JP2020139058A - Refractory material - Google Patents

Abstract

To provide a refractory material having excellent fire resistance.SOLUTION: A refractory material comprises a refractory resin composition containing a matrix component, which is at least one selected from the group consisting of a resin component and an elastomer component, thermally-expandable graphite, and a phosphorus compound. When heated for 5 minutes at 300°C it has an expansion magnification of 20 or more, and a shape retention of 0.7 N or more.SELECTED DRAWING: None

Description

The present invention relates to a refractory material used for buildings, vehicles and the like.

Refractory materials are widely used to ensure the fire resistance of structures such as buildings and various vehicles. As the fireproof material, a resin composition containing a matrix component such as a resin and a heat-expandable graphite blended in the matrix component is known. For example, Patent Document 1 discloses a refractory material composed of a thermosetting resin such as an epoxy resin, a phosphorus compound, and a refractory resin composition containing a heat-expandable graphite. In such a refractory material, when heated, the heat-expandable graphite expands to form a heat insulating layer, thereby ensuring fire resistance.

International Publication No. 2016/117699

In general, it has been attempted to ensure fire resistance of a refractory material by increasing the expansion ratio and shape retention stability at a high temperature of, for example, 500 ° C. or higher, assuming a fire. However, the refractory material may not be able to secure excellent refractory performance only by increasing the expansion ratio at high temperature and the shape retention stability.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a refractory material having more excellent refractory performance.

As a result of studies by the present inventors, the conventional refractory material does not expand sufficiently at a relatively low temperature, the expansion ratio and the shape retention stability are insufficient, and the shape retention stability of the residue is particularly low. It was found that the fire resistance performance at the initial stage was insufficient. As a result of further diligent studies, it was found that the refractory performance of the refractory material can be made more excellent by setting the expansion ratio and the shape holding force when heated at 300 ° C. to a certain value or more, and the following invention Was completed. That is, the present invention provides the following [1] to [8].
[1] A refractory material comprising a fire-resistant resin composition containing at least one matrix component selected from the group consisting of a resin component and an elastomer component, thermally expandable graphite, and a phosphorus compound.
A refractory material having an expansion ratio of 20 times or more and a shape holding power of 0.7 N or more when heated at 300 ° C. for 5 minutes.
[2] The refractory material according to the above [1], wherein the heat-expandable graphite contains a heat-expandable graphite having a volume increase rate of 1.0 ml / g / min or more when heated at 300 ° C. for 10 minutes.
[3] The refractory material according to the above [1] or [2], wherein the expansion ratio when heated at 500 ° C. for 5 minutes is 30 times or more, and the shape holding power is 0.07 N or more.
[4] The refractory material according to any one of the above [1] to [3], wherein the matrix component is an epoxy resin.
[5] The refractory material according to any one of the above [1] to [4], wherein the phosphorus compound contains a lower phosphate.
[6] The refractory material according to any one of the above [1] to [5], wherein the phosphorus compound contains a phosphate.
[7] The refractory material according to any one of the above [1] to [6], wherein the refractory resin composition further contains an inorganic filler.
[8] A fitting provided with the refractory material according to any one of the above [1] to [7].

According to the present invention, it is possible to provide a refractory material having more excellent refractory performance by setting the expansion ratio and the shape holding force at a relatively low temperature to a certain value or more.

Hereinafter, the present invention will be described in more detail.
[Refractory material]
The refractory material of the present invention comprises a refractory resin composition containing a matrix component, a heat-expandable graphite, and a phosphorus compound. The refractory material of the present invention has an expansion ratio of 20 times or more and a shape holding force of 0.7 N or more when heated at 300 ° C. for 5 minutes. If the expansion ratio is less than 20 times or the shape holding force is less than 0.7 N, the refractory material cannot sufficiently exhibit fire resistance in the initial stage of combustion, and it sufficiently prevents the occurrence of fire and the spread of fire. You may not be able to do it.

The refractory material of the present invention preferably has an expansion ratio of 25 times or more when heated at 300 ° C. for 5 minutes. When the expansion ratio at 300 ° C. is higher, the fire resistance performance in the initial stage of combustion can be further improved, and the fire resistance against fire can be further improved.
The upper limit of the expansion ratio when heated at 300 ° C. for 5 minutes is not particularly limited, but is preferably 50 times from the viewpoint of improving the mechanical strength of the expansion residue obtained by low-temperature heating.
Further, the shape retention force when heated at 300 ° C. for 5 minutes is preferably 1.5 N or more in order to improve the fire resistance performance at a low temperature. The upper limit of the shape-retaining force when heated at 300 ° C. for 5 minutes is not particularly limited, but is practically 10 N.

The refractory material of the present invention preferably has an expansion ratio of 30 times or more and a shape holding force of 0.07 N or more when heated at 500 ° C. for 5 minutes. When the expansion ratio and the shape holding force when heated at 500 ° C. for 5 minutes are equal to or higher than the above lower limit values, the fire resistance performance is improved in any temperature range from low temperature to high temperature. Therefore, excellent fire resistance is maintained not only in the initial stage of the fire but also after the fire has developed relatively, so that the fire has better fire prevention characteristics.
The upper limit of the expansion ratio when heated at 500 ° C. for 5 minutes is not particularly limited, but from the viewpoint of improving the mechanical strength of the expansion residue obtained by high-temperature heating, for example, 80 times, preferably 45 times. is there.
Further, the shape holding force when heated at 500 ° C. for 5 minutes is preferably 0.1 N or more in order to further improve the fire resistance performance at a high temperature. The upper limit of the shape-retaining force when heated at 500 ° C. for 5 minutes is not particularly limited, but is practically 10 N.

The expansion ratio in the present invention is obtained by processing a refractory material into a sample having a predetermined thickness, heating the sample at 300 ° C. or 500 ° C., measuring the thickness of the expansion residue, and measuring the thickness of the sample after heating. / Obtained from the thickness of the sample before heating. The shape-retaining force is obtained by measuring the compressive strength of the expansion residue obtained by heating the sample in the same manner. Here, for example, when the thickness is larger than 2 mm, the sample is processed to a thickness of 2 mm, and when the thickness is 2 mm or less, the sample having the same thickness (thickness of 2 mm or less) is used as a sample. Just do it. The details of the method for measuring the expansion ratio and the shape holding force are as shown in Examples described later.

The refractory material of the present invention preferably has good water resistance. Specifically, the elution rate when the refractory material is immersed in warm water at 60 ° C. for 10 days is preferably less than 5% by mass, and more preferably less than 1% by mass. When the water resistance is good, the refractory material can exhibit excellent refractory performance even after being used in an environment in contact with water.
In order to improve the water resistance, the fireproof material preferably contains a lower phosphate described later as a phosphorus compound, and more preferably contains a phosphite.

The shape of the refractory material of the present invention is not particularly limited, but may be, for example, a sheet shape or a shape other than the sheet shape. The thickness of the refractory material is not particularly limited, but is, for example, about 0.1 to 20 mm, preferably about 0.5 to 15 mm.

<Matrix resin>
The matrix resin used in the present invention is at least one selected from a resin component and an elastomer component, and these may be used in combination of two or more.
Examples of the resin component used in the matrix resin include thermosetting resins and thermoplastic resins. The thermosetting resin used in the present invention can be used without particular limitation as long as it is a resin that can be cured by heating to form a matrix component of a refractory material. The thermosetting resin may be a two-component thermosetting resin. The two-component thermosetting resin is, for example, a thermosetting resin composed of a main agent and a curing agent.

(Thermosetting resin)
Examples of the thermosetting resin used in the present invention include synthetic resins such as epoxy resin, urethane resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, and polyimide. The thermosetting resin may be used alone or in combination of two or more.
Among these thermosetting resins, at least one selected from the group consisting of epoxy resin, urethane resin, and phenol resin is preferable, and epoxy resin is more preferable. By using an epoxy resin, the sheet does not become brittle and can maintain toughness even when a large amount of filler components such as heat-expandable graphite and an inorganic filler described later are filled.
The epoxy resin as the thermosetting resin used in the present invention is, for example, a resin composed of an epoxy compound as a main agent and a curing agent. The urethane resin as a thermosetting resin used in the present invention is, for example, a resin composed of a polyol compound as a main agent and a curing agent such as a polyisocyanate compound as a curing agent.
In the present specification, unless otherwise specified, the content of the thermosetting resin means the total of the components constituting the thermosetting resin. For example, in the case of a two-component thermosetting resin, the total amount of the main agent and the curing agent is defined as the "content of the thermosetting resin".

〔Epoxy resin〕
The epoxy resin as the thermosetting resin used in the present invention is not particularly limited, and examples thereof include an epoxy compound alone or one composed of an epoxy compound as a main agent and a curing agent. The epoxy compound is a compound having an epoxy group, and specific examples thereof include a glycidyl ether type and a glycidyl ester type. The glycisyl ether type may be bifunctional or may be trifunctional or higher. The same applies to the glycidyl ester type. The epoxy compound may contain a monofunctional one in order to adjust the degree of cross-linking or the like. Among these, the bifunctional glycidyl ether type is preferable.

Examples of the bifunctional glycidyl ether type epoxy compound include alkylene glycol types such as polyethylene glycol type and polypropylene glycol type, neopentyl glycol type, 1,6-hexanediol type, and aliphatic such as hydrogenated bisphenol A type. Epoxy compounds are exemplified. Further, aromatic epoxy compounds containing an aromatic ring such as bisphenol A type, bisphenol F type, bisphenol AD type, ethylene oxide-bisphenol A type, and propylene oxide-bisphenol A type can be mentioned. Among these, aromatic epoxy compounds such as bisphenol A type and bisphenol F type are preferable.

Examples of the glycidyl ester type epoxy compound include hexahydrophthalic anhydride type, tetrahydrophthalic anhydride type, dimer acid type, and p-oxybenzoic acid type epoxy compounds.
Examples of the trifunctional or higher functional glycidyl ether type epoxy compound include phenol novolac type, orthocresol novolak type, DPP novolak type, dicyclopentadiene phenol type and the like.
These epoxy compounds may be used alone or in combination of two or more.

As the curing agent, a heavy addition type or a catalytic type is used. Examples of the heavy addition type curing agent include polyamine-based curing agents, acid anhydride-based curing agents, polyphenol-based curing agents, and polymercaptans. Examples of the catalyst-type curing agent include tertiary amines, imidazoles, and Lewis acid complexes. These curing agents may be used alone or in combination of two or more.

[Urethane resin]
The urethane resin as the thermosetting resin used in the present invention is not particularly limited, and examples thereof include those composed of a polyol compound as a main agent and a curing agent such as a polyisocyanate compound. Examples of the polyol compound include polyoxyalkylene glycols such as polyoxyethylene glycol, polyoxypropylene glycol and polyoxybutylene glycol, aliphatic diols such as 1,6-hexanediol, acrylic polyols, polyester polyols and polyether polyols. Can be mentioned. These polyol compounds may be used alone or in combination of two or more.
Among the above, polyoxyalkylene glycol is preferable as the main agent, and polyoxypropylene glycol is more preferable.
Examples of the polyisocyanate compound as a curing agent include aromatic polyisocyanates such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, and 4,4'-diphenylmethane diisocyanate, 1,6-. Examples thereof include aliphatic (or alicyclic) polyisocyanates such as hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Further, an adduct or multimer of the polyisocyanate compound, for example, an adduct of tolylene diisocyanate, poly (tolylene diisocyanate), or poly (diphenylmethane diisocyanate) can also be used. These polyisocyanate compounds may be used alone or in combination of two or more.
Among the above, the curing agent is preferably aromatic polyisocyanate or a multimer thereof, and more preferably poly (diphenylmethane diisocyanate).

[Phenolic resin]
The phenolic resin as the thermosetting resin used in the present invention is not particularly limited as long as it is a resin containing two or more phenolic hydroxyl groups in the molecule, and examples thereof include a resol type phenolic resin and a novolak type phenolic resin. From the viewpoint of obtaining a fire-resistant resin composition having a lower viscosity, a phenol resin that is liquid at room temperature (25 ° C.) is preferable, and a liquid resole-type phenol resin is more preferable. The phenolic resin may be used alone or in combination of two or more.

The curing method of the thermosetting resin is not particularly limited and can be carried out by a known method. For example, in the case of the above-mentioned epoxy resin or urethane resin, it can be cured by mixing a main agent and a curing agent and heating them.

(Thermoplastic resin)
Examples of the thermoplastic resin include polyolefin resins such as polypropylene resin, polyethylene resin, poly (1-) butene resin, and polypentene resin, polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, and ethylene vinyl acetate copolymer (EVA). ), Polyphenylene ether resin, (meth) acrylic resin, polyamide resin, polyvinyl chloride resin (PVC), novolak resin, polyurethane resin, polyisobutylene and other synthetic resins. The thermoplastic resin may be used alone or in combination of two or more.
Among these, polyvinyl chloride resin is preferable from the viewpoint of improving fire resistance.

Examples of the polyvinyl chloride-based resin include a polyvinyl chloride homopolymer, a copolymer of a vinyl chloride monomer and a monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer, and a polymer other than vinyl chloride. Examples thereof include a graft copolymer obtained by graft-copolymerizing vinyl, and these may be used alone or in combination of two or more. Further, the chlorinated polyvinyl chloride resin, which is a chlorinated product of the polyvinyl chloride resin, is also included in the polyvinyl chloride resin.

(Elastomer component)
Examples of the elastomer component include rubber and thermoplastic elastomers. The rubbers include natural rubber, isoprene rubber, butadiene rubber, 1,2-polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, chlorinated butyl rubber, ethylene-propylene rubber (EPM), and ethylene-propylene-diene rubber. (EPDM), chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, silicon rubber, fluororubber, urethane rubber and the like can be mentioned.
Examples of the thermoplastic elastomer include a thermoplastic olefin-based elastomer (TPO), a thermoplastic styrene-based elastomer, a thermoplastic ester-based elastomer, a thermoplastic amide-based elastomer, a thermoplastic vinyl chloride-based elastomer, and a combination thereof. Examples of the TPO include thermoplastic elastomers having polyolefins such as polyethylene and polypropylene as hard segments and rubbers such as ethylene-propylene rubber and ethylene-propylene-diene rubber as soft segments. The elastomer component may be used alone or in combination of two or more.
As the elastomer component, EPDM and TPO are preferable from the viewpoint of flexibility, moldability and the like.

The content of the matrix component in the refractory resin composition (that is, the refractory material) of the present invention is, for example, 10 to 80% by mass. By using a matrix component of the lower limit or more, the shape retention of the refractory material is improved. Further, by setting the value to the upper limit or less, it becomes possible to blend a certain amount or more of thermally expandable graphite, a phosphorus compound and the like. From these viewpoints, the content of the matrix component is preferably 12 to 60% by mass, more preferably 13 to 50% by mass.

<Thermal expandable graphite>
The thermally expandable graphite contained in the fire-resistant resin composition of the present invention expands when heated, and powders such as natural scaly graphite, thermally decomposed graphite, and kiss graphite are mixed with an inorganic acid and a strong oxidizing agent. It is a type of crystalline compound that has been treated to produce a graphite interlayer compound and maintains the layered structure of carbon. Examples of the inorganic acid include concentrated sulfuric acid, nitric acid and selenic acid. Examples of the strong oxidizing agent include concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, hydrogen peroxide and the like.
Further, the heat-expandable graphite obtained by the acid treatment as described above may be further neutralized with a neutralizing agent such as ammonia, an aliphatic lower amine, an alkali metal compound, and an alkaline earth metal compound. Examples of the aliphatic lower amine include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, butylamine and the like. Examples of the alkali metal compound and the alkaline earth metal compound include hydroxides such as potassium, sodium, calcium, barium and magnesium, oxides, carbonates, sulfates and organic acid salts.

The particle size of the heat-expandable graphite is preferably 20 to 200 mesh. When it is 20 mesh or more, the degree of expansion of graphite becomes relatively large and the foamability becomes good. When the size is 200 mesh or less, the dispersibility in the matrix resin is good, so that problems such as deterioration of moldability are unlikely to occur.
Further, the heat-expandable graphite may be surface-treated with a silane compound such as a silane coupling agent.
The heat-expandable graphite may be used alone or in combination of two or more.

In the refractory resin composition, the heat-expandable graphite preferably contains heat-expandable graphite having a volume increase rate of 1.0 ml / g / min or more when heated at 300 ° C. for 10 minutes. When the volume increase rate is at least the above lower limit value, the expansion ratio and the shape holding force when heated at 300 ° C. for 5 minutes are increased, and it becomes easy to adjust within the above-mentioned predetermined range.
Although it is not clear why the shape-retaining force is increased by increasing the volume increase rate, the thermally expandable graphite expands in a state of being relatively constrained by the matrix component at a low temperature, so that the volume increase rate is increased. It is presumed that when the coefficient increases and rapidly expands at a low temperature, the internal pressure increases in the expansion residue and the graphite is compacted.

The volume increase rate is more preferably 1.5 ml / g / min or more, further preferably 2.0 ml / g / min or more, from the viewpoint of improving the expansion ratio and the shape retention force when heated at 300 ° C. for 5 minutes. ..
The volume increase rate can be obtained by heating the heat-expandable graphite in an oven at 300 ° C. for 10 minutes and calculating the ratio of the volume increase per unit mass to the heating time (10 minutes).

For the heat-expandable graphite, the volume increase rate of the entire heat-expandable graphite contained in the fire-resistant resin composition is preferably at least the above-mentioned lower limit value, but some of the heat-expandable graphite is at least the above-mentioned lower limit value ( The volume increase rate may be 1.0 ml / g / min or more, preferably 1.5 ml / g / min or more, more preferably 2.0 ml / g / min or more). Therefore, in the present invention, two or more types of thermally expandable graphite having different volumes of thermal expansion may be used as the thermally expandable graphite.
The proportion of the heat-expandable graphite having a volume increase rate equal to or higher than the above-mentioned lower limit is, for example, 30 to 100% by mass, preferably 45 to 100% by mass, and more preferably 60 to 100% by mass with respect to the entire heat-expanded graphite. Is.
The volume increase rate of the heat-expandable graphite of the present invention is not particularly limited, but is, for example, 10 ml / g / min or less.

The volume increase rate is not particularly limited, but the type of treatment agent such as an inorganic acid, a strong oxidizing agent, and a neutralizing agent used to obtain the heat-expandable graphite, the treatment method to obtain the heat-expandable graphite, and the like are appropriately used. It can be adjusted within the above range by adjusting. Further, a commercially available product having a volume increase rate within the above range may be used. Examples of commercially available products include "EXP50S120" and "EXP50S150" manufactured by Fuji Kokuen Industry Co., Ltd., and "QKG" manufactured by QKG.

The expansion start temperature of the heat-expandable graphite is not particularly limited, but it is preferably relatively low from the viewpoint of increasing the volume increase rate of the heat-expandable graphite, for example, 190 ° C. or lower, preferably 170 ° C. or lower, more preferably 155. It is below ° C. Further, the expansion start temperature of the heat-expandable graphite is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, still more preferably 110 ° C. or higher in order to prevent expansion except when a fire occurs.
The expansion start temperature of the thermally expandable graphite may be obtained by, for example, using a rheometer to raise the temperature at a temperature rise temperature of 10 ° C./min and measure the temperature at which the force in the normal direction rises.
Further, in the present invention, two or more types of thermally expandable graphite having different expansion start temperatures may be used. Since the refractory resin composition contains expandable graphite having different expansion start temperatures, the refractory resin composition tends to have excellent fire resistance in a wide temperature range.

The content of the heat-expandable graphite in the refractory resin composition is preferably in the range of 30 to 350 parts by mass, more preferably in the range of 40 to 250 parts by mass, and in the range of 80 to 220 parts by mass. It is more preferable to have. When the content is within these ranges, it becomes easy to adjust the expansion ratio and shape holding force of the refractory material within the above-mentioned predetermined ranges. Further, by setting these upper limits or less, the mechanical strength of the refractory material is less likely to decrease.

<Phosphorus compound>
The above-mentioned phosphorus compounds are phosphorus compounds as flame retardants, and are, for example, lower phosphates, polyphosphates, melamine-based phosphorus compounds, red phosphorus, condensed phosphoric acid esters, halogen-containing phosphoric acid esters, and halogen-containing condensed phosphorus. Examples thereof include acid esters and phosphorus compounds represented by the general formula (1) described later. Examples of the phosphorus compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresildi-2,6-xylenyl phosphate, tris (chloropropyl) phosphate, and tris (tribromo). Neopentyl) phosphate can also be mentioned.
The above-mentioned phosphorus compound works effectively as an aggregate, and the above-mentioned shape-retaining power can be maintained at a high value. Therefore, it becomes easy to improve the fire resistance performance of the refractory material.

The lower phosphate refers to a salt of an inorganic phosphoric acid that is not condensed, that is, is not polymerized, among the salts of the inorganic phosphoric acid, and has one phosphorus atom in one molecule of the inorganic phosphoric acid. .. The inorganic phosphoric acid is not limited to phosphoric acid (orthophosphoric acid), and may be metaphosphoric acid, phosphorous acid, hypophosphorous acid, or the like. The phosphate may be any of a primary phosphate, a secondary phosphate and a tertiary phosphate.
Examples of salts include alkali metal salts such as lithium salt, sodium salt and potassium salt, alkaline earth metal salts such as magnesium salt, calcium salt, strontium salt and barium salt, periodic table 3B metal salts such as aluminum salt, and titanium. Examples thereof include metal salts such as salt, manganese salt, iron salt, nickel salt, copper salt, zinc salt, vanadium salt, chromium salt, molybdenum salt, tungsten salt and other transition metal salts. In addition, ammonium salts, amine salts, for example, guanidine salts or salts of triazine compounds can be mentioned. Among these, a metal salt is preferable, and an aluminum salt is more preferable. The salt of the melamine-based compound is defined as a melamine-based phosphorus compound described later in this specification.

Specific examples of the metal salt of lower phosphoric acid include aluminum primary phosphate, sodium primary phosphate, potassium primary phosphate, calcium primary phosphate, zinc primary phosphate, aluminum secondary phosphate, and sodium secondary phosphate. , Dipotassium Phosphate Phosphate, Calcium Dithernate Phosphate, Zinc Secondary Phosphate, Aluminum Phosphate No. 3, Sodium Phosphate III, Potassium Phosphate III, Calcium Phosphate III, Zinc Triphosphate, Aluminum Phosphate Phosphate, Sodium phosphite, potassium phosphite, calcium phosphite, zinc phosphite, aluminum hypophosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, zinc hypophosphite, aluminum metaphosphate, Examples thereof include sodium metaphosphate, potassium metaphosphate, calcium metaphosphate, zinc metaphosphate and the like. Among these, aluminum phosphate and aluminum phosphite are preferable.

Examples of the polyphosphate include ammonium polyphosphates such as ammonium polyphosphate, melamine-modified ammonium polyphosphate, piperazine polyphosphate, and ammonium polyphosphate, and metal salts of polyphosphate such as aluminum polyphosphate. Among them, ammonium polyphosphate is preferable from the viewpoint of fire resistance, safety, cost, handleability and the like.

Examples of the melamine-based phosphorus compound include salts of melamine or melamine derivatives such as melamine, melem, and melon. Examples of the salt of melamine or a melamine derivative include melamine polyphosphate, melamine pyrophosphate, melamine orthophosphate, melamine polyphosphate, melamine, melamine, melamine polymethaphosphate, melamine organic phosphonate, and melamine phosphinate. Among these, polyphosphates of melamine compounds such as melamine polyphosphate and melamine polyphosphate, melam, and melem are preferable.

Condensation phosphates include, for example, trialkylpolyphosphate, resorcinolpolyphenyl phosphate, bisphenol A polycresyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, hydroquinonepoly (2,6-xysilyl) phosphate and Condensed phosphoric acid esters such as these condensates can be mentioned.
Further, as the halogen-containing condensed phosphoric acid ester, a compound in which a part of the condensed phosphoric acid ester described above is replaced with a chlorine atom can be mentioned. Examples of the halogen-containing phosphoric acid ester include chloroalkyl phosphate esters such as tris (β-chloropropyl) phosphate (TMCPP).

The compounds represented by the general formula (1) are as follows.

In the formula (1), R ¹ and R ³ represent hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms, which are the same or different. R ² is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or carbon. It shows the number 6 to 16 aryloxy groups.
Examples of the compound represented by the above chemical formula include methylphosphonate, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonate, butylphosphonic acid, 2-methylpropylphosphonate, t-butylphosphonic acid, 2, 3-Dimethyl-butylphosphonate, octylphosphonate, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphonate, methylethylphosphonate, methylpropylphosphinic acid, diethylphosphonate, dioctylphosphonate, phenylphosphonate, diethylphenylphosphinic acid , Diphenylphosphonic acid, bis (4-methoxyphenyl) phosphonic acid and the like.
The above phosphorus compounds may be used alone or in combination of two or more.

As the phosphorus compound, a phosphorus compound surface-treated with a silane compound may be used. When a phosphorus compound surface-treated with a silane compound is used, the viscosity of the refractory resin composition can be reduced, and the moldability of the refractory material can be improved.
The content of the phosphorus compound is preferably 20 to 300 parts by mass, more preferably 30 to 270 parts by mass, and further preferably 40 to 240 parts by mass with respect to 100 parts by mass of the matrix component. By setting the content of the phosphorus compound to these lower limit values or more, the shape holding power of the refractory material can be enhanced, and the refractory performance can be further improved. Further, by setting the value to the above upper limit or less, the flexibility and shape retention of the refractory material are less likely to be impaired.

Among the above, the phosphorus compound preferably contains at least one selected from lower phosphates, polyphosphates, and melamine-based phosphorus compounds from the viewpoint of enhancing shape retention and improving fire resistance. ..
At least one selected from the above-mentioned lower phosphates, polyphosphates, and melamine-based phosphorus compounds may be the total amount of the phosphorus compounds in the fire-resistant material, or may be a part of the phosphorus compounds. The content is preferably 20 to 270 parts by mass, more preferably 30 to 250 parts by mass, and further preferably 40 to 200 parts by mass.
Further, from the viewpoint of imparting water resistance to the fire-resistant material, the phosphorus compound more preferably contains at least one selected from lower phosphates and melamine-based phosphorus compounds, and above all, lower phosphates. Is particularly preferable.
From the viewpoint of fire resistance, water resistance and the like, the lower phosphate is preferably at least one of a phosphate and a phosphite, and a phosphate is more preferable. Further, as the lower phosphate, a metal salt is preferable as described above, and aluminum is more preferable as the metal. Therefore, the lower phosphate is preferably at least one of a metal phosphate and a metal phosphite salt, more preferably a metal phosphite salt, and particularly preferably an aluminum phosphite salt.

<Inorganic filler>
The refractory resin composition preferably further contains an inorganic filler in addition to the heat-expandable graphite and the like. The inorganic filler plays an aggregate role, improves the mechanical strength of the refractory material (that is, the expansion residue) after being heated and expanded, and enhances the above-mentioned shape retention force. It also increases the heat capacity of the refractory material.
Specific examples of the inorganic filler are not particularly limited, but for example, metal oxidation of alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, lead oxide, zirconium oxide, antimony oxide, ferrite and the like. Substances, metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, hydrotalcite, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, barium carbonate and other metal carbonates, sulfate Metal sulfates such as calcium, magnesium sulfate, aluminum sulfate, zinc sulfate, barium sulfate, gypsum fiber, calcium silicate, silica, diatomaceous soil, dosonite, talc, kaolin, dolomite, clay, mica, montmorillonite, bentonite, active white clay, sepiolite , Imogolite, sericite, glass fiber, glass beads, silica-based balun, aluminum oxide, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, Examples thereof include lead zirconate titanate, aluminum borate, molybdenum sulfide, silicon carbide, stainless fiber, zinc borate, various magnetic powders, slag fiber, fly ash, and dehydrated sludge. One kind or two or more kinds of these inorganic fillers can be used.
Among the above, from the viewpoint of improving the mechanical strength of the fireproof material, an inorganic metal salt is preferable, and at least one selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, and metal sulfates is preferable. At least one selected from the group consisting of metal carbonates and metal sulfates is more preferable.

The inorganic filler is preferably granular. The average particle size of the inorganic filler is preferably in the range of 0.5 to 200 μm, more preferably in the range of 1 to 50 μm. The average particle size may be determined by the air permeation method.
In the present invention, as the inorganic filler, an inorganic filler surface-treated with a silane compound may be used. When an inorganic filler surface-treated with a silane compound is used, the viscosity of the refractory resin composition can be reduced, and the moldability of the obtained refractory material can be improved.

The content of the inorganic filler in the fire-resistant resin composition with respect to 100 parts by mass of the matrix component is preferably 10 to 300 parts by mass, more preferably 25 to 250 parts by mass, and 45 to 200 parts by mass. Is even more preferable, and 80 to 180 parts by mass is even more preferable.
By setting the inorganic filler to these lower limit values or more, the mechanical strength of the expansion residue after thermal expansion becomes good, and the shape holding power also improves. Further, by setting the value to the upper limit or less, the flexibility can be maintained, the increase in viscosity of the resin composition can be suppressed, and the moldability can be improved.

The refractory resin composition may further contain at least one additive selected from surfactants and plasticizers. By containing these additives, it is possible to suppress the increase in viscosity of the refractory resin composition. From the viewpoint of fire resistance, the additive is preferably a compound containing a phosphorus atom.

<Surfactant>
The surfactant improves the dispersibility of the heat-expandable graphite and the inorganic filler in the refractory resin composition. Therefore, the heat-expandable graphite and the inorganic filler can be easily contained in the refractory resin composition in a large amount. In addition, the increase in viscosity of the refractory resin composition is suppressed, and the workability and the like can be easily improved.
The surfactant may have a hydrophilic group portion and a hydrophobic group portion compatible with the resin component. Specifically, polyether phosphate ester or an amine salt thereof, a phosphate of polyaminoamide and phosphoric acid, polyether polyol polyesteric acid or an amine salt thereof, an amine salt of polyester, an amine salt of polycarboxylic acid, a polyesteric acid amide. Alternatively, fatty acid ester-based surfactants such as amine salts thereof, styrenated phenol, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, glyceryl monoisostearate, and sorbitan monooleate can be mentioned. The amine used in these surfactants may be a polyamine. Of these, polyether phosphate is preferred.
When a surfactant is used, the content in the fire-resistant resin composition is preferably 0.05 to 15 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the matrix resin.

<Plasticizer>
Since the refractory resin composition contains a plasticizer, it becomes easy to increase the workability and the flexibility of the refractory material, and the moldability becomes good. In addition, flexibility is imparted to the refractory material.
Examples of the plasticizing agent include phosphoric acid esters such as triphenyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, di-2-ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), and dibutyl phthalate. Phthalate esters such as heptylphthalate (DHP) and diisodecylphthalate (DIDP), adipate esters such as di-2-ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), dibutyl adipate (DBA), epoxidized soybean oil and the like. Examples thereof include epoxy compounds, trimellitic acid esters such as tri-2-ethylhexyl trimertate (TOTM) and triisononyl trimellitate (TINTM), tar, and petroleum resins. The plasticizer may be used alone or in combination of two or more. Of these, phosphate esters are preferred, and triphenyl phosphate is more preferred.
When a plasticizer is used, its content is preferably 1 to 90 parts by mass, more preferably 5 to 75 parts by mass, and further preferably 10 to 60 parts by mass with respect to 100 parts by mass of the matrix component.

<Processing aid>
The refractory resin composition of the present invention may contain a processing aid. The processing aid may be used in combination with a thermoplastic resin, an elastomer or the like. Examples of processing aids that can be used in combination with thermoplastic resins and elastomers include chlorinated polyethylene, methyl methacrylate-ethyl acrylate copolymers, polymethyl methacrylate, process oils, and acrylic-modified fluororesins. The processing aid may be used alone or in combination of two or more.

Chlorinated polyethylene, methyl methacrylate-ethyl acrylate copolymer, and polymethyl methacrylate are preferably used when polyvinyl chloride is used as a matrix component. The process oil is preferably used when a rubber component is used as the matrix component.
The acrylic-modified fluororesin is a thickener having thermoplasticity, and examples thereof include acrylic-modified PTFE. Examples of the acrylic-modified PTFE include "Metaprene A3000" manufactured by Mitsubishi Chemical Corporation. By using an acrylic-modified fluororesin, the matrix component is thickened when it is softened or melted to improve workability. The acrylic-modified fluororesin can be suitably used when a thermoplastic elastomer, particularly TPO, is used as a matrix component.
The content of the processing aid in the refractory resin composition is preferably 1 to 80 parts by mass, and more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the matrix component.

<Heat stabilizer>
The refractory resin composition may contain a heat stabilizer. The heat stabilizer is not particularly limited, but can be suitably used when polyvinyl chloride is used as a matrix component.
Specific examples of the heat stabilizer include lead heat stabilizers such as lead tribasic lead sulfate, lead tribasic sulfite, lead dibasic lead phosphate, lead stearate, and lead dibasic stearate, and organic tin mercapto. Organic tin heat stabilizers such as organic tin malate, organic tin laurate, dibutyl tin malate, metal soap heat stabilizers such as zinc stearate and calcium stearate, calcium-zinc heat stabilizers, barium-zinc heat stabilizers, barium -Cadmium-based heat stabilizers and the like can be mentioned. These may be used alone or in combination of two or more.
Among these, metal soap heat stabilizers such as calcium-zinc heat stabilizers and calcium stearate are preferable.
The content of the heat stabilizer in the refractory resin composition is not particularly limited, but is preferably 0.5 to 20 parts by mass, more preferably 2 to 15 parts by mass, and further preferably 4 to 12 parts by mass. By setting the content of the heat stabilizer to these lower limit values or more, the thermal stability of the refractory material can be enhanced, and the fire resistance performance can be easily improved. Further, by setting the value to the upper limit or less, the effect commensurate with the content can be exhibited.

<Vulcanizing agent>
The refractory resin composition may contain a vulcanizing agent. The vulcanizer is preferably used when a rubber component is used as the matrix component. In the refractory resin composition, a vulcanizing agent is added to vulcanize the matrix component to form a three-dimensional network structure. Therefore, high rubber elasticity can be imparted to the refractory material.
Examples of the sulfide agent include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dithiocarbamate and the like, and sulfur is preferable among them.
One type of vulcanizing agent may be used alone, or two or more types may be used in combination.
In the fire-resistant resin composition, the content of the vulcanizing agent is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the matrix component. is there. By setting the content of the vulcanizing agent to these lower limit values or more, excellent rubber elasticity can be imparted to the refractory material. Further, by setting the value to the upper limit or less, the effect commensurate with the content can be exhibited.

However, the refractory material may have a three-dimensional network structure formed by a material other than the vulcanizing agent. As such a method, a cross-linking agent other than a vulcanizing agent such as a peroxide cross-linking agent is blended in the fire-resistant resin composition, and the fire-resistant resin composition is cross-linked by heating or the like, or irradiation with an electron beam. Examples thereof include a method of cross-linking a fire-resistant resin composition.

<Other ingredients>
The fire-resistant resin composition contains, as necessary, phenol-based, amine-based, sulfur-based antioxidants, metal damage inhibitors, antistatic agents, stabilizers, lubricants, etc., as long as the object of the present invention is not impaired. It may contain other components other than the above-mentioned components such as pigments and antistatic resins. The content of other components is, for example, 50 parts by mass or less, preferably 30 parts by mass or less, based on 100 parts by mass of the matrix component.

<Manufacturing method of refractory material>
In the method for producing a refractory material of the present invention, it is preferable to first prepare a refractory resin composition by mixing at least a matrix component, a heat-expandable graphite, and a phosphorus compound. Further, when an arbitrary component such as the above-mentioned inorganic filler is blended in the refractory resin composition, in addition to the matrix component, the heat-expandable graphite, and the phosphorus compound, the arbitrary component is also blended and mixed. do it.
The mixing of each component may be carried out by heating as appropriate, but in that case, the temperature of the thermally expandable graphite to be mixed may be controlled so as to be lower than the expansion start temperature.

In the preparation of the fire-resistant resin composition, the apparatus used for mixing each of the above components is not particularly limited, but is a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a Raikai machine, and a planetary type. A known kneader such as a stirrer or a stirrer provided with a stirrer blade can be used.
When a thermosetting resin composed of a main agent and a curing agent is used, the main agent and the curing agent may be mixed separately and mixed with a static mixer, a dynamic mixer or the like immediately before molding.
The refractory resin composition may be diluted with an organic solvent to form a slurry or the like, but it is preferable not to use an organic solvent because a step of removing the organic solvent is not required.

The refractory resin composition obtained as described above may be molded into a desired shape such as a sheet. The method of molding into a desired shape is not particularly limited, but it is preferable to pour it into a mold to form a sheet or the like. When a single-screw extruder, a twin-screw extruder, or the like is used as the kneader, the refractory resin composition may be extruded into a sheet from the extruder. Further, there is also a method of applying a refractory resin composition to a desired thickness on a base material or a release film subjected to a release treatment to form a sheet, and in this case, press as appropriate. And so on.

Here, when the matrix component is either a thermoplastic resin or an elastomer component, a refractory material can be obtained by molding into a desired shape such as a sheet shape.
When the matrix component contains a cross-linking agent such as a vulcanizing agent, the fire-resistant resin composition is vulcanized (crosslinked) by heating the fire-resistant resin composition after molding into a desired shape. However, when the fire-resistant resin composition contains a solvent, it is preferable to obtain a fire-resistant material by drying.
When the matrix component contains a thermosetting resin, the refractory resin composition may be molded into a desired shape and then cured by heating or the like to obtain a refractory material.
When the fire-resistant resin composition is formed into a desired shape and then heated, the heating temperature may be appropriately adjusted depending on the type of cross-linking agent, the type of solvent, the type of thermosetting resin, etc., but the heat of the thermally expanded graphite Adjust to less than the expansion start temperature. By setting the temperature below the thermal expansion start temperature, the expandable graphite in the refractory resin composition is hardly expanded, and the expandable graphite contained in the refractory resin composition is not expanded even in the refractory material. It becomes graphite.
The heating temperature is, for example, 45 to 150 ° C., preferably 50 to 130 ° C., more preferably 60 to 120 ° C. The heating time is not particularly limited, but is, for example, about 1 to 15 hours.

When the matrix component contains a thermosetting resin, it is preferable to cure the refractory resin composition after molding it into a desired shape such as a sheet and before curing by heating. In the present invention, curing makes it easier to improve the expansion ratio and shape retention of the refractory material. The principle is not clear, but since the thermosetting resin is cured in a state of being familiar with the expandable graphite, it becomes easy to trap acids and the like contained in the expandable graphite inside, and the temperature is low (for example, 300 ° C.). Degree) It is presumed that the expandable graphite tends to expand rapidly when heated.
Curing may be performed at a temperature lower than the temperature at which the thermosetting resin is cured. Specifically, the refractory resin composition is cured by allowing it to stand at a temperature of, for example, 10 to 40 ° C, preferably 15 to 35 ° C, for example, 0.5 to 24 hours, preferably 0.5 to 12 hours. It is better to do it by.

<How to use refractory material>
The fireproof material of the present invention can be used for various buildings such as detached houses, apartment houses, high-rise houses, high-rise buildings, commercial facilities, public facilities, various vehicles such as automobiles and trains, and various vehicles such as ships and aircraft. However, among these, it is preferable to be used for buildings.
The refractory material is used by being attached to members constituting the above-mentioned buildings, vehicles, ships, aircraft and the like. For example, in a building, it can be attached to windows, shoji screens, doors, doors, fittings such as bran, pillars, walls such as steel-framed concrete, floors, roofs, etc. to reduce or prevent the invasion of fire and smoke. Of these, it is preferable to use it for fittings. That is, in a preferred embodiment, the fitting comprises the refractory material of the present invention described above.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these examples.
The measurement and evaluation methods in this example are as follows.

<300 ° C expansion factor>
A 100 mm x 100 mm, 2 mm thick sample cut out from a refractory material is placed in a SUS box with an open top, placed on an iron plate, and placed in a muffle furnace consisting of an electric furnace heated to 300 ° C. for 5 minutes. It was heated. If the thickness of the refractory material is less than 2 mm, the sample used is the same as the thickness of the refractory material. The height of the sample after heating was measured with a caliper and used as the thickness after heating. The expansion ratio was calculated by dividing the thickness after heating by the thickness before heating. The expansion ratios when heated at 300 ° C. measured in Examples and Comparative Examples are shown in Tables 1 to 4 based on the following criteria.
A: 25 times or more and 50 times or less B: 20 times or more and less than 25 times C: 10 times or more and less than 20 times D: Less than 10 times <500 ° C expansion ratio>
The expansion ratio at the time of heating at 500 ° C. was determined except that the temperature inside the muffle furnace was changed to 500 ° C. The expansion ratios measured in Examples and Comparative Examples are shown in Tables 1 to 4 based on the following criteria.
A: 45 times or more and 80 times or less B: 30 times or more and less than 45 times C: 15 times or more and less than 30 times D: 15 times or less

<Shape holding power>
The heated sample whose expansion ratio was measured was supplied to a compression tester (“Finger Filling Tester” manufactured by Kato Tech Co., Ltd.), and in an environment of 25 ° C., 0.1 cm / sec with a 0.25 cm ² indenter. It was compressed at a speed, the breaking point stress was measured, and the obtained value was used as the shape holding force. The shape-retaining forces measured in Examples and Comparative Examples are shown in Tables 1 to 4 based on the following criteria.
(Shape retention after heating at 300 ° C)
A: 1.5N or more and 10N or less B: 0.7N or more and less than 1.5N C: 0.3N or more and less than 0.7N D: Less than 0.3N (shape holding power after heating at 500 ° C)
A: 0.1N or more and less than 10N B: 0.07N or more and less than 0.1N C: 0.01N or more and less than 0.07N D: less than 0.01N

<Volume increase rate>
1 g of heat-expandable graphite was prepared, and the volume was measured with a measuring cylinder. Then, 1 g of heat-expandable graphite was placed in a crucible and heated in a muffle furnace composed of an electric furnace whose inside was heated to 300 ° C. for 10 minutes. The heat-expandable graphite after heating was returned to room temperature (25 ° C.), and the volume was measured with a measuring cylinder. The value obtained by subtracting the volume before heating from the volume after heating is taken as the volume increase, and (volume increase per unit mass) / (heating time [10 minutes]) is the volume increase rate (ml / g /) of the heat-expandable graphite. Minutes).

<Water resistance>
A container screw tube containing hot water whose water temperature was maintained at 60 ° C. was prepared. The refractory material was cut out, and 10 samples having a thickness of 20 mm × 50 mm and a thickness of 2 mm were prepared and immersed in warm water maintained at 60 ° C. for 10 days, and the elution rate after 10 days was measured. If the thickness of the refractory material is less than 2 mm, the sample used is the same as the thickness of the refractory material.
The elution rate was calculated from the mass difference between the mass of the container before measurement and the mass of the container that was naturally dried after the sample was pulled up. For the elution rate, the elution amount was determined as a percentage (%) with respect to the original sample mass. The elution rates measured in Examples and Comparative Examples are shown in Tables 1 to 4 as the evaluation results of water resistance based on the following criteria.
A: Less than 1% by mass B: 1% by mass or more and less than 5% by mass C: 5% by mass or more

[Example 1]
The raw materials were weighed according to the formulation shown in Table 1 and mixed at a stirring speed of 1,000 rpm for 1 minute using a three-one motor under the condition of room temperature (25 ° C.) to obtain a refractory resin composition. This refractory resin composition was applied to a release-treated polyethylene terephthalate (PET) film and pressed at room temperature (25 ° C.) at a pressure of 10 MPa to form a sheet having a thickness of about 2 mm. After molding, it was cured at a temperature of 20 to 23 ° C. for 1 hour, and then heated in an oven at 90 ° C. for 10 hours to cure the thermosetting resin. The PET film was peeled off to obtain a sheet-shaped refractory material having a thickness of 2 mm.

[Examples 2 to 7, Comparative Examples 1 to 3]
A refractory material was obtained in the same manner as in Example 1 except that the formulation was changed as described in Table 1.

[Example 8, Comparative Examples 4 and 5]
The procedure was carried out in the same manner as in Example 1 except that the composition was changed as described in Table 1 and the oven temperature at which the thermosetting resin was cured was changed to 110 ° C.

[Examples 9 to 10, Comparative Examples 6 to 7]
Of the components shown in Table 2, components other than expanded graphite and a plasticizer were kneaded with a plast mill at 125 ° C. for 1 minute, then at the time of plasticization, and kneaded at 125 ° C. for 4 minutes. Next, expanded graphite was added and kneaded at 125 ° C. for 3 minutes, and the obtained fire-resistant resin composition was press-molded at 150 ° C. and 19 MPa to form a sheet, and a sheet-like refractory having a thickness of 2 mm was obtained. I got the wood.

[Example 11, Comparative Example 8]
Of the components shown in Table 3, components other than expanded graphite are kneaded with a plast mill at 150 ° C. for 5 minutes, then expanded graphite is added and kneaded at 150 ° C. for 3 minutes. In order to vulcanize the obtained resin composition, it was press-molded under the conditions of 150 ° C. and 15 MPa and molded into a sheet to obtain a sheet-shaped refractory material having a thickness of 2 mm.

[Example 12, Comparative Example 9]
Of the components listed in Table 4, only the resin is kneaded with a plastomill at 180 ° C. for 3 minutes, and then the filler / additive is kneaded at 180 ° C. for 5 minutes. Next, expanded graphite was added and kneaded at 150 ° C. for 3 minutes, and the obtained resin composition was press-molded under the conditions of 150 ° C. and 15 MPa to form a sheet to obtain a sheet-shaped refractory material having a thickness of 2 mm. It was.

The raw materials shown in Tables 1 to 4 are as follows. The blending amounts (parts by mass) shown in Tables 1 to 4 are all active ingredient amounts.
(Thermosetting resin)
Epoxy resin (main agent): Bisphenol F type epoxy compound, trade name "E-807", manufactured by Mitsubishi Chemical Corporation Epoxy resin (hardener): modified aliphatic polypropylene, flexible grade, trade name "FL092", Mitsubishi Chemical Epoxy resin (main agent) manufactured by Sanyo Kasei Kogyo Co., Ltd .: Polyoxypropylene glycol, trade name "Sannicks PP-400", Urethane resin (hardener) manufactured by Sanyo Kasei Kogyo Co., Ltd .: Poly (diphenylmethane diisocyanate), trade name "Millionate MR-200" , Tosoh Co., Ltd. Phenolic resin: Liquid resol resin (nonvolatile content 70%), trade name "ST-611-LV", manufactured by DIC Corporation (thermoplastic resin)
PVC: Polyvinyl chloride, trade name "TK-800", manufactured by Shin-Etsu Chemical Co., Ltd. (elastomer component)
EPDM: Ethylene-propylene-diene rubber, product name "Mitsui EPT3092M, manufactured by Mitsui Chemicals, Inc. TPO: thermoplastic olefin elastomer, product name" Eslex 822 ", manufactured by Sumitomo Chemicals, Inc.

(Thermal expandable graphite)
Thermally expandable graphite (1): Trade name "EXP-50S120", manufactured by Fuji Kokuen Industry Co., Ltd., expansion start temperature 120 ° C.
Thermally expandable graphite (2): Trade name "EXP-50S150", manufactured by Fuji Kokuen Industry Co., Ltd., expansion start temperature 150 ° C.
Thermally expandable graphite (3): Trade name "EXP-50S160", manufactured by Fuji Kokuen Industry Co., Ltd., expansion start temperature 160 ° C.
Thermally expandable graphite (4): trade name "QKG", QKG, expansion start temperature: 160 ° C.
Thermally expandable graphite (5): trade name "CA60N", manufactured by Air Water Inc., expansion start temperature 220 ° C.

Table 5 shows the volume increase rate of the heat-expandable graphite and the volume per unit weight (initial volume) before heating.

(Phosphorus compound)
Phosphate: Tertiary aluminum phosphate (AlPO ₃ ), trade name "Taipoly L2", manufactured by Taihei Kagaku Sangyo Co., Ltd. Polyphosphate: ammonium polyphosphate, trade name "AP422", manufactured by Clarianto Chemicals Subphosphate: Aluminum phosphate, trade name "APA-100", manufactured by Taihei Kagaku Sangyo Co., Ltd. Melamine type: melamine polyphosphate, melam melem, trade name "PHOSMEL-200", manufactured by Nissan Chemical Co., Ltd.

(Inorganic filler)
Calcium carbonate: Product name "BF300", manufactured by Shiraishi Calcium Co., Ltd. Barium sulfate: Product name "W-6", manufactured by Takehara Chemical Industry Co., Ltd. Carbon black: Product name "# 55G", manufactured by Asahi Carbon Co., Ltd.

(Surfactant)
DA-375: Polyether phosphate ester, trade name "Disparon DA-375", manufactured by Kusumoto Kasei Co., Ltd. (plasticizer)
TPP: Triphenyl phosphate, product name "TPP", manufactured by Daihachi Chemical Industry Co., Ltd. DIDP: diisodecyl phthalate, product name "DIDP", manufactured by J-PLUS Co., Ltd. (processing aid)
Chlorinated polyethylene: Product name "135A CPE", Weihai Kinhiro Co., Ltd. Polymethylmethacrylate: Product name "P-530A", Mitsubishi Rayon Co., Ltd. Process oil: Product name "PW90", Idemitsu Co., Ltd. Acrylic modified PTFE: Product name " Metaprene A3000 ", manufactured by Mitsubishi Chemical Co., Ltd. (heat stabilizer)
Calcium stearate: trade name "SC-100", manufactured by Sakai Chemical Co., Ltd. Ca-Zn heat stabilizer: calcium-zinc-based heat stabilizer, trade name "CLZ-16S", manufactured by Mizusawa Chemical Co., Ltd.

In each of the above examples, the expansion ratio when heated at 300 ° C. for 5 minutes was 20 times or more, and the shape holding power was 0.7 N or more, so that the fire resistance performance at low temperature was good and more excellent. We were able to obtain a refractory material with fire resistance. On the other hand, in the comparative example, the expansion ratio when heated at 300 ° C. for 5 minutes was less than 20 times, or the shape holding force was less than 0.7 N, so that the fire resistance performance could not be improved. It was.

Claims (8)

A refractory material comprising a fire-resistant resin composition containing at least one matrix component selected from the group consisting of a resin component and an elastomer component, a heat-expandable graphite, and a phosphorus compound.
A refractory material having an expansion ratio of 20 times or more and a shape holding power of 0.7 N or more when heated at 300 ° C. for 5 minutes. The refractory material according to claim 1, wherein the heat-expandable graphite contains a heat-expandable graphite having a volume increase rate of 1.0 ml / g / min or more when heated at 300 ° C. for 10 minutes. The refractory material according to claim 1 or 2, wherein the expansion ratio when heated at 500 ° C. for 5 minutes is 30 times or more, and the shape holding power is 0.07 N or more. The refractory material according to any one of claims 1 to 3, wherein the matrix component is an epoxy resin. The refractory material according to any one of claims 1 to 4, wherein the phosphorus compound contains a lower phosphate. The refractory material according to any one of claims 1 to 5, wherein the phosphorus compound contains a phosphite. The refractory material according to any one of claims 1 to 6, wherein the refractory resin composition further contains an inorganic filler. A fitting provided with the refractory material according to any one of claims 1 to 7.