JP7221733B2 - refractory material - Google Patents

Description

The present invention relates to fireproof materials used in buildings, vehicles and the like.

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

WO2016/117699

In general, assuming a fire, attempts have been made to increase the expansion ratio and shape retention stability of a refractory material at a high temperature of 500° C. or higher to ensure fire resistance. However, refractory materials may not be able to ensure excellent refractory performance simply by increasing the expansion ratio and shape retention stability at high temperatures.
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 fire resistance performance.

As a result of investigation, the present inventors found that conventional refractory materials do not expand sufficiently at relatively low temperatures, lack expansion ratio and shape retention stability, and especially because the shape retention stability of the residue is low. It was found that the fire resistance performance in the initial stage was insufficient. Further, as a result of further intensive studies, it was found that the fire resistance performance of the fire resistant material can be further improved by setting the expansion ratio and shape retention force when heated at 300 ° C. to a certain value or more, and the following present invention. completed. That is, the present invention provides the following [1] to [8].
[1] A fire-resistant 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 when heated at 300° C. for 5 minutes and a shape retention force of 0.7 N or more.
[2] The refractory material according to [1] above, wherein the thermally expandable graphite has 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 [1] or [2] above, which has an expansion ratio of 30 times or more when heated at 500° C. for 5 minutes and a shape retention force of 0.07 N or more.
[4] The fireproof material according to any one of [1] to [3] above, wherein the matrix component is an epoxy resin.
[5] The refractory material according to any one of [1] to [4] above, wherein the phosphorus compound contains a lower phosphate.
[6] The refractory material according to any one of [1] to [5] above, wherein the phosphorus compound contains a phosphite.
[7] The fire-resistant material according to any one of [1] to [6] above, wherein the fire-resistant resin composition further contains an inorganic filler.
[8] Fittings comprising the refractory material according to any one of [1] to [7] above.

ADVANTAGE OF THE INVENTION According to this invention, the expansion ratio and shape retention force under a comparatively low temperature are made into more than a fixed value, and it can provide the fire-resistant material which has more excellent fire-resistant performance.

The present invention will be described in more detail below.
[Refractory material]
The refractory material of the present invention comprises a refractory resin composition containing a matrix component, thermally 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 retention 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 retention force is less than 0.7 N, the refractory material cannot sufficiently exhibit fire resistance in the initial stage of combustion, and the occurrence and spread of fire can be sufficiently prevented. There is a risk that you will not be able to

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. By increasing the expansion ratio at 300° C., the fire resistance in the initial stage of combustion can be further increased, and the fire resistance can be further improved.
The upper limit of the expansion ratio when heated at 300° C. for 5 minutes is not particularly limited, but it is preferably 50 times from the viewpoint of improving the mechanical strength of the expansion residue obtained by low-temperature heating.
Moreover, 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 low temperatures. Although the upper limit of the shape retention force when heated at 300° C. for 5 minutes is not particularly limited, it is practically 10 N.

The refractory material of the present invention preferably has an expansion ratio of 30 times or more when heated at 500° C. for 5 minutes, and a shape retention force of 0.07 N or more. When the expansion ratio and shape retention force when heated at 500° C. for 5 minutes are equal to or higher than the above lower limits, the fire resistance is improved in any temperature range from low temperature to high temperature. As a result, excellent fire resistance is maintained not only in the early stage of fire but also after fire has developed relatively, resulting in better fire resistance.
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, it is, for example, 80 times, preferably 45 times. be.
Moreover, the shape retention 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 high temperatures. Although the upper limit of the shape retention force when heated at 500° C. for 5 minutes is not particularly limited, it is practically 10 N.

The expansion ratio in the present invention is obtained by processing a refractory material into a sample of a predetermined thickness, heating the sample at 300 ° C. or 500 ° C., measuring the thickness of the expansion residue obtained, and measuring the thickness of the sample after heating. / It is obtained from the thickness of the sample before heating. The shape-retaining power is obtained by measuring the compressive strength of the expanded residue obtained by heating the above sample in the same manner. Here, for example, if the thickness of the sample is greater than 2 mm, it is processed to a thickness of 2 mm. Just do it. The details of the method for measuring the expansion ratio and the shape retention 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 hot water at 60° C. for 10 days is preferably less than 5% by mass, more preferably less than 1% by mass. Good water resistance allows the refractory material to exhibit excellent fire resistance performance even after being used in an environment in contact with water.
In order to improve water resistance, the refractory material preferably contains a lower phosphate, which will be 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. Although the thickness of the refractory material is not particularly limited, it 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 resin components and elastomer components, and these may be used in combination of two or more.
A thermosetting resin and a thermoplastic resin are mentioned as a resin component used for matrix resin. The thermosetting resin used in the present invention is not particularly limited as long as it can be cured by heating to form the matrix component of the refractory material. The thermosetting resin may be a two-component thermosetting resin. A two-liquid type thermosetting resin is, for example, a thermosetting resin composed of a main agent and a curing agent.

(Thermosetting resin)
Examples of thermosetting resins used in the present invention include synthetic resins such as epoxy resins, urethane resins, phenol resins, urea resins, melamine resins, unsaturated polyester resins, and polyimides. A thermosetting resin may be used individually by 1 type, and may use 2 or more types together.
Among these thermosetting resins, at least one selected from the group consisting of epoxy resins, urethane resins and phenol resins is preferable, and epoxy resins are more preferable. By using an epoxy resin, the sheet does not become brittle even when filled with a large amount of filler components such as thermally expandable graphite and an inorganic filler to be described later, and it is possible to maintain toughness.
An epoxy resin as a 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. A 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 this specification, unless otherwise specified, the content of the thermosetting resin means the sum of the components constituting the thermosetting resin. For example, in the case of a two-liquid type 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. Epoxy compounds are compounds having an epoxy group, and specific examples thereof include glycidyl ether type and glycidyl ester type. Glydisyl ether type may be bifunctional or polyfunctional such as trifunctional or more. 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. Among these, a bifunctional glycidyl ether type is preferred.

Examples of the bifunctional glycidyl ether type epoxy compound include, for example, polyethylene glycol type, polypropylene glycol type alkylene glycol type, neopentyl glycol type, 1,6-hexanediol type, hydrogenated bisphenol A type aliphatic Epoxy compounds are exemplified. Furthermore, 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 are listed. Among these, aromatic epoxy compounds such as bisphenol A type and bisphenol F type are preferred.

Examples of the glycidyl ester type epoxy compounds include hexahydrophthalic anhydride type, tetrahydrophthalic anhydride type, dimer acid type and p-oxybenzoic acid type epoxy compounds.
Examples of tri- or more functional glycidyl ether type epoxy compounds include phenol novolak type, ortho-cresol 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.

A polyaddition type or a catalyst type is used as the curing agent. Examples of polyaddition-type curing agents include polyamine curing agents, acid anhydride curing agents, polyphenol curing agents, polymercaptan, and the like. 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, but examples thereof include those composed of a polyol compound as a main agent and a curing agent such as a polyisocyanate compound. Examples of polyol compounds 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. is 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.
Polyisocyanate compounds that are curing agents include, for example, 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, aromatic polyisocyanates such as 4,4′-diphenylmethane diisocyanate, 1,6- Aliphatic (or alicyclic) polyisocyanates such as hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Adducts or polymers of the above polyisocyanate compounds, for example, adducts of tolylene diisocyanate, poly(tolylene diisocyanate), and poly(diphenylmethane diisocyanate) can also be used. These polyisocyanate compounds may be used alone or in combination of two or more.
Among these, the curing agent is preferably aromatic polyisocyanate or its polymer, 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 contains two or more phenolic hydroxyl groups in the molecule, and examples thereof include resol-type phenolic resins and novolak-type phenolic resins. From the viewpoint of obtaining a fire-resistant resin composition with a lower viscosity, a phenolic resin that is liquid at room temperature (25° C.) is preferred, and a resol-type phenolic resin that is liquid is more preferred. A phenol resin may be used individually by 1 type, and 2 or more types may be used together.

The method for curing the thermosetting resin is not particularly limited, and can be performed by a known method. For example, the epoxy resin or urethane resin can be cured by mixing the main agent and the curing agent and heating.

(Thermoplastic resin)
Examples of thermoplastic resins include polyolefin resins such as polypropylene resin, polyethylene resin, poly(1-)butene resin, polypentene resin, polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, ethylene vinyl acetate copolymer (EVA ), polycarbonate resins, polyphenylene ether resins, (meth)acrylic resins, polyamide resins, polyvinyl chloride resins (PVC), novolac resins, polyurethane resins, 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.

Polyvinyl chloride resins include, for example, polyvinyl chloride homopolymers, copolymers of vinyl chloride monomers and monomers having unsaturated bonds copolymerizable with vinyl chloride monomers, and polymers other than vinyl chloride containing chlorides. Examples thereof include graft copolymers obtained by graft copolymerizing vinyl, and these may be used alone or in combination of two or more. In addition, chlorinated polyvinyl chloride-based resins, which are chlorinated polyvinyl chloride-based resins, are also included in polyvinyl chloride-based resins.

(elastomer component)
Elastomer components include rubbers, thermoplastic elastomers, and the like. 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), ethylene-propylene-diene rubber. (EPDM), chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, silicone rubber, fluororubber, urethane rubber, and the like.
Thermoplastic elastomers include thermoplastic olefin elastomers (TPO), thermoplastic styrene elastomers, thermoplastic ester elastomers, thermoplastic amide elastomers, thermoplastic vinyl chloride elastomers, and combinations thereof. TPO includes 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.
EPDM and TPO are preferable as the elastomer component from the viewpoint of flexibility and moldability.

The content of the matrix component in the fire resistant resin composition (that is, fire resistant material) of the present invention is, for example, 10 to 80% by mass. By using a matrix component with a lower limit value or higher, the shape retention of the refractory material is improved. Moreover, by setting the content to the upper limit or less, it becomes possible to mix thermally expandable graphite, a phosphorus compound, or the like in a predetermined amount or more. 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. It is a type of crystalline compound that maintains the layered structure of carbon by processing to produce a graphite intercalation compound. Examples of inorganic acids include concentrated sulfuric acid, nitric acid, and selenic acid. Examples of strong oxidizing agents include concentrated nitric acid, perchloric acid, perchlorates, permanganates, bichromates, and hydrogen peroxide.
The thermally expandable graphite obtained by acid treatment as described above may be further neutralized with a neutralizing agent such as ammonia, lower aliphatic amines, alkali metal compounds, alkaline earth metal compounds and the like. Examples of aliphatic lower amines include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, butylamine and the like. Examples of the alkali metal compounds and alkaline earth metal compounds include hydroxides, oxides, carbonates, sulfates, organic acid salts of potassium, sodium, calcium, barium, magnesium and the like.

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

The thermally expandable graphite in the refractory resin composition preferably contains thermally expandable graphite having a volume increase rate of 1.0 ml/g/min or more when heated at 300° C. for 10 minutes. If the volume increase rate is equal to or higher than the above lower limit, the expansion ratio and the shape retention force when heated at 300° C. for 5 minutes are increased, making it easier to adjust within the above-described predetermined range.
It is not clear why the shape-retaining force increases as the volume increase rate increases, but thermally expandable graphite expands in a state relatively constrained by the matrix component at low temperatures, so the volume increase rate This is presumed to be due to the fact that the internal pressure increases in the expansion residue and the graphite is compacted when the σ increases and the graphite expands rapidly at low temperatures.

The volume increase rate is more preferably 1.5 ml/g/min or more, and even more preferably 2.0 ml/g/min or more, from the viewpoint of improving the expansion ratio and shape retention force when heated at 300° C. for 5 minutes. .
The volume increase rate can be obtained by heating the thermally 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).

In the thermally expandable graphite, the volume increase rate of the entire thermally expandable graphite contained in the refractory resin composition is preferably at least the above lower limit value, but some of the thermally expandable graphite is at least the above lower limit value ( 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 volume increase rates may be used as the thermally expandable graphite.
The proportion of thermally expandable graphite whose volume increase rate is equal to or higher than the above lower limit is, for example, 30 to 100% by mass, preferably 45 to 100% by mass, more preferably 60 to 100% by mass, based on the total thermally expandable graphite. is.
The volume increase rate of the thermally 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. It can be adjusted within the above range by adjusting. Moreover, you may use the commercial item whose volume increase rate will be in the said range. Commercially available products include "EXP50S120" and "EXP50S150" manufactured by Fuji Graphite Industry Co., Ltd., and "QKG" manufactured by QKG.

The expansion starting temperature of the thermally expandable graphite is not particularly limited, but it is preferably relatively low from the viewpoint of increasing the volume increase rate of the thermally expandable graphite. ℃ or less. The expansion start temperature of thermally expandable graphite is preferably 100° C. or higher, more preferably 105° C. or higher, and even more preferably 110° C. or higher, in order to prevent expansion except when fire occurs.
The expansion start temperature of the thermally expandable graphite may be determined by, for example, using a rheometer to raise the temperature at a rate of 10° C./min and measuring the temperature at which the force in the normal direction rises.
Moreover, in the present invention, two or more types of thermally expandable graphite having different expansion initiation temperatures may be used. By containing expandable graphite having different expansion initiation temperatures, the fire resistant resin composition tends to have excellent fire resistance in a wide temperature range.

The content of thermally 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 even more preferable to have By setting the content within these ranges, it becomes easier to adjust the expansion ratio and shape retention force of the refractory material within the above-described predetermined ranges. In addition, by making the content equal to or less than these upper limits, the mechanical strength of the refractory material and the like are made less likely to decrease.

<Phosphorus compound>
The above phosphorus compounds are phosphorus compounds as flame retardants, and examples include lower phosphates, polyphosphates, melamine-based phosphorus compounds, red phosphorus, condensed phosphates, halogen-containing phosphates, halogen-containing condensed phosphorus Examples thereof include acid esters and phosphorus compounds represented by general formula (1) described later. In addition, phosphorus compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, tris(chloropropyl) phosphate, tris(tribromo Also included are neopentyl) phosphates.
The above-described phosphorus compound effectively acts as an aggregate, making it possible to maintain the above-described shape retention force at a high value. Therefore, it becomes easy to improve the fireproof performance of the fireproof material.

A lower phosphate refers to a salt of an inorganic phosphoric acid that is not condensed, that is, is not polymerized, among the salts of inorganic phosphoric acids, 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), but may be metaphosphoric acid, phosphorous acid, hypophosphorous acid, or the like. The phosphate may be a primary phosphate, a secondary phosphate, or a tertiary phosphate.
Salts include alkali metal salts such as lithium salts, sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts, calcium salts, strontium salts and barium salts; salts of group 3B metals of the periodic table such as aluminum salts; metal salts such as salts, manganese salts, iron salts, nickel salts, copper salts, zinc salts, vanadium salts, chromium salts, molybdenum salts, transition metal salts such as tungsten salts. Also included are ammonium salts, amine salts such as guanidine salts and salts of triazine compounds. Among these, metal salts are preferred, and aluminum salts are more preferred. In this specification, the salt of the melamine-based compound is defined as a melamine-based phosphorus compound to be described later.

Specific examples of metal salts of lower phosphates include monoaluminum phosphate, monobasic sodium phosphate, monobasic potassium phosphate, monobasic calcium phosphate, monobasic zinc phosphate, dibasic aluminum phosphate, and dibasic sodium phosphate. , dibasic potassium phosphate, dibasic calcium phosphate, dibasic zinc phosphate, tribasic aluminum phosphate, tribasic sodium phosphate, tribasic potassium phosphate, tribasic calcium phosphate, tribasic zinc phosphate, aluminum phosphite, sodium phosphite, potassium phosphite, calcium phosphite, zinc phosphite, aluminum hypophosphite, sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, zinc hypophosphite, aluminum metaphosphate, sodium metaphosphate, potassium metaphosphate, calcium metaphosphate, zinc metaphosphate and the like. Among these, aluminum phosphate and aluminum phosphite are preferred.

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

Melamine-based phosphorus compounds include salts of melamine or melamine derivatives such as melamine, melem and melon. Salts of melamine or melamine derivatives include melamine polyphosphate, melamine pyrophosphate, melamine orthophosphate, melamine/melam/melem polyphosphate, melamine polymetaphosphate, melamine organic phosphonate, and melamine organic phosphinate. Among these, polyphosphates of melamine compounds such as melamine polyphosphate, melamine polyphosphate, melam and melem are preferred.

Examples of condensed phosphate esters include trialkyl polyphosphate, resorcinol polyphenyl phosphate, bisphenol A polycresyl phosphate, resorcinol poly(di-2,6-xylyl) phosphate, hydroquinone poly(2,6-xylyl) phosphate, and Condensed phosphate esters such as these condensates are included.
Further, examples of the halogen-containing condensed phosphate include compounds in which a portion of the above-described condensed phosphate is substituted with a chlorine atom. Halogen-containing phosphates include chloroalkyl phosphates such as tris(β-chloropropyl)phosphate (TMCPP).

式（１）中、Ｒ¹及びＲ³は、同一又は異なって、水素、炭素数１～１６の直鎖状もしくは分岐状のアルキル基、又は、炭素数６～１６のアリール基を示す。Ｒ²は、水酸基、炭素数１～１６の直鎖状もしくは分岐状のアルキル基、炭素数１～１６の直鎖状あるいは分岐状のアルコキシル基、炭素数６～１６のアリール基、又は、炭素数６～１６のアリールオキシ基を示す。
上記化学式で表される化合物としては、例えば、メチルホスホン酸、メチルホスホン酸ジメチル、メチルホスホン酸ジエチル、エチルホスホン酸、プロピルホスホン酸、ブチルホスホン酸、２－メチルプロピルホスホン酸、ｔ－ブチルホスホン酸、２，３－ジメチル－ブチルホスホン酸、オクチルホスホン酸、フェニルホスホン酸、ジオクチルフェニルホスホネート、ジメチルホスフィン酸、メチルエチルホスフィン酸、メチルプロピルホスフィン酸、ジエチルホスフィン酸、ジオクチルホスフィン酸、フェニルホスフィン酸、ジエチルフェニルホスフィン酸、ジフェニルホスフィン酸、ビス（４－メトキシフェニル）ホスフィン酸等が挙げられる。
上記リン化合物は、１種単独で使用してもよいし、２種以上を併用してもよい。 Moreover, the compound represented by General formula (1) is as follows.

In formula (1), R ¹ and R ³ are the same or different and represent hydrogen, a linear or branched alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms. R ² is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or carbon It represents an aryloxy group of numbers 6-16.
Examples of compounds represented by the above chemical formula include methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methylpropylphosphonic acid, t-butylphosphonic acid, 2, 3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid , diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid and the like.
The phosphorus compounds may be used singly or in combination of two or more.

A phosphorus compound surface-treated with a silane compound may be used as the phosphorus compound. When a phosphorus compound surface-treated with a silane compound is used, the viscosity of the fire-resistant resin composition can be lowered, and the moldability of the fire-resistant 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, still more preferably 40 to 240 parts by mass, based on 100 parts by mass of the matrix component. By making the content of the phosphorus compound equal to or higher than these lower limit values, the shape retention force of the refractory material can be enhanced, and the fire resistance performance can be further improved. In addition, by making it equal to or less than the above upper limit, the flexibility, shape retention, etc. of the refractory material are made less likely to be impaired.

Among the above phosphorus compounds, from the viewpoint of enhancing shape retention and improving fire resistance, it is preferable that at least one selected from lower phosphates, polyphosphates, and melamine-based phosphorus compounds be included. .
At least one selected from the lower phosphates, polyphosphates, and melamine-based phosphorus compounds described above may be the total amount of the phosphorus compounds in the refractory 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, still more preferably 40 to 200 parts by mass.
In addition, from the viewpoint of imparting water resistance to the refractory material, the phosphorus compound more preferably contains at least one selected from lower phosphates and melamine-based phosphorus compounds among these, especially lower phosphates is particularly preferred.
From the viewpoint of fire resistance, water resistance, etc., the lower phosphate is preferably at least one of phosphate and phosphite, and more preferably phosphite. As described above, the lower phosphate is preferably a metal salt, and the metal is more preferably aluminum. Therefore, the lower phosphate is preferably at least one of a metal phosphate and a metal phosphite, more preferably a metal phosphite, and particularly preferably an aluminum phosphite.

<Inorganic filler>
The fire-resistant resin composition preferably contains an inorganic filler in addition to thermally expandable graphite. The inorganic filler plays a role of aggregate, improves the mechanical strength of the refractory material (that is, the expansion residue) after being heated and expanded, and enhances the above-described shape retention force. It also increases the heat capacity of the refractory material.
Specific examples of inorganic fillers are not particularly limited, but metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, lead oxide, zirconium oxide, antimony oxide, ferrite, etc. 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, sulfuric acid Metal sulfates such as calcium, magnesium sulfate, aluminum sulfate, zinc sulfate, and barium sulfate, gypsum fiber, calcium silicate, silica, diatomaceous earth, dawsonite, talc, kaolin, dolomite, clay, mica, montmorillonite, bentonite, activated clay, sepiolite , imogolite, sericite, glass fiber, glass beads, silica-based balloon, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balloon, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, 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. One or more of these inorganic fillers can be used.
Among the above, from the viewpoint of improving the mechanical strength of the refractory material, inorganic metal salts are 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 preferred.

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

The content of the inorganic filler with respect to 100 parts by mass of the matrix component in the fire-resistant resin composition is preferably 10 to 300 parts by mass, more preferably 25 to 250 parts by mass, and 45 to 200 parts by mass. is more preferable, and 80 to 180 parts by mass is even more preferable.
By setting the amount of the inorganic filler to these lower limits or more, the mechanical strength of the expansion residue after thermal expansion is improved, and the shape retention is also improved. Moreover, by making it below the upper limit, while maintaining flexibility, it can suppress the increase in the viscosity of a resin composition, and can improve moldability.

The fire-resistant resin composition may further contain at least one additive selected from surfactants and plasticizers. By containing these additives, it is possible to suppress an increase in the viscosity of the fire-resistant 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 thermally expandable graphite and the inorganic filler in the fire resistant resin composition. Therefore, it becomes easier to contain a large amount of the thermally expandable graphite and the inorganic filler in the fire-resistant resin composition. Moreover, it becomes easy to suppress the increase in the viscosity of the fire-resistant resin composition and to improve the workability and the like.
The surfactant preferably has a hydrophilic group portion and a hydrophobic group portion compatible with the resin component. Specifically, polyether phosphate or its amine salt, polyaminoamide and phosphoric acid phosphate, polyether polyol polyester acid or its amine salt, polyester amine salt, polycarboxylic acid amine salt, polyester acid amide or fatty acid ester surfactants such as amine salts thereof, styrenated phenols, polyoxyethylene oleyl ethers, polyoxyethylene alkyl ethers, glyceryl monoisostearate, and sorbitan monooleate. The amines used in these surfactants may be polyamines. Among these, polyether phosphate is preferred.
When using a surfactant, 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, relative to 100 parts by mass of the matrix resin.

<Plasticizer>
By containing a plasticizer, the refractory resin composition can easily improve the workability and the flexibility of the refractory material, resulting in good moldability. Also, flexibility is imparted to the refractory material.
Examples of plasticizers 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), di Phthalates such as heptyl phthalate (DHP) and diisodecyl phthalate (DIDP), adipates such as di-2-ethylhexyl adipate (DOA), diisobutyl adipate (DIBA), dibutyl adipate (DBA), epoxidized soybean oil Epoxy compounds, trimellitate esters such as tri-2-ethylhexyl trimellitate (TOTM) and triisononyl trimellitate (TINTM), tar, and petroleum resins. A plasticizer may be used individually by 1 type, or may use 2 or more types together. Among 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, still more preferably 10 to 60 parts by mass, based on 100 parts by mass of the matrix component.

<Processing aid>
The fire resistant resin composition of the present invention may contain processing aids. Processing aids are preferably used in combination with thermoplastic resins, elastomers, and the like. Examples of processing aids that can be used in combination with thermoplastic resins and elastomers include chlorinated polyethylene, methyl methacrylate-ethyl acrylate copolymer, polymethyl methacrylate, process oil, and acrylic-modified fluororesin. Processing aids may be used singly or in combination of two or more.

Chlorinated polyethylene, methyl methacrylate-ethyl acrylate copolymer, polymethyl methacrylate are preferably used when polyvinyl chloride is used as the matrix component. Process oil is preferably used when a rubber component is used as the matrix component.
The acryl-modified fluororesin is a thickener having thermoplasticity, and includes acryl-modified PTFE and the like. Examples of acrylic-modified PTFE include "Metaprene A3000" manufactured by Mitsubishi Chemical Corporation. By using the acrylic-modified fluororesin, the viscosity increases when the matrix component softens or melts, improving workability. 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 fire-resistant resin composition is preferably 1-80 parts by mass, more preferably 3-50 parts by mass, per 100 parts by mass of the matrix component.

<Heat stabilizer>
The fire resistant resin composition may contain a heat stabilizer. Although the heat stabilizer is not particularly limited, it can be suitably used when polyvinyl chloride is used as the matrix component.
Specific examples of heat stabilizers include lead heat stabilizers such as tribasic lead sulfate, tribasic lead sulfite, dibasic lead phosphite, lead stearate, dibasic lead stearate, organic tin mercapto, Organotin heat stabilizers such as organotin malate, organotin laurate, and dibutyltin 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. These may be used alone, or two or more of them may be used in combination.
Among these, metal soap heat stabilizers such as calcium-zinc heat stabilizers and calcium stearate are preferred.
The content of the heat stabilizer in the fire-resistant 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 even more preferably 4 to 12 parts by mass. By making the content of the heat stabilizer equal to or higher than these lower limit values, the thermal stability of the refractory material is enhanced, making it easier to improve the refractory performance and the like. Moreover, by making it below the upper limit, an effect corresponding to the content can be exhibited.

<Vulcanizing agent>
The fire resistant resin composition may contain a vulcanizing agent. A vulcanizing agent is preferably used when a rubber component is used as the matrix component. By adding a vulcanizing agent to the fire-resistant resin composition, the matrix component is vulcanized to form a three-dimensional network structure. Therefore, high rubber elasticity can be imparted to the refractory material.
Examples of the vulcanizing agent include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dithiocarbamate, etc. Among these, sulfur is preferred.
A vulcanizing agent may be used individually by 1 type, and 2 or more types may be used together.
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, based on 100 parts by mass of the matrix component. be. By setting the content of the vulcanizing agent to these lower limits or more, it is possible to impart excellent rubber elasticity to the refractory material. Moreover, by making it below the upper limit, an effect corresponding to the content can be exhibited.

However, the refractory material may have a three-dimensional network structure other than the vulcanizing agent. Examples of such a method include a method in which a cross-linking agent other than a vulcanizing agent such as a peroxide cross-linking agent is added to the fire-resistant resin composition, and the fire-resistant resin composition is cross-linked by heating or the like; and a method of cross-linking the fire-resistant resin composition.

<Other ingredients>
The fire-resistant resin composition may optionally contain antioxidants such as phenolic, amine-based, and sulfur-based antioxidants, metal damage inhibitors, antistatic agents, stabilizers, lubricants, Other components other than the components described above, such as pigments and tackifier resins, may also be included. The content of other components is, for example, 50 parts by mass or less, preferably 30 parts by mass or less with respect to 100 parts by mass of the matrix component.

<Method for manufacturing refractory material>
In the method for producing a refractory material of the present invention, first, at least a matrix component, thermally expandable graphite, and a phosphorus compound are mixed to prepare a refractory resin composition. In addition, when blending optional components such as the above inorganic fillers in the refractory resin composition, in addition to the matrix component, thermally expandable graphite, and phosphorus compound, the optional components are also blended and mixed. do it.
Although each component may be mixed by heating appropriately, in this case, the temperature of the mixed thermally expandable graphite may be controlled so as to be lower than the expansion start temperature.

In the preparation of the refractory resin composition, the device used for mixing the above components is not particularly limited, but a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader mixer, a kneading roll, a Raikai machine, a planetary type A known kneader such as a stirrer or a stirrer equipped with stirring blades can be used.
When using a thermosetting resin composed of a main agent and a curing agent, the main agent and the curing agent may be separately mixed and mixed by a static mixer, 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 unnecessary.

The fire-resistant 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 and make it into a shape such as a sheet. When a single-screw extruder, a twin-screw extruder, or the like is used as the kneader, the fire-resistant resin composition may be extruded in the form of a sheet from the extruder. In addition, a method of coating a fire-resistant resin composition to a desired thickness on a base material or a release film that has been subjected to a release treatment and forming it into a sheet may also be mentioned. etc.

Here, when the matrix component is either a thermoplastic resin or an elastomer component, the refractory material can be obtained by molding it into a desired shape such as a sheet shape.
Further, when the matrix component contains a cross-linking agent such as a vulcanizing agent, the fire-resistant resin composition is vulcanized (cross-linked) by heating the fire-resistant resin composition after molding into a desired shape. Alternatively, when the refractory resin composition contains a solvent, the refractory material may be obtained by drying.
Further, when the matrix component contains a thermosetting resin, the fire-resistant resin composition may be molded into a desired shape and then cured by heating to obtain a fire-resistant material.
When heating the refractory resin composition after molding it into a desired shape, 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. Adjust below the expansion start temperature. When the temperature is less than the thermal expansion start temperature, the expandable graphite in the fire-resistant resin composition is hardly expanded, and the expandable graphite contained in the fire-resistant resin composition is not expanded even in the fire-resistant 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. Also, the heating time is not particularly limited, but is, for example, about 1 to 15 hours.

Moreover, when the matrix component contains a thermosetting resin, it is preferable to perform curing after molding the fire-resistant resin composition 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. Although the principle is not clear, since the thermosetting resin is hardened in a state familiar with the expandable graphite, it becomes easy to trap the acid contained in the expandable graphite inside, and the temperature is low (for example, 300 ° C. degree) This is presumed to be because expansive graphite tends to expand rapidly when heated.
Curing is preferably performed at a temperature below the temperature at which the thermosetting resin is cured. Specifically, the refractory resin composition is cured, for example, at a temperature of 10 to 40° C., preferably 15 to 35° C., for example, for 0.5 to 24 hours, preferably 0.5 to 12 hours. It should be done by

<How to use refractory materials>
The fireproof material of the present invention can be used in various buildings such as single-family houses, collective housing, high-rise housing, high-rise buildings, commercial facilities, and public facilities, various vehicles such as automobiles and trains, and various vehicles such as ships and aircraft. However, among these, it is preferable to use it for buildings.
Refractory materials are used by being attached to members constituting the above buildings, vehicles, ships, aircraft, and the like. For example, in buildings, it can be attached to fittings such as windows, shojis, doors, doors, sliding doors, pillars, walls such as steel-framed concrete, floors, roofs, etc., to reduce or prevent the intrusion of fire and smoke. Among these, it is preferable to use it for fittings. That is, in a preferred embodiment, fittings are provided with the refractory material of the present invention described above.

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

<300°C expansion ratio>
A sample of 100 mm x 100 mm and a thickness of 2 mm cut from a refractory material is placed in a SUS box with an open top, placed on an iron plate, and heated to 300 ° C. inside for 5 minutes in a muffle furnace consisting of an electric furnace. heated. When the thickness of the refractory material is less than 2 mm, the thickness of the sample is the same as that of the refractory material. The height of the sample after heating was measured with a vernier caliper to determine 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 when heated to 500°C was obtained except that the temperature inside the muffle furnace was changed to 500°C. 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: Less than 15 times

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

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

<Water resistance>
A container screw tube containing hot water maintained at a water temperature of 60° C. was prepared. Ten samples of 20 mm×50 mm and 2 mm in thickness were prepared by cutting out the refractory material, immersed in hot water maintained at 60° C. for 10 days, and the elution rate after 10 days was measured. When the thickness of the refractory material is less than 2 mm, the thickness of the sample is the same as that of the refractory material.
The dissolution rate was calculated from the weight difference between the weight of the container before measurement and the weight of the container that had been air-dried after pulling up the sample. The elution rate was obtained as a percentage (%) of the elution amount with respect to the original sample mass. The elution rates measured in Examples and Comparative Examples are shown in Tables 1 to 4 as 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]
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 at room temperature (25° C.) to obtain a fire-resistant resin composition. This fire-resistant 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 with 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-like refractory material with 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 shown 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 formulation was changed as shown in Table 1 and the temperature of the oven was changed to 110° C. when curing the thermosetting resin.

[Examples 9-10, Comparative Examples 6-7]
Among the components shown in Table 2, the components other than the expanded graphite and the plasticizer were kneaded at 125°C for 1 minute in a Plastomill, then the plasticizer was added and kneaded at 125°C for 4 minutes. Next, expandable graphite is added and kneaded at 125° C. for 3 minutes, and the resulting refractory resin composition is press-molded under conditions of 150° C. and 19 MPa into a sheet to form a refractory sheet having a thickness of 2 mm. got the wood.

[Example 11, Comparative Example 8]
Among the components shown in Table 3, the components other than the expanded graphite are kneaded in a Plastomill at 150° C. for 5 minutes, then the 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 conditions of 150° C. and 15 MPa, and molded into a sheet shape to obtain a sheet-shaped refractory material having a thickness of 2 mm.

[Example 12, Comparative Example 9]
Among the components shown in Table 4, only the resin is kneaded at 180° C. for 3 minutes in a plastomill, and then the filler/additives are kneaded at 180° C. for 5 minutes. Next, expanded graphite was added and kneaded at 150°C for 3 minutes, and the resulting resin composition was press-molded at 150°C and 15 MPa to form a sheet to obtain a sheet-like refractory material having a thickness of 2 mm. rice field.

Each raw material described in Tables 1 to 4 is as follows. All of the compounding amounts (parts by mass) shown in Tables 1 to 4 are amounts of active ingredients.
(Thermosetting resin)
Epoxy resin (main agent): bisphenol F type epoxy compound, trade name "E-807", manufactured by Mitsubishi Chemical Corporation Epoxy resin (curing agent): modified aliphatic polyamine, flexible grade, trade name "FL092", Mitsubishi Chemical Urethane resin (main agent) manufactured by Co., Ltd.: Polyoxypropylene glycol, trade name “Sannics PP-400”, manufactured by Sanyo Chemical Industries, Ltd. Urethane resin (curing agent): Poly (diphenylmethane diisocyanate), trade name “Millionate MR-200” ”, manufactured by Tosoh Co., Ltd. Phenolic resin: liquid resol resin (70% non-volatile content), 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, trade name "Mitsui EPT3092M, manufactured by Mitsui Chemicals, Inc. TPO: Thermoplastic olefin elastomer, trade name "Slex 822," manufactured by Sumitomo Chemical Co., Ltd.

(Thermal expandable graphite)
Thermally expandable graphite (1): trade name “EXP-50S120”, manufactured by Fuji Graphite Industry Co., Ltd., expansion start temperature 120 ° C.
Thermally expandable graphite (2): trade name “EXP-50S150”, manufactured by Fuji Graphite Industry Co., Ltd., expansion start temperature 150 ° C.
Thermally expandable graphite (3): trade name “EXP-50S160” manufactured by Fuji Graphite Industry Co., Ltd., expansion start temperature 160 ° C.
Thermally expandable graphite (4): trade name “QKG”, QKG company, 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 thermally expandable graphite and the volume per unit weight (initial volume) before heating.

(Phosphorus compound)
Phosphate: tertiary aluminum phosphate (AlPO ₃ ), trade name “Thai Poly L2”, manufactured by Taihei Chemical Industry Co., Ltd. Polyphosphate: ammonium polyphosphate, trade name “AP422”, manufactured by Clariant Chemicals Phosphite: Aluminum phosphite, trade name "APA-100", manufactured by Taihei Chemical Industry 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, trade name "Disparon DA-375", manufactured by Kusumoto Kasei Co., Ltd. (plasticizer)
TPP: triphenyl phosphate, trade name "TPP", manufactured by Daihachi Chemical Industry Co., Ltd. DIDP: diisodecyl phthalate, trade name "DIDP", manufactured by J-Plus (processing aid)
Chlorinated polyethylene: trade name “135A CPE” manufactured by Weihai Kinko Co., Ltd. Polymethyl methacrylate: trade name “P-530A” manufactured by Mitsubishi Rayon Co., Ltd. Process oil: trade name “PW90” manufactured by Idemitsu Acryl-modified PTFE: trade name “ Metaprene A3000", manufactured by Mitsubishi Chemical Corporation (heat stabilizer)
Calcium stearate: trade name "SC-100", manufactured by Sakai Chemical Co., Ltd. Ca-Zn heat stabilizer: calcium-zinc heat stabilizer, trade name "CLZ-16S", manufactured by Mizusawa Chemical Co., Ltd.

In each of the above examples, the expansion ratio was 20 times or more when heated at 300 ° C. for 5 minutes, and the shape retention force was 0.7 N or more, so the fire resistance performance at low temperatures was good and more excellent. A refractory material having fire resistance was obtained. 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 retention force was less than 0.7 N, so the fire resistance could not be excellent. rice field.

Claims (7)

A fire-resistant 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 when heated at 300 ° C. for 5 minutes and a shape retention force of 0.7 N or more,
A refractory material, wherein the thermally expandable graphite has a volume increase rate of 1.0 ml/g/min or more when heated at 300° C. for 10 minutes. 2. The refractory material according to claim 1 , which has an expansion ratio of 30 times or more and a shape retention force of 0.07 N or more when heated at 500° C. for 5 minutes. 3. The fireproof material according to claim 1, wherein said matrix component is an epoxy resin. 4. The refractory material according to any one of claims 1 to 3 , wherein the phosphorus compound comprises a lower phosphate. Refractory material according to any one of claims 1 to 4 , wherein the phosphorus compound comprises a phosphite. The fire-resistant material according to any one of claims 1 to 5 , wherein the fire-resistant resin composition further contains an inorganic filler. A fitting comprising the refractory material according to any one of claims 1 to 6 .