust the melting temperature, flexibility, tackiness and the like of the rubber-based resin.

The above-mentioned halides such as chloroprene rubber are preferable because they themselves have high flame retardancy, crosslink occurs by a dehalogenation reaction by heat, and the strength of the heat-expandable refractory layer is improved.

The thermoplastic resin and / or rubber substance may be cross-linked or modified within a range that does not impair the performance of the heat-expandable refractory layer. There is no particular limitation on the timing of crosslinking or modification, and it may be performed at any stage.
That is, a previously crosslinked, modified thermoplastic resin and / or rubber substance may be used, and crosslinking and modification may be performed simultaneously when other components such as a phosphorus compound and an inorganic filler described later are compounded, Crosslinking or modification may be performed after blending other components with the thermoplastic resin and / or rubber substance.

The method for crosslinking the above thermoplastic resin and / or rubber substance is not particularly limited, and a usual crosslinking method for the resin, for example, a crosslinking method using various crosslinking agents, peroxides, etc., electron beam irradiation And the like.

The epoxy resin used in the present invention is not particularly limited, but is basically a resin obtained by reacting a monomer having an epoxy group with a curing agent.

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, bisphenol A type and bisphenol F type. , Propylene oxide-bisphenol A type, hydrogenated bisphenol A type, and the like.

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 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, as a polyaddition type,
Examples of the catalyst type include polyamines, acid anhydrides, polyphenols and polymercaptans, and tertiary amines, imidazoles, Lewis acid complexes and the like. The curing method of these epoxy resins is not particularly limited, and can be performed by a known method.

The epoxy resin may be provided with flexibility, and the method for providing flexibility includes the following method.

(1) Increase the molecular weight between crosslinking points. (2) Reduce the crosslink density. (3) Introduce a soft molecular structure. (4) Add a plasticizer. (5) Introduce an interpenetrating network (IPN) structure. (6) Disperse and introduce rubber-like particles. (7) Introduce microvoids.

The method (1) is a method in which the distance between the cross-linking points is increased by reacting in advance using an epoxy monomer having a long molecular chain and / or a curing agent, thereby exhibiting flexibility. As the curing agent, for example, polypropylene diamine or the like is used.

The above-mentioned method (2) is a method in which an epoxy monomer having a small number of functional groups and / or a curing agent are reacted to reduce the crosslink density in a certain region to thereby exhibit flexibility. For example, a bifunctional amine is used as a curing agent, and a monofunctional epoxy is used as an epoxy monomer.

The method (3) 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.

The method (4) is a method in which a non-reactive diluent such as DOP, tar or petroleum resin is added as a plasticizer.

The method (5) is a method in which flexibility is exhibited by an interpenetrating network (IPN) structure in which a resin having another soft structure is introduced into the crosslinked structure of the epoxy resin.

The method (6) is a method in which liquid or granular rubber particles are mixed and dispersed in an epoxy resin matrix. Polyester ether or the like is used as the epoxy resin matrix.

The method (7) is a method in which microvoids of 1 μm or less are introduced into an epoxy resin matrix to exhibit flexibility. A polyether having a molecular weight of 1,000 to 5,000 is added as an epoxy resin matrix.

By adjusting the rigidity and flexibility of the epoxy resin, a flexible sheet can be formed from a hard plate-like material, and can be applied to various parts requiring fire resistance.

The above-mentioned heat-expandable layered inorganic substance is a heat-expandable layered inorganic substance which expands when heated, and examples thereof include vermiculite, kaolin, mica, and heat-expandable graphite. Among these, thermally expandable graphite or vermiculite is preferred.

The heat-expandable graphite is a conventionally known substance. Powders such as natural scale graphite, pyrolytic graphite, and quiche graphite are mixed with inorganic acids such as concentrated sulfuric acid, nitric acid and selenic acid, concentrated nitric acid and perchloric acid. A crystalline compound that has been treated with a strong oxidizing agent such as perchlorate, permanganate, dichromate, hydrogen peroxide, etc. to produce a graphite intercalation compound, while maintaining a layered structure of carbon. It is.

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

As the aliphatic lower amine, for example,
Monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, butylamine and the like can be mentioned. As the alkali metal compound and the alkaline earth metal compound, for example, potassium, sodium,
Examples include hydroxides, oxides, carbonates, sulfates, and organic acid salts of calcium, barium, magnesium, and the like.

The particle size of the heat-expandable graphite is preferably from 20 to 200 mesh. When the particle size is smaller than 200 mesh, the degree of expansion of graphite is small, and a sufficient refractory and 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. Or, when kneading with an epoxy resin, the dispersibility becomes poor, and a decrease in physical properties is inevitable.

Commercial products of the neutralized heat-expandable graphite include, for example, “Frame Cut GRE” manufactured by Tosoh Corporation.
P-EG "," GRAFG "manufactured by UCAR Carbon
urad160 "," GRAFGurad220 "and the like.

As the above vermiculite, for example,
"Vermiculite" manufactured by Kinsei Matech Co., Ltd. and the like.

The phosphorus compound added for improving the flame retardancy is not particularly restricted but includes, for example, red phosphorus; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylide. Various phosphates such as lenyl diphenyl phosphate; metal phosphates such as sodium phosphate, potassium phosphate and magnesium phosphate; 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.

[0053]

Embedded image

In the formula (1), R ¹ and R ³ represent hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or
Represents 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 6-1
6 represents an aryloxy group.

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 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. Examples of commercially available products include “AP422” and “AP462” manufactured by Hoechst, “Sumisafe P” manufactured by Sumitomo Chemical Co., Ltd., and “Terage C” manufactured by Chisso.
60 ”,“ 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-methyl Propylphosphonic acid, t-butylphosphonic acid, 2,3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, Examples include dioctylphosphinic 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. The above phosphorus compounds may be used alone or in combination of two or more.

The inorganic filler is not particularly restricted but includes, for example, metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide and ferrites; Water-containing inorganic substances such as calcium, magnesium hydroxide, aluminum hydroxide, and hydrotalcite; metal carbonates such as basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, and barium carbonate; calcium sulfate, gypsum fiber, and silica Calcium salts such as calcium acid; 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, dewatered sludge, and the like. Among these, hydrous inorganic substances and metal carbonates are preferred.

The above-mentioned water-containing inorganic substances such as magnesium hydroxide and aluminum hydroxide endothermic due to water generated by the dehydration reaction at the time of heating. It is preferable because the strength is improved. Magnesium hydroxide and aluminum hydroxide have different temperature ranges in which the dehydrating effect is exhibited, so the combined use expands the temperature range in which the dehydrating effect is exhibited, and a more effective temperature rise suppression effect is obtained. Is sometimes preferred.

The above-mentioned metal carbonate is considered to form a residue having high shape retention after combustion by the reaction with the phosphorus compound. In particular, when ammonium polyphosphate is used as the phosphorus compound, a residue having high shape retention is formed after combustion.

Among the above metal carbonates, alkali metal carbonates such as sodium carbonate; magnesium carbonate;
Alkaline earth metal carbonates such as calcium carbonate and strontium carbonate; and metal carbonates of the Periodic Table IIb such as zinc carbonate are preferred.

Generally, the above-mentioned inorganic filler is considered to contribute to an increase in heat capacity because it functions as an aggregate. The inorganic filler may be used alone or in combination of two or more.

The particle size of the inorganic filler is 0.5 to
400 μm is preferred, more preferably 1 to 100 μm
It is. When the addition amount of the inorganic filler is small, since the dispersibility is greatly affected, a small particle size is preferable,
When the particle size is less than 0.5 μm, secondary aggregation occurs and dispersibility deteriorates. When the amount of the inorganic filler is large,
Although the viscosity of the resin composition increases and the moldability decreases as the high filling progresses, those having a large particle diameter are preferable because the viscosity of the resin composition can be reduced by increasing the particle diameter. However, when the particle size exceeds 400 μm, the surface properties of the molded article and the mechanical properties of the resin composition are reduced.

It is more preferable to use a filler having a large particle size and a filler having a small particle size in combination.
By using in combination, it is possible to highly fill the refractory sheet while maintaining the mechanical performance.

Examples of the commercially available aluminum hydroxide include “H-42M” having a particle size of 1 μm (manufactured by Showa Denko KK) and “H-31” having a particle size of 18 μm (manufactured by Showa Denko KK). Commercially available calcium carbonate products include, for example, "Whiteton SB Red" having a particle size of 1.8 [mu] m (manufactured by Bihoku Kagaku Co., Ltd.) and "FB300" having a particle size of 8 [mu] m (manufactured by Bihoku Kagaku Co., Ltd.).

The refractory resin composition of the present invention may further contain an antioxidant such as a phenol-based, amine-based or sulfur-based antioxidant, a metal harm inhibitor, an antistatic agent, and a stabilizer as long as the physical properties are not impaired. , A cross-linking agent, a lubricant, a softener, a pigment and the like may be added.

In the refractory resin composition of the present invention, the compounding amount of the inorganic filler is 5 to 100 parts by weight of the resin component.
0 to 400 parts by weight is preferred. 5 inorganic fillers
If the amount is less than 0 parts by weight, the amount of the residue after combustion is reduced, so that a sufficient refractory heat insulating layer cannot be obtained. In addition, since the ratio of combustibles increases, flame retardancy decreases. On the other hand, if it exceeds 400 parts by weight, the compounding ratio of the resin component decreases, and the adhesive strength becomes insufficient.

In the refractory resin composition of the present invention, the amount of the thermally expandable layered inorganic material is preferably 20 to 350 parts by weight based on 100 parts by weight of the resin component. If the amount of the thermally expandable layered inorganic material is less than 20 parts by weight, the expansion ratio will be insufficient, and sufficient fire resistance and fire prevention performance will not be obtained. On the other hand, 350
When the amount is more than the weight part, the cohesive force is insufficient, so that the strength as a molded product cannot be obtained.

When a hard and cohesive residue is required, the total amount of the thermally expandable layered inorganic substance and the phosphorus compound is preferably 20 to 350 parts by weight based on 100 parts by weight of the resin component. When the total amount of the heat-expandable layered inorganic substance and the phosphorus compound is less than 20 parts by weight, the expanded heat insulating layer is not formed, so that sufficient fire resistance cannot be obtained. Does not stand use. More preferably, it is 20 to 200 parts by weight.

Further, the weight ratio of the thermally expandable layered inorganic material to the phosphorus compound (thermally expandable layered inorganic material / phosphorus compound) is:
0.01 to 9 is preferred. By setting the weight ratio of the thermally expandable layered inorganic material to the phosphorus compound to 0.01 to 9, it becomes possible to obtain the shape retention and high fire resistance of the expanded heat insulating layer. If the compounding ratio of the heat-expandable layered inorganic material is too large,
The thermally expandable layered inorganic material, particularly graphite, expanded during combustion is scattered, and a sufficient expanded heat insulating layer is not formed. On the other hand, if the compounding ratio of the phosphorus compound is too large, the expansion ratio of the expanded heat insulating layer becomes small, and sufficient fire resistance cannot be exhibited.

The refractory sheet obtained from the resin composition of the present invention preferably has tackiness. Having tackiness means having properties that enable temporary fixing, and broadly having tackiness and / or adhesion. When the fire-resistant sheet of the present invention has adhesiveness, in a fire-resistant covering material described later, lamination with a face material becomes easy, and temporary fixing of the fire-resistant covering material becomes possible, thereby improving workability.

In order to impart tackiness to the refractory sheet of the present invention, for example, a method of adding a tackifier to the resin component of the above resin composition may be mentioned. The tackifier is not particularly limited, and includes, for example, tackifier resins, plasticizers, oils and fats, and low-polymerized polymers.

Examples of the tackifying resin include rosin, rosin derivative, dammar resin, copal, cumarone-indene resin, polyterpene, non-reactive phenol resin, alkyd resin, petroleum hydrocarbon resin, xylene resin, epoxy resin and the like. Is mentioned.

It is difficult for the plasticizer alone to impart tackiness to the refractory sheet, but by using it together with a tackifier resin, the tackiness can be improved. Examples of the plasticizer include a phthalate ester plasticizer, a phosphate ester plasticizer, an adipate ester plasticizer, a sebacic acid ester plasticizer, a ricinoleate ester plasticizer, a polyester plasticizer, and an epoxy plasticizer. Agents, chlorinated paraffins and the like.

The above fats and oils have the same action as plasticizers, and can be used for the purpose of imparting plasticity and as a tackifier. Examples of the fats and oils include animal fats and oils, vegetable fats and oils, mineral oils, silicone oils and the like.

The low polymer of the polymer can be used for the purpose of improving cold resistance, adjusting fluidity, etc., in addition to imparting tackiness. Examples of the high polymer low polymer include a low polymer of the above rubber substance and a low polymer of a poly (1-) butene resin.

The resin composition of the present invention is obtained by melt-kneading 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-roller and a raikai machine. Can be obtained by Further, a fire-resistant sheet which is a sheet-like molded product of the present invention is obtained by molding the above resin composition into a sheet or the like by a molding method such as press molding, extrusion molding, calender molding, and particularly, calendering. Molding and press molding are preferred.

In the fire-resistant sheet-like molded article of the present invention,
In order to increase the orientation ratio of the thermally expandable layered inorganic material in the sheet to 60% or more, the following method is particularly preferable irrespective of the simple blending. That is, if the molding method is such that calender molding is performed after kneading the resin composition, it is possible to obtain a sheet having an orientation ratio of 90% or more, and if press molding is performed after kneading, the orientation ratio is 60%. The above sheet can be obtained.

[0079]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. The evaluation method is as follows.

(1) Orientation ratio: Using a high-definition digital microscope “VH-6300” manufactured by KEYENCE, a vertical cross section of a sheet surface of 4 mm was observed at a magnification of 25 to 50 times. The angle between the thermally expandable graphite present in the 4 mm vertical cross section and the sheet surface was measured at five or more points, and the ratio of those within ± 10 degrees from the parallel was calculated. Furthermore, the vertical cross-section of five 4 mm portions was arbitrarily observed repeatedly, and the average of the calculated ratios was determined to be the orientation ratio.

(2) Expansion ratio (α): Frames were attached to the four sides so that expansion was possible only on the upper surface, and the heat-resistant sheet was expanded under the following conditions, and the orientation ratio of expansion ratio was measured. Condition 1: A sheet of 100 × 100 mm was attached to an iron plate of the same size and expanded in a direction perpendicular to the sheet surface. Condition 2: A sheet having a size of 100 × 100 mm was cut at a sample thickness (mm), bonded together so that the cross section was on the upper surface, and hot-pressed for 1 minute to expand in the direction of the original cross section of the sheet. Orientation ratio of expansion ratio (α) = expansion ratio under condition 2 (times) /
Expansion ratio (times) under condition 1 However, heating was all performed in an electric furnace at 600 ° C. for 10 minutes.

(3) Spread of expansion in the horizontal direction during heating (β): A sheet of 60 × 60 mm is heated and expanded in such a manner that expansion in the horizontal direction is not hindered at all, and the area in the horizontal direction after expansion is increased. The initial ratio was measured. (Β) = horizontal area after expansion / initial area However, all heating was performed at 600 ° C. for 10 minutes in an electric furnace.

(3) Change in adiabatic temperature: 100 × 100 m
m sheet was attached to an iron plate of the same size, and a lath wire mesh was attached to the surface opposite to the iron plate surface. Using a cone calorimeter "CONE2" manufactured by ATLAS, and radiating heat 50kW
/ M ² in the vertical direction. Heating was performed for 15 minutes from the iron plate side, the temperature on the back side was observed, and the change in the adiabatic temperature was determined by the following equation.
And less than 10 ° C. was evaluated as ○. Change in adiabatic temperature (° C) = backside temperature without frame-backside temperature with frame

The evaluation of the change in the adiabatic temperature is based on the fact that when there is no binding such as a frame at the end of the sheet, the expansion during heating spreads not only in the vertical direction but also in the horizontal direction with respect to the sheet. It is a check to determine whether or not the heat insulating property exhibited by the heat-expandable sheet during heating is lower than when the heat-insulating temperature is provided. It is considered that the resin cannot be sufficiently exerted without the end restraint, and the performance is considered to be effectively exerted when the temperature is lower than 10 ° C.

Examples 1-3 The butyl rubber (“Butyl 065” manufactured by Exxon Chemical Co., Ltd.), polybutene (“Polybutene 100R” manufactured by Idemitsu Petrochemical Co., Ltd.), and hydrogenated petroleum resin (manufactured by Tonex Co., Ltd.) in the amounts shown in Table 1 were used. Escolets 5320 "), ammonium polyphosphate (" Exolit422 "manufactured by Clariant),
Thermal expansive graphite (Tosoh “Frame Cut GREP-
EG "), aluminum hydroxide (" Heidilite H-31 ", manufactured by Showa Denko KK), and calcium carbonate (" Whiteton BF-300 ", manufactured by Bihoku Powder Chemical Co., Ltd.). A heat-expandable refractory sheet was prepared using a calender molding machine or a press molding machine. Changes in the orientation ratio, expansion ratio and adiabatic temperature of the obtained heat-expandable refractory sheet were measured and are shown in Table 1.

Comparative Example 1 A commercially available refractory paint, "Intmex" (Chemie
(Manufactured by Linz AG), and a fire resistance test was performed in the same manner as in the example. Table 1 shows the results.

Comparative Example 2 A fire resistance performance test was performed in the same manner as in the example using "Heat Mel Silence" (a product of Furukawa Techno Material Co., Ltd.) which is a commercially available fire resistant paint. Table 1 shows the results.

[0088]

[Table 1]

As is clear from Table 1, in the vertical cross section of the refractory sheet, the orientation ratio, which is the ratio of those in which the thermally expandable layered inorganic substance is oriented within a range of ± 10 degrees from the direction parallel to the sheet surface, is shown. When it is high, the orientation ratio (α) of the expansion ratio becomes small, and the spread (β) in the horizontal direction becomes small. That is, expansion in any direction except the direction perpendicular to the refractory sheet surface is suppressed, and expansion in the horizontal direction is suppressed. As a result, it can be seen that the refractory sheet works effectively in the change of the adiabatic temperature indicating the expansion performance inherently possessed.

[0090]

The fire-resistant sheet of the sheet-shaped molded article comprising the fire-resistant resin composition of the present invention has a heat-expandable layered inorganic material contained in the fire-resistant sheet material, which is parallel to the sheet surface, plus or minus 10%.
Since the ratio of those oriented in the range of the degree is high, thermal expansion in the vertical direction is promoted, and a good expanded heat insulating layer can be formed, which is useful as a fire-resistant material for buildings.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 21/02 C09K 21/02 E04B 1/94 E04B 1/94 U // B29L 7:00 B29L 7:00 F-term (reference) 2E001 DE01 GA24 HD11 HF12 JA00 JD02 JD08 LA16 MA08 4F071 AA14 AA15 AA20 AA24 AA31 AA50 AA51 AA54 AA69 AA77 AB03 AH03 BA01 BB03 BB04 BC01 4F204 AE10 AG01 FA03 AC03 BA03 AC03 BA03 AC03 BA03 AC03 AC091 BB021 BB111 BB161 BD031 BD121 BN151 CC031 CG011 CH071 CK021 CL001 CP031 DA026 DJ006 DJ036 DJ056 FA016 FD010 FD130 FD140 FD340 GL00

Claims (5)

[Claims] 1. A resin composition containing a heat-expandable layered inorganic material, wherein the heat-expandable layered inorganic material present in an arbitrary vertical cross section of a sheet from the resin composition is positively increased from parallel to the sheet surface. A fire-resistant resin composition, characterized in that the ratio (orientation ratio) of those oriented within a range of minus 10 degrees is 60% or more. 2. The fire-resistant resin composition according to claim 1, wherein the heat-expandable layered inorganic substance is heat-expandable graphite. 3. The resin composition according to claim 1, wherein the refractory resin composition comprises
The refractory resin composition according to claim 1 or 2, wherein the composition contains 20 to 350 parts by weight of a thermally expandable layered inorganic material with respect to 0 parts by weight. 4. A sheet-shaped molded article comprising the refractory resin composition according to claim 1. 5. The sheet-like molded product according to claim 4, wherein the sheet-like molded product is formed by a calender molding method or a press molding method.